阅读说明：本技术 固化性组合物、膜、滤色器、滤色器的制造方法、固体摄像元件、图像显示装置及高分子化合物 (Curable composition, film, color filter, method for producing color filter, solid-state imaging element, image display device, and polymer compound ) 是由 伊藤纯一 深见祐太朗 金子祐士 尾田和也 小泉宙梦 于 2020-02-07 设计创作，主要内容包括：本发明提供一种包含颜料以及满足下述条件1及下述条件2中的至少一个的树脂的固化性组合物、由上述固化性组合物形成的膜、滤色器、使用了上述固化性组合物的滤色器的制造方法、包含上述膜或上述滤色器的固体摄像元件及图像显示装置以及高分子化合物；条件1：上述树脂包含阴离子结构、与上述阴离子结构进行离子键合的季铵阳离子结构及在相同的侧链具有自由基聚合性基团的结构单元；条件2：上述树脂包含在侧链具有季铵阳离子结构及连接有自由基聚合性基团的基团的结构单元。(The invention provides a curable composition containing a pigment and a resin satisfying at least one of the following conditions 1 and 2, a film formed by the curable composition, a color filter, a method for manufacturing the color filter using the curable composition, a solid-state imaging element and an image display device containing the film or the color filter, and a polymer compound; condition 1: the resin contains an anionic structure, a quaternary ammonium cationic structure ionically bonded to the anionic structure, and a structural unit having a radical polymerizable group in the same side chain; condition 2: the resin contains a structural unit having a quaternary ammonium cation structure and a group to which a radical polymerizable group is bonded in a side chain.)

1. A curable composition comprising a pigment and a resin satisfying at least one of the following conditions 1 and 2:

condition 1: the resin comprises an anionic structure, a quaternary ammonium cationic structure ionically bonded to the anionic structure, and a structural unit having a radical polymerizable group in the same side chain;

condition 2: the resin contains a structural unit having a quaternary ammonium cationic structure and a group to which a radical polymerizable group is bonded in a side chain.

2. The curable composition according to claim 1,

the resin contains at least one of a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1),

in the formula (A1), R^A1Represents a hydrogen atom or an alkyl group, A^A1Represents a structure containing a group in which a proton is separated from an acid group, R^A2And R^A3Each independently represents an alkyl or aralkyl group, L^A1A substituent having a valence of 1 when mA is 1, a linking group having a valence of mA when mA is 2 or more, and L^A2A linker representing a valence of nA +1, L^A3Represents a 2-valent linking group, R^A4nA represents an integer of 1 or more, mA represents an integer of 1 or more, and when mA is 2 or more, R is 2 or more^A2R of 2 or more^A3And L of 2 or more^A2Respectively the same or different, and when mA is 2 or more, in the presence of a quaternary ammonium cationIn the mA structures, R contained in one structure is selected from^A2And R^A3Optionally with R selected from those contained in other structures^A2And R^A3At least one of nA and mA is 2 or more, L is 2 or more^A3And R is 2 or more^A4Each being the same or different, R^A2、R^A3And L^A2At least 2 of which are optionally bonded to form a ring;

in the formula (B1), R^B1Represents a hydrogen atom or an alkyl group, L^B1Represents a 2-valent linking group, R^B2And R^B3Each independently represents an alkyl group, L^B2Represents a nB +1 valent linking group, L^B3Represents a 2-valent linking group, R^B4Represents a hydrogen atom or an alkyl group, nB represents an integer of 1 or more, and when nB is 2 or more, L is 2 or more^B3And R is 2 or more^B4Each being the same or different, R^B2、R^B3、L^B1And L^B2At least 2 of which are optionally bonded to form a ring.

3. The curable composition according to claim 2,

nA in the formula (A1) is 1, L^A2And L^A3The bond (A) represents any one of groups represented by the following formulae (C1) to (C4), or nB in the formula (B1) is 1, L^B2And L^B3Represents any one of groups represented by the following formulae (C1) to (C4);

in the formulae (C1) to (C4), L^C1、L^C2And L^C3Each independently represents a single bond or a 2-valent linking group, a wavy line portion represents a bonding site to a nitrogen atom in formula (A1) or formula (B1), and a dotted line portion represents a bonding site to R in formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

4. The curable composition according to any one of claims 1 to 3,

the content of the structural unit represented by the formula (A1) and the structural unit represented by the formula (B1) in the resin is 1 to 60% by mass.

5. The curable composition according to any one of claims 1 to 4,

the resin has a radical polymerizable group, and further contains a structural unit D different from the structural unit represented by the formula (A1) and the structural unit represented by the formula (B1).

6. The curable composition according to claim 5,

the resin further contains a structural unit represented by the following formula (D1) as the structural unit D,

in the formula (D1), R^D1～R^D3Each independently represents a hydrogen atom or an alkyl group, X^D1represents-COO-, -CONR^D6Or arylene radical, R^D6Represents a hydrogen atom, an alkyl group or an aryl group, R^D4Represents a 2-valent linking group, L^D1Represents a group represented by the following formula (D2), formula (D3) or formula (D3'), R^D5A linking group having a valence of (n +1), X^D2Represents an oxygen atom or-NR^D7-，R^D7Represents a hydrogen atom, an alkyl group or an aryl group, R^DRepresents a hydrogen atom or a methyl group, nD represents an integer of 1 or more, and when nD is 2 or more, X is 2 or more^D2And R is 2 or more^DRespectively, are the same or different from each other,

in the formulae (D2), (D3) and (D3'), X^D3Represents an oxygen atom or-NH-, X^D4Represents an oxygen atom or COO-, R^e1～R^e3Each independently represents a hydrogen atom or an alkyl group, R^e1～R^e3At least 2 of which are optionally bonded to form a ring structure, X^D5Represents an oxygen atom or-COO-, R^e4～R^e6Each independently represents a hydrogen atom or an alkyl group, R^e4～R^e6At least 2 of which are optionally bonded to form a ring structure, and the dotted line portion indicates the bonding position with other structures.

7. The curable composition according to any one of claims 1 to 6,

the resin further contains a structural unit represented by the following formula (D5),

in the formula (D5), R^D9Represents a hydrogen atom or an alkyl group, X^D6Represents an oxygen atom or-NR^C-，R^CRepresents a hydrogen atom, an alkyl group or an aryl group, L^D3Denotes a 2-valent linking group, Y^D1Represents an alkyleneoxy group or an alkylenecarbonyloxy group, Z^D1Represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, p represents an integer of 1 or more, and when p is 2 or more, p Y s^D1The same or different.

8. The curable composition according to any one of claims 1 to 7, which comprises an oxime compound as a photopolymerization initiator.

9. The curable composition according to any one of claims 1 to 8, further comprising a polymerizable compound.

10. The curable composition according to any one of claims 1 to 9, which is used for forming a colored layer or an infrared absorbing layer of a color filter.

11. A film formed from the curable composition of any one of claims 1 to 10.

12. A color filter formed from the curable composition according to any one of claims 1 to 10.

13. A method of manufacturing a color filter, comprising:

a step of applying the curable composition according to any one of claims 1 to 10 to a support to form a composition layer;

exposing the composition layer to light in a pattern;

and forming a colored pattern by removing the unexposed portion by development.

14. A method of manufacturing a color filter, comprising:

a step of applying the curable composition according to any one of claims 1 to 10 to a support to form a composition layer, and curing the composition layer to form a cured layer;

a step of forming a photoresist layer on the cured layer;

a step of patterning the photoresist layer by exposure and development to obtain a resist pattern;

and etching the cured layer using the resist pattern as an etching mask.

15. A solid-state imaging element comprising the film according to claim 11 or the color filter according to claim 12.

16. An image display device comprising the film of claim 11 or the color filter of claim 12.

17. A polymer compound comprising at least one of a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1);

in the formula (A1), R^A1Represents a hydrogen atom or an alkyl group, A^A1Represents a structure containing a group in which a proton is separated from an acid group, R^A2And R^A3Each independently represents an alkyl or aralkyl group, L^A1A substituent having a valence of 1 when mA is 1, a linking group having a valence of mA when mA is 2 or more, and L^A2A linker representing a valence of nA +1, L^A3Represents a 2-valent linking group, R^A4nA represents an integer of 1 or more, mA represents an integer of 1 or more, and when mA is 2 or more, R is 2 or more^A2R of 2 or more^A3And L of 2 or more^A2When mA is 2 or more, R contained in one of the structures is selected from the mA structures of the structure containing the quaternary ammonium cation^A2And R^A3Optionally with R selected from those contained in other structures^A2And R^A3At least one of nA and mA is 2 or more, L is 2 or more^A3And R is 2 or more^A4Each being the same or different, R^A2、R^A3And L^A2At least 2 of which are optionally bonded to form a ring;

in the formula (B1), R^B1Represents a hydrogen atom or an alkyl group, L^B1Represents a 2-valent linking group, R^B2And R^B3Each independently represents an alkyl group, L^B2Represents a nB +1 valent linking group, L^B3Represents a 2-valent linking group, R^B4Represents a hydrogen atom or an alkyl group, nB represents an integer of 1 or more, and when nB is 2 or more, L is 2 or more^B3And R is 2 or more^B4Each being the same or different, R^B2、R^B3、L^B1And L^B2At least 2 of which are optionally bonded to form a ring.

18. The polymer compound according to claim 17, wherein,

nA in the formula (A1) is 1, L^A2And L^A3The bond (A) represents any one of groups represented by the following formulae (C1) to (C4), or nB in the formula (B1) is 1, L^B2And L^B3Represents any one of groups represented by the following formulae (C1) to (C4);

in the formulae (C1) to (C4), L^C1、L^C2And L^C3Each independently represents a 2-valent linking group, each wave line portion represents a bonding site to a nitrogen atom in the formula (A1) or the formula (B1), and each wave line portion represents a bonding site to R in the formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

Technical Field

The present invention relates to a curable composition, a film, a color filter, a method for producing a color filter, a solid-state imaging element, an image display device, and a polymer compound.

Background

In recent years, the spread of digital cameras, mobile phones with cameras, and the like has led to a great increase in the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors. Color filters are used as core devices for displays and optical elements.

The color filter is manufactured by using a curable composition containing a colorant and a resin. In general, when a pigment is used as the colorant, the pigment is dispersed in the curable composition by using a dispersant or the like.

Patent document 1 discloses an invention related to: (A) a weight average molecular weight of 3X 10, wherein a polymerizable double bond group of a specific structure is bonded to only one terminal of a polymer main chain of a polymer component having the specific structure⁴The radiation-sensitive coloring composition comprises a copolymer comprising at least a monofunctional macromonomer, a quaternary ammonium salt monomer having a specific structure, and a monomer having at least one molecule of an acid amide group having a specific structure, (B) a radiation-sensitive compound, and (C) a pigment.

Further, patent document 2 describes an electrodeposition coating composition having a weight average molecular weight of 3,000 to 30,00, which is obtained by reacting 0.5 to 30 mass% of a carboxylic acid compound selected from acrylic acid, methacrylic acid, maleic acid and the like, 0.5 to 30 mass% of a reaction product of glycidyl acrylate or glycidyl methacrylate having a specific structure and a quaternary ammonium salt, 10 to 40 mass% of a monomer having at least one hydroxyl group selected from hydroxyalkyl acrylates and hydroxyalkyl methacrylates having 2 to 5 carbon atoms, and 10 to 70 mass% of an unsaturated monomer selected from alkyl acrylates and alkyl methacrylates having 2 to 5 carbon atoms at 60 to 120 ℃, and comprises 10 to 15% by mass of an acrylate copolymer having a dielectric constant of 3.0 to 6.0 when the thickness of a dried coating film is 1 to 2.5 μm and 1 to 5% by mass of a pigment having an average particle diameter of 20 to 150nm and selected from the group consisting of anthraquinone-based pigments and phthalocyanine-based pigments.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 10-254133

Patent document 2: korean laid-open patent No. 2001-0066314

Disclosure of Invention

Technical problem to be solved by the invention

Further improvement in adhesion to a support is desired for a film formed using a cured composition.

The purpose of the present invention is to provide a curable composition capable of forming a film having excellent adhesion to a support. Also provided are a film formed from the curable composition, a color filter, a method for producing a color filter using the curable composition, a solid-state imaging element and an image display device each including the film or the color filter, and a novel polymer compound.

Means for solving the technical problem

Typical embodiments of the present invention are as follows.

< 1 > a curable composition comprising a pigment and a resin of at least one of the following condition 1 and the following condition 2:

condition 1: the resin contains an anionic structure, a quaternary ammonium cationic structure ionically bonded to the anionic structure, and a structural unit having a radical polymerizable group in the same side chain;

condition 2: the resin contains a structural unit having a quaternary ammonium cation structure and a group to which a radical polymerizable group is bonded in a side chain.

< 2 > the curable composition according to < 1 >, wherein,

the resin contains at least one of a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1).

[ chemical formula 1]

In the formula (A1), R^A1Represents a hydrogen atom or an alkyl group, A^A1Represents a structure containing a group in which a proton is separated from an acid group, R^A2And R^A3Each independently represents an alkyl or aralkyl group, L^A1A substituent having a valence of 1 when mA is 1, a linking group having a valence of mA when mA is 2 or more, and L^A2A linker representing a valence of nA +1, L^A3Represents a 2-valent linking group, R^A4nA represents an integer of 1 or more, mA represents an integer of 1 or more, and when mA is 2 or more, R is 2 or more^A2R of 2 or more^A3And L of 2 or more^A2The mA may be the same or different, and may be 2 or more, including in the seasonmA of the ammonium cation structure selected from R contained in one of the structures^A2And R^A3At least one of (A) and (B) may be selected from R contained in other structures^A2And R^A3At least one of nA and mA is 2 or more, L is 2 or more^A3And R is 2 or more^A4May be the same or different, R^A2、R^A3And L^A2At least 2 of which may be bonded to form a ring;

in the formula (B1), R^B1Represents a hydrogen atom or an alkyl group, L^B1Represents a 2-valent linking group, R^B2And R^B3Each independently represents an alkyl group, L^B2Represents a nB +1 valent linking group, L^B3Represents a 2-valent linking group, R^B4Represents a hydrogen atom or an alkyl group, nB represents an integer of 1 or more, and when nB is 2 or more, L is 2 or more^B3And R is 2 or more^B4May be the same or different, R^B2、R^B3、L^B1And L^B2At least 2 of which may be bonded to form a ring.

< 3 > the curable composition according to < 2 >, wherein

nA in the above formula (A1) is 1, L^A2And L^A3The bond (A) represents any one of groups represented by the following formulae (C1) to (C4), or nB in the formula (B1) is 1, L^B2And L^B3Represents any one of groups represented by the following formulae (C1) to (C4);

[ chemical formula 2]

In the formulae (C1) to (C4), L^C1、L^C2And L^C3Each independently represents a single bond or a 2-valent linking group, a wavy line portion represents a bonding site to a nitrogen atom in formula (A1) or formula (B1), and a dotted line portion represents a bonding site to R in formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

< 4 > the curable composition according to any one of < 1 > to < 3 >, wherein,

the content of the structural unit represented by the formula (a1) and the structural unit represented by the formula (B1) in the resin is 1 to 60% by mass.

< 5 > the curable composition according to any one of < 1 > to < 4 >, wherein,

the resin has a radical polymerizable group, and further contains a structural unit D different from the structural unit represented by the formula (A1) and the structural unit represented by the formula (B1).

< 6 > the curable composition according to < 5 >, wherein,

the resin further contains a structural unit represented by the following formula (D1) as the structural unit D.

[ chemical formula 3]

In the formula (D1), R^D1～R^D3Each independently represents a hydrogen atom or an alkyl group, X^D1represents-COO-, -CONR^D6Or arylene radical, R^D6Represents a hydrogen atom, an alkyl group or an aryl group, R^D4Represents a 2-valent linking group, L^D1Represents a group represented by the following formula (D2), formula (D3) or formula (D3'), R^D5A linking group having a valence of (n +1), X^D2Represents an oxygen atom or NR^D7-，R^D7Represents a hydrogen atom, an alkyl group or an aryl group, R^DRepresents a hydrogen atom or a methyl group, nD represents an integer of 1 or more, and when nD is 2 or more, X is 2 or more^D2And R is 2 or more^DMay be the same or different.

[ chemical formula 4]

In the formulae (D2), (D3) and (D3'), X^D3Represents an oxygen atom or-NH-, X^D4To representOxygen atom or COO-, R^e1～R^e3Each independently represents a hydrogen atom or an alkyl group, R^e1～R^e3At least 2 of which may be bonded to form a ring structure, X^D5Represents an oxygen atom or-COO-, R^e4～R^e6Each independently represents a hydrogen atom or an alkyl group, R^e4～R^e6At least 2 of which may be bonded to form a ring structure, and the dotted line portion indicates the bonding position with other structures.

< 7 > the curable composition according to any one of < 1 > to < 6 >, wherein,

the resin also contains a structural unit represented by the following formula (D5).

[ chemical formula 5]

In the formula (D5), R^D9Represents a hydrogen atom or an alkyl group, X^D6Represents an oxygen atom or NR^C-，R^CRepresents a hydrogen atom, an alkyl group or an aryl group, L^D3Denotes a 2-valent linking group, Y^D1Represents an alkyleneoxy group or an alkylenecarbonyloxy group, Z^D1Represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, p represents an integer of 1 or more, and when p is 2 or more, p Y s^D1May be the same or different.

< 8 > the curable composition according to any one of < 1 > to < 7 > comprising an oxime compound as a photopolymerization initiator.

< 9 > the curable composition according to any one of < 1 > to < 8 > further comprising a polymerizable compound.

< 10 > the curable composition according to any one of < 1 > to < 9 > for forming a colored layer or an infrared absorbing layer of a color filter.

< 11 > a film formed from the curable composition of any one of < 1 > to < 10 >.

< 12 > a color filter formed from the curable composition of any one of < 1 > to < 10 >.

< 13 > a method for manufacturing a color filter, comprising:

a step of applying the curable composition of any one of < 1 > to < 10 > to a support to form a composition layer;

exposing the composition layer to light in a pattern;

and forming a colored pattern by removing the unexposed portion by development.

< 14 > a method for manufacturing a color filter, comprising:

a step of applying the curable composition described in any one of < 1 > to < 10 > to a support to form a composition layer, and curing the composition layer to form a cured layer;

forming a photoresist layer on the cured layer;

a step of patterning the photoresist layer by exposure and development to obtain a resist pattern;

and etching the cured layer using the resist pattern as an etching mask.

< 15 > a solid-state imaging element comprising < 11 > the film or < 12 > the color filter.

< 16 > an image display device comprising < 11 > said film or < 12 > said color filter.

< 17 > a polymer compound comprising at least one of a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1);

[ chemical formula 6]

In the formula (A1), R^A1Represents a hydrogen atom or an alkyl group, A^A1Represents a structure containing a group in which a proton is separated from an acid group, R^A2And R^A3Each independently represents an alkyl or aralkyl group, L^A1Stands for a valence of 1 when mA is 1A substituent(s) of (A), a linking group representing a mA valence when mA is 2 or more, L^A2A linker representing a valence of nA +1, L^A3Represents a 2-valent linking group, R^A4nA represents an integer of 1 or more, mA represents an integer of 1 or more, and when mA is 2 or more, R is 2 or more^A2R of 2 or more^A3And L of 2 or more^A2The mA may be the same or different, and when mA is 2 or more, R contained in one structure is selected from mA structures containing quaternary ammonium cation^A2And R^A3At least one of (A) and (B) may be selected from R contained in other structures^A2And R^A3At least one of nA and mA is 2 or more, L is 2 or more^A3And R is 2 or more^A4May be the same or different, R^A2、R^A3And L^A2At least 2 of which may be bonded to form a ring;

in the formula (B1), R^B1Represents a hydrogen atom or an alkyl group, L^B1Represents a 2-valent linking group, R^B2And R^B3Each independently represents an alkyl group, L^B2Represents a nB +1 valent linking group, L^B3Represents a 2-valent linking group, R^B4Represents a hydrogen atom or an alkyl group, nB represents an integer of 1 or more, and when nB is 2 or more, L is 2 or more^B3And R is 2 or more^B4May be the same or different, R^B2、R^B3、L^B1And L^B2At least 2 of which may be bonded to form a ring.

< 18 > the polymer compound according to < 17 > wherein,

nA in the above formula (A1) is 1, L^A2And L^A3The bond (A) represents any one of groups represented by the following formulae (C1) to (C4), or nB in the formula (B1) is 1, L^B2And L^B3Represents any one of groups represented by the following formulae (C1) to (C4);

[ chemical formula 7]

In the formulae (C1) to (C4), L^C1、L^C2And L^C3Each independently represents a 2-valent linking group, each wave line portion represents a bonding site to a nitrogen atom in the formula (A1) or the formula (B1), and each wave line portion represents a bonding site to R in the formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

Effects of the invention

The present invention provides a curable composition capable of forming a film having excellent adhesion to a support. Also provided are a film formed from the curable composition, a color filter, a method for producing a color filter using the curable composition, a solid-state imaging element and an image display device each including the film or the color filter, and a novel polymer compound.

Drawings

FIG. 1 is a schematic view showing the measurement positions of the undercut width in the cured product on the pattern in the examples.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.

In the labeling of a group (atomic group) in the present specification, a substituted or unsubstituted label also includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" means that an alkyl group having a substituent (substituted alkyl) is included as well as an alkyl group having no substituent (unsubstituted alkyl).

In the present specification, unless otherwise specified, "exposure" refers to not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include actinic rays or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser light, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methacrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents both or either of acryloyl group and methacryloyl group.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent values measured by GPC (gel permeation chromatography).

In the present specification, the near infrared ray means light having a wavelength of 700 to 2,500 nm.

In the present specification, the solid component means the mass of the component excluding the solvent from all the components of the composition.

In the present specification, a pigment means a compound that is hardly soluble in a solvent. For example, the solubility of the pigment is preferably 0.1g or less, more preferably 0.01g or less, for both 100g of water at 23 ℃ and 100g of propylene glycol monomethyl ether acetate at 23 ℃.

In the present specification, the term "step" is included in the term not only in an independent step but also in a case where the term cannot be clearly distinguished from other steps as long as the intended action of the step is achieved.

In the present specification, unless otherwise specified, each component contained in the composition may contain 2 or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to the component.

In the present specification, unless otherwise specified, a wavy line portion or an asterisk (asterisk) in the structural formula indicates a bonding site with another structure.

In the present specification, a combination of preferred embodiments is a more preferred embodiment.

(curable composition)

The curable composition of the present invention contains a pigment and a resin (hereinafter, also referred to as a "specific resin") satisfying at least one of the following conditions 1 and 2.

Condition 1: the resin contains an anionic structure, a quaternary ammonium cationic structure ionically bonded to the anionic structure, and a structural unit having a radical polymerizable group in the same side chain;

condition 2: the resin contains a quaternary ammonium cation structure and a structural unit having a radical polymerizable group-bonded group in a side chain.

The curable composition of the present invention can provide a film having excellent adhesion to a support. The reason why the above-described effects can be obtained is presumed as follows.

The specific resin in the curable composition of the present invention satisfies at least one of the above condition 1 and the above condition 2, and thereby contains a quaternary ammonium cationic structure and a radical polymerizable group in the same side chain.

By the electrostatic interaction of the quaternary ammonium structures with each other, the following can be presumed: in the polymerization of the radical polymerizable group contained in the side chain having the same structure as the quaternary ammonium cation, the polymerization of the radical polymerizable group in the molecule of the specific resin (intramolecular crosslinking) is suppressed, and for example, the polymerization between the specific resin molecule and another specific resin molecule (intermolecular crosslinking) is easily caused, and therefore, a film having excellent adhesion to the support can be obtained.

Here, neither of patent documents 1 and 2 describes or suggests a curable composition containing a resin satisfying at least one of the above conditions 1 and 2.

The curable composition of the present invention is considered to be excellent also in the pattern shape of a pattern obtained using the curable composition. This is presumably because the molecules are easily crosslinked by the electrostatic interaction between the quaternary ammonium structures, and the curability of the curable composition is improved.

In addition, when the curable composition of the present invention further contains a polymerizable compound described later, the electrostatic interaction between the quaternary ammonium structures described above tends to cause polymerization between the resin and the polymerizable compound more easily than polymerization between the resins, and thus the curable composition tends to be excellent in curability and the curable composition tends to be excellent in the pattern shape of a pattern obtained by curing the curable composition.

The curable composition of the present invention can easily improve the storage stability of the curable composition by including the specific resin. This is presumably because the electrostatic interaction described above suppresses the aggregation of the pigment.

The curable composition of the present invention contains the specific resin, and thereby generation of development residue at the time of forming the pattern is easily suppressed. This is presumably because the side chain contains the quaternary ammonium structure, which increases the hydrophilicity of the specific resin and facilitates removal of the development residue.

The curable composition of the present invention contains a specific resin, and thus, the retardation defect can be easily suppressed. The "delayed defect" is a phenomenon that, when a certain period of time (for example, 12 hours to 3 days) has elapsed after a curable composition is applied to a support or the like to form a composition layer and patterning by exposure, development or the like is performed, a defect in the obtained pattern (for example, a granular aggregate is generated on the composition layer with the elapse of time, and such a component is not easily removed by development, and therefore remains on the support to become a defect or the like) is allowed. In the curable composition of the present invention, it is presumed that the occurrence of aggregation of the pigment in the composition layer is also suppressed by the electrostatic interaction, and therefore, the retardation defect is easily suppressed.

The curable composition of the present invention can be preferably used as a curable composition for color filters. In particular, it can be preferably used as a composition for forming pixels of color filters.

The curable composition of the present invention can be preferably used as a curable composition for a solid-state imaging device, and can be more preferably used as a curable composition for forming a pixel of a color filter used in a solid-state imaging device.

The curable composition of the present invention can be preferably used as a curable composition for a display device, and can be more preferably used as a color composition for forming a pixel of a color filter used in a display device.

The curable composition of the present invention can also be used as a composition for forming a color microlens. Examples of a method for producing a color microlens include the methods described in japanese patent application laid-open No. 2018-010162.

The curable composition of the present invention will be described in detail below.

< pigment >

The curable composition of the present invention contains a pigment.

Examples of the pigment include a white pigment, a black pigment, a color pigment, a transparent pigment, and a near-infrared-absorbing pigment. In the present invention, the white pigment includes not only pure white but also light gray (for example, off-white, light gray, etc.) pigment close to white.

The pigment may be either an inorganic pigment or an organic pigment, and an organic pigment is preferable because dispersion stability can be more easily improved.

The pigment preferably has a maximum absorption wavelength in the wavelength range of 400 to 2,000nm, and more preferably has a maximum absorption wavelength in the wavelength range of 400 to 700 nm.

When a pigment having a maximum absorption wavelength in the wavelength range of 400 to 700nm (preferably, a color pigment) is used, the curable composition of the present invention can be preferably used as a curable composition for forming a colored layer or an infrared absorbing layer in a color filter.

Examples of the colored layer include a red colored layer, a green colored layer, a blue colored layer, a magenta colored layer, a cyan colored layer, and a yellow colored layer.

The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5nm or more, more preferably 10nm or more. The upper limit is preferably 180nm or less, more preferably 150nm or less, and still more preferably 100nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the curable composition is good. In the present invention, the primary particle diameter of the pigment can be determined from an image photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the diameter of a perfect circle (equivalent circle diameter) having the projected area and the same area is calculated as the primary particle diameter of the pigment. The average primary particle diameter in the present invention is an arithmetic average of the primary particle diameters of the primary particles of 400 pigments. The primary particles of the pigment are independent particles that are not aggregated.

[ color pigments ]

The color pigment is not particularly limited, and a known color pigment can be used. Examples of the color pigment include pigments having an absorption maximum wavelength in a wavelength range of 400 to 700 nm. Examples thereof include yellow pigments, orange pigments, red pigments, green pigments, violet pigments, and blue pigments. Specific examples thereof include the following.

A color index Yellow Pigment (Pigment Yellow) (hereinafter, also referred to simply as "PY".) 1,2, 3,4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 182, 176, 187, 177, 193, 187, 177, 188, 193, 185, 200, 152, 150, 152, 188, 150, 194, and 214 times a Polymethine (polymethylene), 233 (or more, yellow pigment) such as Quinoline (Quinoline) type,

C.i. Pigment Orange (hereinafter, also simply referred to as "PO") 2,5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, Orange pigments),

Pigment Red (Pigment Red) (hereinafter, also referred to simply as "PR") 1,2, 3,4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 264, 254, 255, 264, 270, 272, xanthene (296, xanthene series), 296, 295, and more than two or more pigments of the series of Red (Pigment Red) 294, Pigment Red series)

C.i. Pigment Green (hereinafter, also simply referred to as "PG") 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, Green Pigment),

C.i. Pigment Violet (hereinafter, also simply referred to as "PV"), 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), and the like (or more, Violet pigments),

C.i. Pigment Blue (hereinafter, also referred to simply as "PB") 1,2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo system), 88 (methine/Polymethine system), and the like (above, Blue pigments).

From the viewpoint of more easily obtaining the effects of the present invention, the curable composition of the present invention preferably contains a green pigment as a pigment, more preferably contains a halogenated phthalocyanine, and further preferably contains PG 36 and/or PG 58.

The curable composition of the present invention preferably contains both the green pigment and the yellow pigment. The yellow pigment in this case preferably includes PY 150 and/or PY 185.

Green pigment-

The green pigment can be a zinc halide phthalocyanine pigment having 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms in an average number in 1 molecule. Specific examples thereof include the compounds described in International publication No. 2015/118720. As the green pigment, a compound described in chinese patent application publication No. 106909027, a phthalocyanine compound having a phosphate as a ligand, or the like can be used.

Blue pigments

Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include compounds described in paragraphs 0022 to 0030 of Japanese patent application laid-open No. 2012 and 247591 and paragraph 0047 of Japanese patent application laid-open No. 2011 and 157478.

Yellow pigments

Further, as the yellow pigment, a pigment described in japanese patent application laid-open No. 2017-201003, or a pigment described in japanese patent application laid-open No. 2017-197719 can be used.

As the yellow pigment, a metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, 2 or more metal ions, and a melamine compound can be used.

[ chemical formula 8]

In the formula, R¹And R²Each independently being-OH or-NR⁵R⁶，R³And R⁴Independently of one another is ═ O or ═ NR⁷，R⁵～R⁷Each independently is a hydrogen atom or an alkyl group. R⁵～R⁷The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. The substituents are preferably halogen atoms, hydroxyl groups, alkoxy groups, cyano groups and amino groups.

The metallic azo pigment can be described in, for example, paragraphs 0011 to 0062 and 0137 to 0276 of Japanese patent application laid-open No. 2017-171912, paragraphs 0010 to 0062 and 0138 to 0295 of Japanese patent application laid-open No. 2017-171913, paragraphs 0011 to 0062 and 0139 to 0190 of Japanese patent application laid-open No. 2017-171914, and paragraphs 0010 to 0065 and 0142 to 0222 of Japanese patent application laid-open No. 2017-171915, which are incorporated herein by reference.

Red pigment-

As the red pigment, a dioxopyrrolopyrrole-based pigment having a structure substituted with at least one bromine atom as described in Japanese patent application laid-open No. 2017-201384, a dioxopyrrolopyrrole-based pigment as described in paragraphs 0016 to 0022 of Japanese patent No. 6248838, and the like can be used. As the red pigment, a compound having a structure in which an aromatic ring group obtained by introducing a group to which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can be used. As such a compound, a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.

[ chemical formula 9]

In the above formula, R¹¹And R¹³Each independently represents a substituent, R¹²And R¹⁴Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n11 and n13 each independently represents an integer of 0 to 4, X¹²And X¹⁴Each independently represents an oxygen atom, a sulfur atom or a nitrogen atom when X¹²When it is an oxygen atom or a sulfur atom, m12 represents 1, and X represents¹²When it is a nitrogen atom, m12 represents 2, when X is¹⁴When it is an oxygen atom or a sulfur atom, m14 represents 1, and X represents¹⁴When it is a nitrogen atom, m14 represents 2. As R¹¹And R¹³The substituent represented by the above-mentioned substituent T includes the groups described above, and preferable examples thereof include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an amido group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, and a sulfo group.

In the present invention, 2 or more color pigments may be used in combination. When 2 or more kinds of color pigments are used in combination, 2 or more kinds of color pigments may be combined to form black. Examples of such a combination include the following (1) to (7). In the case where 2 or more color pigments are contained in the curable composition and 2 or more color pigments are combined to give black, the curable composition of the present invention can be preferably used as a near infrared ray transmission filter.

(1) The mode containing red pigment and blue pigment.

(2) The embodiment containing a red pigment, a blue pigment and a yellow pigment.

(3) The mode containing a red pigment, a blue pigment, a yellow pigment and a violet pigment.

(4) The pigment composition contains a red pigment, a blue pigment, a yellow pigment, a violet pigment and a green pigment.

(5) The embodiment containing red pigment, blue pigment, yellow pigment and green pigment.

(6) The embodiment containing red pigment, blue pigment and green pigment.

(7) The mode containing a yellow pigment and a violet pigment.

[ white pigment ]

Examples of the white pigment include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. The white pigment is preferably particles having a titanium atom, and more preferably titanium oxide. The white pigment is preferably particles having a refractive index of 2.10 or more at 25 ℃ with respect to light having a wavelength of 589 nm. The refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

The white pigment may be titanium oxide described in "titanium oxide physical properties and applied technology published on pages 13 to 45, 1991, 6 and 25 months, and published in the journal of the art".

The white pigment is not limited to being composed of a single inorganic substance, and particles compounded with other raw materials may be used. For example, particles having vacancies or other raw materials inside, particles in which a large number of inorganic particles are attached to core particles, core and shell composite particles including core particles composed of polymer particles and shell layers composed of inorganic nanoparticles are preferably used. As the core and shell composite particles including the core particles composed of the polymer particles and the shell layers composed of the inorganic nanoparticles, for example, the descriptions of paragraphs 0012 to 0042 of jp 2015-047520 a can be referred to, and the contents thereof are incorporated in the present specification.

The white pigment can also use hollow inorganic particles. The hollow inorganic particle refers to an inorganic particle having a cavity structure inside, and refers to an inorganic particle having a cavity surrounded by a shell. Examples of the hollow inorganic particles include those described in japanese patent application laid-open publication nos. 2011-075786, 2013/061621, 2015-164881, and the like, and the contents thereof are incorporated herein.

[ Black pigment ]

The black pigment is not particularly limited, and a known black pigment can be used. For example, carbon black, titanium black, graphite and the like are preferable, and carbon black and titanium black are more preferable. Titanium black is black particles containing titanium atoms, and is preferably titanium suboxide or titanium oxynitride. The surface of the titanium black may be modified as necessary for the purpose of improving dispersibility, suppressing aggregation, and the like. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a treatment of a water repellent substance as shown in japanese patent laid-open No. 2007-302836 can also be used. As the Black Pigment, a color index (c.i.) Pigment Black 1,7 and the like can be preferably cited. In the titanium black, each particle has a small primary particle diameter and an average primary particle diameter. Specifically, the average primary particle diameter is preferably 10 to 45 nm. Titanium black can also be used as the dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50, and the like can be cited. As to the above dispersion, reference can be made to the descriptions in paragraphs 0020 to 0105 of Japanese patent application laid-open No. 2012-169556, the contents of which are incorporated in the present specification. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M-C, 13R-N, 13M-T (product name: manufactured by Mitsubishi Materials Corporation), Tilack D (product name: Ako Kasei Co., Ltd.).

[ near Infrared ray absorption pigment ]

The near infrared ray absorbing pigment is preferably an organic pigment. Also, the near infrared ray absorption pigment preferably has a maximum absorption wavelength in a range of a wavelength of more than 700nm and 1,400nm or less. The maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1,200nm or less, more preferably 1,000nm or less, and further preferably 950nm or less. And the absorbance A of the near infrared ray absorption pigment at a wavelength of 550nm₅₅₀And absorbance A at the maximum absorption wavelength_maxIn a ratio of₅₅₀/A_maxPreferably 0.1 or less, more preferably 0.05 or less, further preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, and may be, for example, 0.0001 or more, or 0.0005 or more. When the ratio of absorbance is in the above range, a near-infrared absorbing pigment having excellent visible light transparency and near-infrared shielding properties can be obtained. In the present invention, the maximum absorption wavelength of the near-infrared absorbing pigment and the value of absorbance at each wavelength are values obtained from the absorption spectrum of a film formed using a curable composition containing the near-infrared absorbing pigment.

The near-infrared absorbing pigment is not particularly limited, and examples thereof include a pyrrolopyrrole compound, a rutinic compound, an oxonol compound, a squarylium compound, a cyanine compound, a ketanium compound, a phthalocyanine compound, a naphthalocyanine compound, a pyrylium compound, an Auzlenium compound, an indigo compound, and a pyrromethene compound, at least one compound selected from the group consisting of a pyrrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable, a pyrrolopyrrole compound or a squarylium compound is more preferable, and a pyrrolopyrrole compound is particularly preferable.

[ transparent pigment ]

Examples of the transparent pigment include titanium oxide, zirconium oxide, silica, zinc oxide, barium sulfate, barium carbonate, alumina white, calcium carbonate, and calcium stearate.

Of these, the coloring power is preferably small, and titanium oxide or zirconium oxide is more preferable, and zirconium oxide is further preferable.

The content of the pigment in the total solid content of the curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

[ pigment derivative ]

The curable composition of the present invention may contain a pigment derivative. In the present invention, it is also preferable to use a pigment and a pigment derivative in combination. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group, or a phthalimide methyl group. The coloring group constituting the pigment derivative may preferably include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perinone skeleton, a perylene skeleton, a Thioindigo (Thioindigo) skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinoline yellow skeleton, a shire (threne) skeleton, a metal complex skeleton, and the like, and a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinoline yellow skeleton, an isoindoline skeleton, and a phthalocyanine skeleton, more preferably an azo skeleton and a benzimidazolone skeleton. The acid group of the pigment derivative is preferably a sulfo group or a carboxyl group, and more preferably a sulfo group. The basic group having a pigment derivative is preferably an amino group, and more preferably a tertiary amino group. Specific examples of the pigment derivative include compounds described in examples described later and compounds described in Japanese patent laid-open publication Nos. 2011-252065, paragraphs 0162 to 0183. The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. The pigment derivative may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

< specific resin >

The curable composition of the present invention contains a resin (specific resin) that satisfies at least one of the following conditions 1 and 2.

Condition 1: the resin contains an anionic structure, a quaternary ammonium cationic structure ionically bonded to the anionic structure, and a structural unit having a radical polymerizable group in the same side chain.

Condition 2: the resin contains a quaternary ammonium cation structure and a structural unit having a radical polymerizable group-bonded group in a side chain.

The specific resin in the present invention may be any of a linear polymer compound, a star polymer compound, and a comb polymer compound, or a star polymer compound having a specific terminal group as described in jp 2007-277514 a and the like having a plurality of branch points, and the form of the resin is not limited.

The molecular weight (when having a molecular weight distribution, the weight average molecular weight) of the side chain in condition 1 or condition 2 is preferably 50 to 1500, more preferably 100 to 1000.

The specific resin is preferably an addition polymerization type resin, and more preferably an acrylic resin. In the case where the specific resin is an addition polymerization type resin, examples of the side chain in condition 1 or condition 2 include a molecular chain bonded to a molecular chain formed by addition polymerization and a molecular chain formed by a method other than addition polymerization.

Also, the specific resin may be a dispersant. In the present specification, a resin used mainly for dispersing particles such as a pigment is also referred to as a dispersant. Among these, the use of the specific resin is an example, and the specific resin can be used for purposes other than this.

[ Condition 1]

In the anionic structure, the quaternary ammonium cationic structure ionically bonded to the anionic structure, and the structural unit having a radical polymerizable group in the same side chain in the above condition 1, the anionic structure and the quaternary ammonium cationic structure may be ionically bonded or dissociated.

The side chains in the condition 1 may have at least one anionic structure, quaternary ammonium cationic structure, and radical polymerizable group, respectively, or may have at least one selected from the group consisting of an anionic structure, a quaternary ammonium cationic structure, and a radical polymerizable group in one side chain.

-anionic structure-

The anion structure in the above condition 1 is not particularly limited, and preferable examples thereof include anions derived from an acid group such as a carboxylate anion, a sulfonate anion, a phosphonate anion, a phosphate anion, and a phenolate anion, and carboxylate anions.

The anionic structure in the above condition 1 may be directly bonded to the main chain of the resin. For example, when a carboxyl group (side group) included in a structural unit derived from acrylic acid in an acrylic resin is anionized, the carboxyl group is an anionic structure directly bonded to the main chain of the resin.

The distance (number of atoms) between the main chain when the anionic structure is bonded to the quaternary ammonium cationic structure and the quaternary ammonium cationic structure is preferably 4 to 70 elements, more preferably 4 to 50 elements, and still more preferably 4 to 30 elements.

In the present specification, the distance of 2 structures in the polymer compound means the number of atoms of a linking group connecting 2 structures at the shortest distance.

The distance between the quaternary ammonium cation structure and the radical polymerizable group is preferably 2 to 30 elements, more preferably 3 to 20 elements, and further preferably 4 to 15 elements.

The distance between the radical polymerizable group and the main chain is preferably 6 to 100 elements, more preferably 6 to 70 elements, and further preferably 6 to 50 elements.

Quaternary ammonium cation structure (condition 1)

As the quaternary ammonium cation structure in the above condition 1, a structure in which at least 3 of 4 groups contained in 4 carbon atoms bonded to a nitrogen atom are hydrocarbon groups is preferable, and at least 3 are alkyl groups is more preferable.

At least one of the 4 groups containing 4 carbon atoms bonded to the nitrogen atom contains a linking group having a bonding site to a radical polymerizable group. The linking group is preferably a 2-to 6-valent linking group, more preferably a 2-to 4-valent linking group, and still more preferably a 2-or 3-valent linking group. Examples of the linking group include L in the formula (A1)^A2The group shown.

Also, it is preferable that only 1 of 4 groups containing 4 carbon atoms bonded to the nitrogen atom is the above-mentioned linking group.

Preferably, 2 or 3 of the 4 groups containing 4 carbon atoms are alkyl groups having 1 to 4 carbon atoms and 2 are alkyl groups having 1 to 4 carbon atoms, and preferably 1 of the remaining 2 groups is a hydrocarbon group having 4 to 20 carbon atoms. The 2 or 3 alkyl groups may be the same group or different groups.

The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.

The hydrocarbon group having 4 to 20 carbon atoms is preferably an alkyl group having 4 to 20 carbon atoms or a benzyl group.

In the above condition 1, in the case where the side chain includes a plurality of quaternary ammonium cationic structures, the quaternary ammonium cationic structures are bonded to each other through the linking group, and the quaternary ammonium cationic structures may form a ring structure with each other. Examples of the ring structure to be formed include a ring structure represented by the following formula. In the following formula, a represents a bonding site to a linking group including a bonding site of a radical polymerizable group.

[ chemical formula 10]

A radical polymerizable group (condition 1) -

The radical polymerizable group is preferably a group having an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group, (meth) allyl group, (meth) acrylamide group, (meth) acryloyloxy group, vinylphenyl group, and the like, and from the viewpoint of reactivity, a (meth) acryloyloxy group or vinylphenyl group is preferable, and a (meth) acryloyloxy group is more preferable.

[ Condition 2]

In the side chain in the above condition 2, the quaternary ammonium cationic structure is linked to the radical polymerizable group. That is, 1 side chain has both at least one quaternary ammonium cationic structure and at least one radical polymerizable group.

The side chain in the above condition 2 may have at least one quaternary ammonium cationic structure and at least one radical polymerizable group, respectively, and may have a plurality of at least one selected from the quaternary ammonium cationic structure and the radical polymerizable group in one side chain.

The distance (atomic number) between the main chain and the quaternary ammonium cation structure is preferably 4 to 20 elements, more preferably 4 to 15 elements, and most preferably 4 to 10 elements.

The distance between the quaternary ammonium cation structure and the polymerizable group is preferably 2 to 30 elements, more preferably 3 to 20 elements, and further preferably 4 to 15 elements.

The distance between the polymerizable group and the main chain is preferably 6 to 50 elements, more preferably 6 to 30 elements, and further preferably 6 to 20 elements.

Quaternary ammonium cation structure (condition 2)

As the quaternary ammonium cation structure in the above condition 2, a structure in which at least 2 of 4 groups containing 4 carbon atoms bonded to a nitrogen atom are hydrocarbon groups, more preferably at least 2 are alkyl groups, is preferable.

The above-mentioned hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably an alkyl group or a phenyl group.

The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. The 2 alkyl groups may be the same or different.

At least one of the 4 groups containing 4 carbon atoms bonded to the nitrogen atom is a linking group containing a bonding site to a radical polymerizable group, and at least one is a linking group containing a bonding site to a main chain in the specific resin.

The linking group to the radical polymerizable group is preferably a 2-to 6-valent linking group, more preferably a 2-to 4-valent linking group, and still more preferably a 2-or 3-valent linking group. Examples of the linking group include L in the formula (B1)^B2The group shown.

The linking group containing a bonding site with the main chain in the specific resin is preferably a linking group having a valence of 2. Examples of the linking group include L in the formula (B1)^B1The group shown.

The counter anion of the quaternary ammonium cationic structure in the above condition 2 may be present in the specific resin, may be present in other components contained in the curable composition, and is preferably present in the specific resin.

A radical polymerizable group (condition 2) -

The radical polymerizable group is preferably a group having an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group, (meth) allyl group, (meth) acrylamide group, (meth) acryloyloxy group, vinylphenyl group, and the like, and from the viewpoint of reactivity, a (meth) acryloyloxy group or vinylphenyl group is preferable, and a (meth) acryloyloxy group is more preferable.

(structural unit represented by formula (A1) and structural unit represented by formula (B1))

The resin preferably contains at least one of a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (B1).

The resin containing a structural unit represented by the following formula (a1) is a resin satisfying condition 1, and the resin containing a structural unit represented by the following formula (B1) is a resin satisfying condition 2.

[ chemical formula 11]

In the formula (A1), R^A1Represents a hydrogen atom or an alkyl group, A^A1Denotes compounds containing protons separated from acid groupsStructure of the radical R^A2And R^A3Each independently represents an alkyl or aralkyl group, L^A1A substituent having a valence of 1 when mA is 1, a linking group having a valence of mA when mA is 2 or more, and L^A2A linker representing a valence of nA +1, L^A3Represents a 2-valent linking group, R^A4nA represents an integer of 1 or more, mA represents an integer of 1 or more, and when mA is 2 or more, R is 2 or more^A2R of 2 or more^A3And L of 2 or more^A2The same or different mA may be used, and when mA is 2 or more, R contained in one structure is selected from mA structures containing quaternary ammonium cation^A2And R^A3At least one of (A) and (B) may be selected from R contained in other structures^A2And R^A3At least one of nA and mA is 2 or more, L is 2 or more^A3And R is 2 or more^A4May be the same or different, R^A2、R^A3And L^A2At least 2 of which may be bonded to form a ring;

in the formula (B1), R^B1Represents a hydrogen atom or an alkyl group, L^B1Represents a 2-valent linking group, R^B2And R^B3Each independently represents an alkyl group, L^B2Represents a nB +1 valent linking group, L^B3Represents a 2-valent linking group, R^B4Represents a hydrogen atom or an alkyl group, nB represents an integer of 1 or more, and when nB is 2 or more, L is 2 or more^B3And R is 2 or more^B4May be the same or different, R^B2、R^B3、L^B1And L^B2At least 2 of which may be bonded to form a ring.

In the formula (A1), R^A1Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula (A1), A^A1The structure of the compound containing a group in which a proton is separated from an acid group is shown, and examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, a phosphonate group, and a phenolic hydroxyl group, and a carboxyl group is preferable. A. the^A1The number of acid groups contained in (1) may be 1, or may be plural, and preferably 1. And, A^A1The acid group in (A) may be the same as that in (A1)R^A1The bonded carbon atoms are directly bonded or may be bonded through a linking group. The linking group is preferably a hydrocarbon group, an ether bond (-O-), an ester bond (-COO-), an amide bond (-CONH-) or 2 or more groups bonded thereto. The hydrocarbon group includes a 2-valent hydrocarbon group, preferably an alkylene group or an arylene group, and more preferably an alkylene group or a phenylene group having 1 to 20 carbon atoms. In the present specification, unless otherwise specified, the hydrogen atom in the amide bond may be substituted with a known substituent such as an alkyl group or an aryl group.

In the formula (A1), R is preferred^A2And R^A3Each independently is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, yet more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the formula (A1), R^A2Or R^A3In the case of an aralkyl group, the aralkyl group is preferably a C7-22 aralkyl group, more preferably a C7-10 aralkyl group, and still more preferably a benzyl group.

In the formula (A1), L^A1When mA is 2 or more, a hydrocarbon group having a mA valence is preferable, and a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing mA hydrogen atoms from a structure in which 2 or more of these are bonded is more preferable. When mA is 1, L^A1The alkyl group, the aryl group or the aralkyl group is preferable, and the alkyl group having 4 to 20 carbon atoms or the benzyl group is more preferable.

In the formula (A1), L^A2Any of the groups represented by the formulae (C1-1) to (C4-1) described later is preferable.

In the formula (A1), L^A3Preferred is an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), an alkylene group or an arylene group, and more preferred is an ester bond or a phenylene group.

In the formula (A1), R^A4Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula (A1), nA is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

In the formula (A1), mA is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 3.

In the formula (B1), R^B1Preferably the number of hydrogen atoms or carbon atoms1 to 4 alkyl groups, more preferably a hydrogen atom or a methyl group.

In the formula (B1), L^B1The linking group having a valence of 2 is preferably a hydrocarbon group, an ether bond (-O-), an ester bond (-COO-), an amide bond (-CONH-) or a group having at least 2 of these groups bonded. The hydrocarbon group includes a 2-valent hydrocarbon group, preferably an alkylene group or an arylene group, and more preferably an alkylene group or a phenylene group having 1 to 20 carbon atoms.

In the formula (B1), R is preferred^B2And R^B3Each independently an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the formula (B1), L^B2Any of the groups represented by the formulae (C1-1) to (C4-1) described later is preferable.

In the formula (B1), L^B3Preferred is an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), an alkylene group or an arylene group, and more preferred is an ester bond or a phenylene group.

In the formula (B1), nB is preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.

L of the formula (A1)^A2Or L in the formula (B1)^B2Any of the groups represented by the following formulae (C1-1) to (C4-1) is preferred.

[ chemical formula 12]

In the formulae (C1-1) to (C4-1), L^C11Represents a linking group of nC1+1 valence, L^C21Represents a linking group of nC2+1 valence, L^C31Each represents a hydrocarbon group having a valence of nC3+1, nC1 to nC3 each independently represents an integer of 1 or more, a wavy line portion represents a bonding site to a nitrogen atom in the formula (A1) or the formula (B1), and a group represents a bonding site to R in the formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

And L in the formula (C3-1)^C21Indicates that it may be bonded to any one of the carbon atoms in the cyclohexane ring in the formula (C3-1).

In the formula (C1-1) or the formula (C2-1), L^C11The compound preferably has a nC1+ 1-valent hydrocarbon group, ether bond, ester bond, or a group in which 2 or more of these are bonded, and more preferably a saturated aliphatic hydrocarbon, aromatic hydrocarbon, ether bond, ester bond, or a group in which nC1+1 hydrogen atoms are removed from a structure in which 2 or more of these are bonded.

In the formula (C1-1) or the formula (C2-1), nC1 is preferably 1 to 10, preferably 1 to 4, and more preferably 1 or 2.

In the formula (C3-1), L^C21Preferably, the compound has a valence of nC2+1, and is a hydrocarbon group, ether bond, ester bond or a group in which 2 or more of these are bonded, and more preferably a saturated aliphatic hydrocarbon, aromatic hydrocarbon, ether bond, ester bond or a group in which nC2+1 hydrogen atoms are removed from the structure in which 2 or more of these are bonded.

In the formula (C3-1), nC2 is preferably 1 to 10, preferably 1 to 4, and more preferably 1 or 2.

In the formula (C4-1), L^C31Saturated aliphatic hydrocarbons, aromatic hydrocarbons, or groups obtained by removing nC3+1 hydrogen atoms from 2 or more structures to which these are bonded are preferable.

In the formula (C4-1), nC3 is preferably 1 to 10, preferably 1 to 4, and more preferably 1 or 2.

In the formula (A1), L^A2Preferably a group represented by the formula (C1-1), the formula (C2-1) or the formula (C3-1)^A3Is an ester bond.

In the formula (A1), L^A2In the case of a group represented by the formula (C4-1), L is preferred^A3Is phenylene.

In the formula (B1), L^B2In the case of a group represented by the formula (C1-1), the formula (C2-1) or the formula (C3-1), L^B3Ester linkages are preferred.

In the formula (B1), L^B2In the case of a group represented by the formula (C4-1), L^B3Phenylene radicals are preferred.

When the specific resin contains at least one of the structural unit represented by formula (A1) and the structural unit represented by formula (B1), nA in formula (A1) is 1, and L is^A2And L^A3The bond (C) represents any one of the groups represented by the following formulae (C1) to (C4) or nB in the formula (B1) is 1, preferably L^B2And L^B3Is represented by the following formula (C1) to the following formula (C4)Any one of the above embodiments.

[ chemical formula 13]

In the formulae (C1) to (C4), L^C1、L^C2And L^C3Each independently represents a single bond or a 2-valent linking group, a wavy line portion represents a bonding site to a nitrogen atom in formula (A1) or formula (B1), and a dotted line portion represents a bonding site to R in formula (A1)^A4Bound carbon atom or R in the formula (B1)^B4The bonding site of the bonded carbon atom.

L in the formula (C3)^C2Indicates that the compound may be bonded to any carbon atom in the cyclohexane ring in the formula (C3).

In the formula (C1) or the formula (C2), L^C1The compound preferably has a 2-valent hydrocarbon group, ether linkage, ester linkage or 2 or more groups bonded thereto, more preferably an alkylene group, arylene group, ether linkage, ester linkage or 2 or more groups bonded thereto, and still more preferably an alkylene group having 1 to 20 carbon atoms, phenylene group, ether linkage or 2 or more groups bonded thereto.

In the formula (C3), L^C2The compound preferably has a 2-valent hydrocarbon group, ether linkage, ester linkage or 2 or more groups bonded thereto, more preferably an alkylene group, arylene group, ether linkage, ester linkage or 2 or more groups bonded thereto, and still more preferably an alkylene group having 1 to 20 carbon atoms, phenylene group, ether linkage or 2 or more groups bonded thereto.

In the formula (C4), L^C3The alkyl group having a valence of 2, an ether bond, an ester bond or a group in which 2 or more of these are bonded are preferable, the alkylene group, the arylene group, the ether bond, the ester bond or a group in which 2 or more of these are bonded are more preferable, and the alkylene group having 1 to 20 carbon atoms is more preferable.

The structural unit represented by formula (a1) preferably includes the following structures, but is not limited to these. In the following specific examples, n represents an integer of 1 or more.

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

In addition, the following structure can be mentioned as the structure of the cationic portion containing a quaternary ammonium cationic structure and a radical polymerizable group.

[ chemical formula 18]

The structural unit represented by the formula (B1) includes, but is not limited to, the following structures.

[ chemical formula 19]

[ chemical formula 20]

In these structures, at least a part of the structural unit having a quaternary ammonium cation structure may be a structure represented by formula (a 1-1-1') with respect to formula (a1-1-1) (the partial structure in formula (a-1)).

Specifically, the structure represented by the formula (C1) contained in the structural unit having a quaternary ammonium cation structure may be a structure represented by the formula (C2). The structure of the formula (A1-1-1') is, for example, a structural isomer in the reaction of an amine compound with a compound having an epoxy group and an acryloyl group.

[ chemical formula 21]

The specific resin may have 1 kind alone, or may have 2 or more kinds of structural units represented by the formula (a 1).

The specific resin may have 1 kind alone, or may have 2 or more kinds of structural units represented by the formula (B1).

The content (total content when 2 or more species are included) of the structural unit represented by the formula (a1) and the structural unit represented by the formula (B1) is preferably 1 to 60% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 20% by mass, based on the total mass of the specific resin.

[ structural unit D ]

The specific resin preferably also has a radical polymerizable group, and further contains a structural unit represented by formula (a1) and a structural unit D different from the structural unit represented by formula (B1).

The radical polymerizable group in the structural unit D is preferably a group having an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group, (meth) allyl group, (meth) acrylamide group, (meth) acryloyloxy group, vinylphenyl group, and the like, and from the viewpoint of reactivity, a (meth) acryloyloxy group or vinylphenyl group is preferable, and a (meth) acryloyloxy group is more preferable.

[ structural Unit represented by the formula (D1) ]

The specific resin preferably further contains a structural unit represented by the following formula (D1) as the structural unit D.

[ chemical formula 22]

In the formula (D1), R^D1～R^D3Each independently represents a hydrogen atom or an alkyl group, X^D1represents-COO-, -CONR^D6Or arylene radical, R^D6Represents a hydrogen atom, an alkyl group or an aryl group, R^D4Represents a 2-valent linking group, L^D1Represents a group represented by the following formula (D2), formula (D3) or formula (D3'), R^D5A linking group having a valence of (n +1), X^D2Represents an oxygen atom or NR^D7-，R^D7Represents a hydrogen atom, an alkyl group or an aryl group, R^DRepresents a hydrogen atom or a methyl group, nD represents an integer of 1 or more, and when nD is 2 or more, X is 2 or more^D2And R is 2 or more^DMay be the same or different.

[ chemical formula 23]

In the formulae (D2), (D3) and (D3'), X^D3Represents an oxygen atom or-NH-, X^D4Represents an oxygen atom or COO-, R^e1～R^e3Each independently represents a hydrogen atom or an alkyl group, R^e1～R^e3At least 2 of which may be bonded to form a ring structure, X^D5Represents an oxygen atom or-COO-, R^e4～R^e6Each independently represents a hydrogen atom or an alkyl group, R^e4～R^e6At least 2 of which may be bonded to form a ring structure, and the dotted line portion indicates the bonding position with other structures.

In the curable composition, by using a specific resin containing a structural unit represented by the above formula (D1), the obtained film tends to be excellent in deep layer curability.

The reason why the above-described effects can be obtained is not clear, but is presumed as follows.

In the resin having a structural unit represented by the formula (D1), it is considered that the range of movement of the (meth) acryloyl group in the composition is increased and the reactivity is excellent by having a group represented by the formula (D2), the formula (D3) or the formula (D3') as a polar group in a side chain. Further, it is considered that the presence of the group represented by the formula (D2), the formula (D3) or the formula (D3') is excellent in suppressing aggregation of resins with each other and dispersibility, and the (meth) acryloyl group is more likely to react, and therefore, a curable composition having excellent deep curability is easily obtained.

Further, by containing the structural unit represented by the formula (D1), a highly reactive (meth) acryloyl group can be introduced into a position separated from the main chain through the group represented by the formula (D2), the formula (D3), or the formula (D3'). Therefore, it is considered that the probability that the (meth) acryloyl groups in the resin molecules do not react with each other but react with each other between the resin molecules or with other crosslinking components (for example, polymerizable compounds and the like) in the composition is increased, and that the crosslinking reaction proceeds with good efficiency even in a composition having a high pigment concentration, and the deep-layer curability and the pattern shape can be improved.

Further, it is considered that since the structural unit represented by the formula (D1) has a relatively long side chain structure and the side chain has a polar group represented by the formula (D2), the formula (D3) or the formula (D3'), the adsorption property to the pigment is improved and three-dimensional repulsion for suppressing aggregation of pigment particles is exhibited. As a result, it is considered that the dispersibility of the pigment is improved.

Further, it is considered that since the specific resin has a structural unit represented by the formula (D4) described later, a carboxylic acid serving as an adsorptive group can be introduced at a position separated from the main chain, and the pigment adsorption property is improved and the dispersion stability is improved.

Further, it is considered that the introduction of the structural unit represented by the formula (D1) improves the substrate adhesion and the pattern shape by making the above-mentioned deep-layer curability excellent, and further, the dispersion stability of the curable composition is improved by having the structural unit represented by the formula (D4) described later.

From the viewpoint of deep curability, R in the formula (D1) is preferable^D1～R^D3Each independently is a hydrogen atom or a methyl group, more preferablyA hydrogen atom. And, from the viewpoint of deep curability, R^D1Is a hydrogen atom or a methyl group, and R^D2And R^D3Further preferred is a hydrogen atom. L is^D1In the case of a group represented by the formula (D2), R^D1Further preferred is methyl, L^D1In the case of a group represented by the formula (D3) or the formula (D3'), R^D1Further preferred is a hydrogen atom.

From the viewpoint of deep curability, X in the formula (D1)^D1is-COO-or CONR^D6-COO-is more preferable. X^D1In the case of an arylene group, a 2-valent aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is further preferable. X^D1When it is COO-, it is preferable that the carbon atom in-COO-and R in the formula (D1)^D1The bonded carbon atoms are bonded. X^D1is-CONR^D6when-is-CONR is preferred^D6The carbon atom in (A) and R in the formula (D1)^D1The bonded carbon atoms are bonded.

R^D6Preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

From the viewpoint of deep curability, R in the formula (D1)^D4The group in which a hydrocarbon group or a hydrocarbon group of 2 or more is bonded to 1 or more structures selected from ether bonds and ester bonds is preferable, and the group in which a hydrocarbon group or a hydrocarbon group of 2 or more is bonded to 1 or more ester bonds is more preferable.

R in the formula (D1)^D4Preferably 2 or more groups selected from the group consisting of alkylene groups, ether groups, carbonyl groups, phenylene groups, cycloalkylene groups and ester bonds, and more preferably 2 or more groups selected from the group consisting of alkylene groups, ether groups and ester bonds.

In addition, from the viewpoint of deep curability, R in the formula (D1)^D4The total number of atoms is preferably 2 to 60, more preferably 2 to 50, and particularly preferably 2 to 40.

Further, from the viewpoint of deep curability, R^D4Particularly preferably a group selected from the group consisting of a hydrocarbon group, an alkyleneoxy group, an alkylenecarbonyloxy group and any group represented by the following structure, and R is as defined above^D5Is alkylene or alkylene of 2 or moreAnd a group bonded to 1 or more structures selected from an ether bond and an ester bond.

[ chemical formula 24]

In the above formula, preferably, the cross-hatched part represents a bonding position with another structure, and X in the formula (D1)^D1Bonding site, wave line part representation and L^D1The bonding position of (2).

And, in the above formula, L^F1And L^F2Each independently represents a hydrocarbon group, and n represents an integer of 0 or more.

Also preferred is L^F1And L^F2Each independently an alkylene group having 2 to 20 carbon atoms.

Also preferred is L^F1And L^F2In the same manner as the groups.

Also preferably, n is 0 to 100.

From the viewpoint of deep curing properties, nD in formula (D1) is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

From the viewpoint of deep curability, R in the formula (D1) is preferable^D5The group is a 2-valent linking group, more preferably an alkylene group or a group in which 1 or more structures selected from ether linkages and ester linkages are bonded to an alkylene group or 2 or more alkylene groups, still more preferably an alkyleneoxyalkylene group, and particularly preferably a methyleneoxy-n-butenyl group.

In addition, from the viewpoint of deep curability, R in the formula (D1)^D5The total number of atoms is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 20.

From the viewpoint of deep curability, X in the formula (D1)^D2Oxygen atoms are preferred.

R^D7Preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

R^DPreferably a hydrogen atom.

L in the formula (D1) from the viewpoint of dispersibility^D1The group represented by the formula (D2) is preferable, and the group represented by the formula (D3) or the formula (D3') is preferable from the viewpoint of pattern shape and suppression of development residue.

In the above formulae (D2), (D3) and (D3'), preferably, R is^D4The wave line part of the bonding part of (2) is represented by R^D5The bonding site of (3).

From the viewpoint of deep curability and dispersibility, X in the formula (D2)^D3Oxygen atoms are preferred.

And, from the viewpoint of deep curability and dispersibility, L^D1In the case of a group represented by the formula (D2), R is particularly preferred^D4Is a group selected from ethylene, n-propylene, isopropylene, n-butylene and isobutylene, and R is^D5Is an ethylene group.

X in the formula (D3) or (D3 ') is X in the formula (D3) or (D3') from the viewpoint of deep-layer curability, pattern shape, and development residue suppression^D4preferably-COO-. X^D4In the case of the above-mentioned-COO-, the oxygen atom in-COO-and R are preferable^e1The bonded carbon atoms are bonded.

R in the formula (D3) or the formula (D3 ') is R in the formula (D3) or the formula (D3') from the viewpoints of deep-layer curability, pattern shape, and development residue suppression^e1～R^e3Preferably a hydrogen atom.

And, L^D1In the case of the group represented by the formula (D3) or the formula (D3'), R is particularly preferable from the viewpoint of deep curability, pattern shape and suppression of development residue^D4Is a group in which a hydrocarbon group, 2 or more hydrocarbon groups and 1 or more structures selected from ether bonds and ester bonds are bonded, or an arbitrary group represented by the following structure, and R^D5The alkylene group or the group in which 1 or more structures selected from ether bonds and ester bonds are bonded to 2 or more alkylene groups.

As the group represented by the formula (D2), preferred are groups represented by the following formula (D2-1) or formula (D2-2).

Further, as the group represented by the formula (D3), a group represented by the following formula (D3-1) or formula (D3-2) can be preferably mentioned.

[ chemical formula 25]

The dotted line and wavy line portions in formulae (D2-1), (D2-2), (D3-1) and (D3-2) are the same as those in formulae (D2) and (D3), and preferred embodiments are also the same.

In the structures of formula (D3-1) and formula (D3-2), at least a part of the structures may be represented by formula (D3-1 ') relative to formula (D3-1) and formula (D3-2') relative to formula (D3-2). With respect to the structure of the formula (D3-1'), as an example, a carboxylic acid compound exists as a structural isomer when reacting with a compound having an epoxy group and an acryloyl group. With respect to the structure of the formula (D3-2'), as an example, a phenol compound exists as a structural isomer when reacting with a compound having an epoxy group and an acryloyl group.

[ chemical formula 26]

The structural unit represented by the formula (D1) is preferably represented by the following structures, but is not limited thereto. In the following specific examples, m represents an integer of 2 or more, and n represents an integer of 1 or more.

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

The specific resin may have 1 kind alone, or may have 2 or more kinds of structural units represented by the formula (D1).

The content of the structural unit represented by the formula (D1) is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and particularly preferably 1 to 60% by mass, based on the total mass of the specific resin, from the viewpoints of developability, pattern shape, dispersion stability, and deep-layer curability.

[ structural Unit represented by the formula (D4) ]

From the viewpoint of dispersion stability and developability, the specific resin preferably further has a structural unit represented by the following formula (D4).

[ chemical formula 30]

In the formula (D4), R^D8Represents a hydrogen atom or an alkyl group, X^D5represents-COO-, -CONR^BOr arylene radical, R^BRepresents a hydrogen atom, an alkyl group or an aryl group, L^D2Represents a group in which 2 or more groups selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms are bonded to 1 or more groups selected from an ether bond and an ester bond, and further L^D2At X^D5In the case of an arylene group, it may be a single bond.

R in the formula (D4)^D8Preferably a hydrogen atom.

From the viewpoint of dispersion stability, X in the formula (D4)^D5preferably-COO-or-CONR^B-COO-is more preferable. X^D5In the case of-COO-, the carbon atom in-COO-and R in the formula (D4) are preferable^D8The bonded carbon atoms are bonded. X^D5is-CONR^DBIn case of-CONR, it is preferably-CONR^DBThe carbon atom in (A) and R in the formula (D4)^D8The bonded carbon atoms are bonded.

R^BPreferably a hydrogen atom or an alkyl group, more preferably hydrogenAn atom.

L in the formula (D4) from the viewpoint of dispersion stability^D2The aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which 2 or more aliphatic hydrocarbon groups having 1 to 10 carbon atoms are bonded to 1 or more ester bonds is preferable, the aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable, and the alkylene group having 1 to 10 carbon atoms is particularly preferable.

The structural unit represented by the formula (D4) is preferably represented by the following structures, but is not limited thereto. In the following specific examples, n represents an integer of 1 or more.

[ chemical formula 31]

The specific resin may have 1 kind alone, or may have 2 or more kinds of structural units represented by the formula (D4).

The content of the structural unit represented by the formula (D4) is preferably 20 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 20 to 60% by mass, based on the total mass of the specific resin, from the viewpoints of developability, pattern shape, and dispersion stability.

[ structural Unit represented by the formula (D5) ]

The specific resin preferably further has a structural unit represented by the following formula (D5) from the viewpoint of dispersion stability, and more preferably further has a structural unit represented by the above formula (D4) and a structural unit represented by the following formula (D5) from the viewpoint of dispersion stability and developability.

[ chemical formula 32]

In the formula (D5), R^D9Represents a hydrogen atom or an alkyl group, X^D6Represents an oxygen atom or NR^C-，R^CRepresents a hydrogen atom, an alkyl group or an aryl group, L^D3Denotes a 2-valent linking group, Y^D1To representAlkyleneoxy or alkylenecarbonyloxy, Z^D1Represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, p represents an integer of 1 or more, and when p is 2 or more, p Y s^D1May be the same or different.

R in the formula (D5)^D9Preferably a hydrogen atom or a methyl group, more preferably a methyl group.

From the viewpoint of dispersion stability, X in the formula (D5)^D6Oxygen atoms are preferred.

R^CPreferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

L in the formula (D5) from the viewpoint of dispersion stability^D3The total number of atoms is preferably 2 to 30, more preferably 3 to 20, and particularly preferably 4 to 10.

And, from the viewpoint of dispersion stability, L in the formula (D5)^D3A group having a urethane bond or a urea bond is preferable, a group having a urethane bond is more preferable, and a group in which an alkylene group is bonded to a urethane bond is particularly preferable.

From the viewpoint of dispersion stability, Y in the formula (D5)^D1Alkylene carbonyloxy is preferred. And p of Y^D1When a plurality of structures are contained, the structures may be arranged randomly or may be arranged in blocks.

The number of carbon atoms of the alkylenecarbonyloxy group is preferably 2 to 30, more preferably 3 to 10, and particularly preferably 5 to 8, from the viewpoint of dispersion stability.

From the viewpoint of dispersion stability, p is an integer of 1 or more, preferably 3 or more.

P is preferably 100 or less, more preferably 60 or less, and particularly preferably 40 or less.

From the viewpoint of dispersion stability, Z in the formula (D5)^D1The aliphatic hydrocarbon group has preferably 1 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and particularly preferably 6 to 20 carbon atoms.

And, from the viewpoint of dispersion stability, Z^D1The above alkyl group in (1) is preferably a branched alkyl group.

The structural unit represented by the formula (D5) is preferably represented by the following structures, but is not limited thereto. In the following specific examples, n represents an integer of 1 or more, and a and b each independently represent an integer of 1 or more.

Further, it is preferable that a oxyalkylene carbonyl structures or alkyleneoxy structures and b oxyalkylene carbonyl structures or alkyleneoxy structures are arranged in a random order.

[ chemical formula 33]

The specific resin may have 1 kind alone, or may have 2 or more kinds of structural units represented by the formula (D5).

From the viewpoint of developability and dispersion stability, the content of the structural unit represented by the formula (D5) is preferably 5 to 80 mass%, more preferably 5 to 70 mass%, and particularly preferably 5 to 60 mass% with respect to the total mass of the specific resin.

[ other structural units ]

The specific resin may have other structural units than the structural units represented by the above formula (a1), formula (B1), formula (D1), formula (D4), and formula (D5).

The other constituent units are not particularly limited, and may include known constituent units.

[ Properties of specific resin ]

-weight average molecular weight-

The weight average molecular weight (Mw) of the specific resin is preferably 1,000 or more, more preferably 1,000 to 200,000, and particularly preferably 1,000 to 100,000.

-ethylenic unsaturation valence-

The ethylenic unsaturated bond value of the specific resin is preferably 0.01 to 2.5mmol/g, more preferably 0.05 to 2.3mmol/g, still more preferably 0.1 to 2.2mmol/g, and particularly preferably 0.1 to 2.0mmol/g, from the viewpoint of deep curability, pattern shape, and substrate adhesion.

The ethylenic unsaturated bond valence of a specific resin means the molar amount of ethylenic unsaturated groups per 1g of the solid content of the specific resin, and is measured by the method described in the examples.

Acid value-

From the viewpoint of developability, the acid value of the specific resin is preferably 30 to 110mgKOH/g, more preferably 40 to 90 mgKOH/g.

The acid value was measured by the method described in examples.

Amine value-

The amine value of the specific resin is preferably 0.03 to 0.8mmol/g, more preferably 0.1 to 0.5mmol/g, from the viewpoint of adhesion to the support.

The amine value was measured by the method described in examples.

The curable composition may contain 1 kind of the specific resin alone, or may contain 2 or more kinds of the specific resins.

The content of the specific resin is preferably 10 to 45% by mass, more preferably 12 to 40% by mass, and particularly preferably 14 to 35% by mass, based on the total solid content of the curable composition, from the viewpoint of adhesion to a support and storage stability.

The content of the specific resin is preferably 20 to 60 parts by mass, more preferably 22 to 55 parts by mass, and particularly preferably 24 to 50 parts by mass, based on 100 parts by mass of the pigment content, from the viewpoint of adhesion to the support and storage stability.

The method for synthesizing the specific resin is not particularly limited, and the specific resin can be synthesized by a known method or by applying a known method.

For example, a method may be mentioned in which a precursor of the above-mentioned specific resin is synthesized by a known method, and then a group having a radical polymerizable group in the structural unit represented by the above-mentioned formula (a1) or formula (B1) is introduced by a polymer reaction.

The structural unit represented by the formula (a1) is introduced by, for example, a reaction between a carboxyl group contained in the precursor of the specific resin and an amine compound and a compound having an epoxy group and an acryloyl group. The structural unit represented by the formula (a1) is introduced by the reaction of an amine compound contained in the precursor of the specific resin with a compound having a halogenated group and an acryloyl group.

The structural unit represented by the formula (B1) is introduced by the reaction between an amino group contained in the precursor of the specific resin and a compound having an epoxy group and an acryloyl group. The structural unit represented by the formula (B1) is introduced by the reaction between an amino group of the precursor of the specific resin and a compound having a halogenated group and an acryloyl group.

The structural unit represented by the formula (D1) is introduced by, for example, a reaction between a carboxyl group contained in the precursor of the specific resin and a compound having an epoxy group and an acryloyl group, a reaction between a hydroxyl group contained in the precursor of the specific resin and a compound having an isocyanate group and an acryloyl group, or the like.

These synthetic methods are only examples, and the synthetic method of the specific resin is not particularly limited.

When the specific resin is a star polymer compound or a star polymer compound having a specific terminal group, these polymer compounds can be synthesized, for example, by the synthesis method described in jp 2007-a 277514 a.

The specific resin is composed of different structural units such as a structural unit responsible for developability, a structural unit responsible for dispersibility, and a structural unit responsible for curability, and the composition of the specific resin is preferably homogenized in order to effectively exhibit different functions.

As a method for homogenizing the composition of the above specific resin, for example, a method of dropping a monomer into a reaction system so as to match the consumption rates of different monomer species can be cited. In general, the reaction rate can be adjusted by increasing the initial concentration in the reaction system of a monomer species having a low consumption rate and dropping a monomer species having a high consumption rate to generate a concentration difference in the reaction system.

Specific examples of the specific resin in the present invention include PA-1 to PA-22 and PB-1 to PB-18 in examples described later.

[ content ]

The content of the specific resin in the total solid content of the curable composition is preferably 5 to 50% by mass. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. The content of the specific resin having an acid group in the total solid content of the curable composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

In addition, from the viewpoint of curability, developability, and film-forming properties, the total content of the polymerizable compound and the specific resin described below in the total solid content of the curable composition is preferably 10 to 65% by mass. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less. The specific resin is preferably contained in an amount of 30 to 300 parts by mass per 100 parts by mass of the polymerizable compound. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

< polymerizable Compound >

The curable composition of the present invention preferably contains a polymerizable compound. The compound corresponding to the specific resin is not a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid, or heat can be used. In the present invention, the polymerizable compound is preferably a compound having an ethylenically unsaturated group, for example. Examples of the ethylenically unsaturated group include a vinyl group, (meth) allyl group, and (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be any of monomers, prepolymers, oligomers, and other chemical forms, and monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3,000. The upper limit is more preferably 2,000 or less, and still more preferably 1,500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more.

The polymerizable compound preferably contains 3 or more ethylenically unsaturated groups, more preferably 3 to 15 ethylenically unsaturated groups, and still more preferably 3 to 6 ethylenically unsaturated groups. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of the polymerizable compound include those described in the paragraphs 0095 to 0108 of Japanese patent laid-open No. 2009-288705, 0227 of Japanese patent laid-open No. 2013-029760, 0254 to 0257 of Japanese patent laid-open No. 2008-29292970, 0034 to 0038 of Japanese patent laid-open No. 2013-253224, 0477 of Japanese patent laid-open No. 2012-208494, 048367 of Japanese patent laid-open No. 2017-0483, and 6031807, and these are incorporated herein by reference.

As the polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD-330; Nippon Kayaku Co., Ltd., manufactured by Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARADDPHA; Nippon Kayaku Co., manufactured by Ltd., manufactured by NK Ester A-DPH-12E; Shin Nakamura Chemical Co., manufactured by Ltd.) and a compound having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, RTSR 454, OMER 499, sold by SASR company). Further, as the polymerizable compound, diglycerol EO (ethylene oxide) -modified (meth) acrylate (M-460; TOAGOSEI CO., LTD., manufactured by LTD.), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., manufactured by Ltd., NK EsterA-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku Co., manufactured by Ltd., KAYARAD HDDA), RP-1040(Nippon Kayaku Co., manufactured by Ltd.), ARONIXTO-2349(TOAGOSEI CO., manufactured by LTD., manufactured by LTD., NK OligoUA-7200(Shin-Nakamura Co., manufactured by Ltd., 8UH-1006, 8UH-1012(TAISEI FINE CHEMICAL CO., manufactured by LTD., LIGHT ACRYLATE POB-A0 (OEISKYHA, CHEMIC Co., manufactured by LTD., etc.) can be used.

Also, as the polymerizable compound, 3-functional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, trimethylolpropane-propylene oxide-modified tri (meth) acrylate, trimethylolpropane-ethylene oxide-modified tri (meth) acrylate, isocyanurate-ethylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferably used. Commercially available products of 3-functional (meth) acrylate compounds include ARONIXM-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (Shin-Nakamura Chemical Co., manufactured by LtdD.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltdu.) and THE like.

As the polymerizable compound, a compound having an acid group can be used. By using the polymerizable compound having an acid group, the polymerizable compound in the unexposed portion of the film formed from the curable composition can be easily removed during development, and the generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and the like, and a carboxyl group is preferable. Commercially available products of polymerizable compounds having an acid group include ARONIXM-510, M-520, and ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.). The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1mgKOH/g or more, the solubility in a film of a developer is good, and when it is 40mgKOH/g or less, it is advantageous in terms of production and handling.

It is also preferable that the polymerizable compound is a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are sold as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

The polymerizable compound having an alkyleneoxy group can be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and still more preferably a 3-6 functional (meth) acrylate compound having 4-20 ethyleneoxy groups. Commercially available products of polymerizable compounds having an alkyleneoxy group include, for example, SR-494 which is a 4-functional (meth) acrylate having 4 ethyleneoxy groups manufactured by SARTOMER corporation, and KAYARAD TPA-330 which is a 3-functional (meth) acrylate having 3 isobutynyleneoxy groups.

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can be used. Commercially available products of polymerizable compounds having a fluorene skeleton include OGSOLEA-0200 and EA-0300 (a (meth) acrylate monomer having a fluorene skeleton manufactured by Osaka Gas Chemical Co., Ltd.).

As the polymerizable compound, a compound substantially not containing an environmental control substance such as toluene is also preferably used. Commercially available products of such a compound include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, acrylic carbamates as disclosed in JP-B-48-041708, JP-B-51-037193, JP-B-02-032293 and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. It is also preferable to use polymerizable compounds having an amine structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238. Further, commercially available compounds such as UA-7200(Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (KYOEISHA CHEMICAL Co., LTD.) can also be used as the polymerizable compound.

The content of the polymerizable compound in the total solid content of the curable composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less. The polymerizable compound may be used in a single amount of 1 kind, or 2 or more kinds may be used in combination. When 2 or more kinds are used in combination, the total of these is preferably in the above range.

< photopolymerization initiator >

The curable composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light from an ultraviolet region to a visible region is preferable. The photopolymerization initiator is preferably a photo radical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and the like), acylphosphine compounds, hexaarylbisimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α -hydroxyketone compounds, α -aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α -hydroxyketone compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a diphenylketone compound, an acetophenone compound, a cyclopentadiene-benzene-imidazole compound, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of an oxime compound, an α -hydroxyketone compound, an α -aminoketone compound, and an acylphosphine compound, and further preferably an oxime compound from the viewpoint of easily obtaining the effects of the present invention. As the photopolymerization initiator, reference can be made to paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173 and Japanese patent application laid-open No. 6301489, and these contents are incorporated in the present specification.

Commercially available products of the α -hydroxyketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available products of the α -aminoketone compound include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Co., Ltd.). As commercially available acylphosphine compounds, IRGACURE-819 and DAROCUR-TPO (manufactured by BASF) can be mentioned.

Examples of oxime compounds include a compound described in Japanese patent laid-open No. 2001-233842, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pp.1653-1660), a compound described in J.C.S.Perkin II (1979, pp.156-162), a compound described in Journal of Photopharmaceuticals Science and Technology (1995, pp.202-232), a compound described in Japanese patent laid-open No. 2000-630685, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2004-534797, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in Japanese patent laid-open No. 2017-019766, a compound described in Japanese patent laid-open No. 6065596, A compound described in International publication No. 2015/152153, a compound described in International publication No. 2017/051680, a compound described in Japanese patent laid-open publication No. 2017-198865, a compound described in paragraphs No. 0025 to 0038 of International publication No. 2013/167515, and the like. Specific examples of the oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutyl-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04 (manufactured by BASF Co., Ltd.), TR-PBG-304(Changzhou Tronly New Electronic Materials CO., LTD., manufactured by Inc.), and ADEKA OPTOMERN 1919 (photopolymerization initiator 2 described in ADEKA CORATION, Japanese patent application laid-open No. 2012-014052). Further, as the oxime compound, a compound having low coloring property or a compound having high transparency and being less likely to be discolored is also preferably used. Examples of commercially available products include ADEKA ARKLSNCI-730, NCI-831 and NCI-930 (manufactured by ADEKA CORPORATION).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese patent laid-open publication No. 2014-137466. And this matter is incorporated into this specification.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in Japanese patent application laid-open No. 2013-164471. These are incorporated into the present specification.

In the present invention, an oxime compound having a nitro group can also be used as a photopolymerization initiator. Oxime compounds having a nitro group are also preferred as dimers. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and ADEKA ARKLSNCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples thereof include OE-01 to OE-75 as described in International publication No. 2015/036910.

Specific examples of oxime compounds preferably used in the present invention will be shown below, but the present invention is not limited to these.

[ chemical formula 34]

[ chemical formula 35]

The photopolymerization initiator used in the present invention is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.

Further, from the viewpoint of more easily obtaining the effects of the present invention, the molar absorption coefficient of the photopolymerization initiator used in the present invention at a wavelength of 365nm is preferably 1,000 L.mol^-1·cm^-1More preferably 3,000 L.mol or more^-1·cm^-1Above, 5,000 L.mol is more preferable^-1·cm^-1The above. The maximum value is not particularly limited, but is preferably 100,000 L.mol^-1·cm^-1The following. The molar absorption coefficient of the photopolymerization initiator can be measured by a known method. For example, a spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) is preferable, and measurement is performed at a concentration of 0.01g/L using an ethyl acetate solvent.

As the photopolymerization initiator, a 2-functional or 3-or more-functional photo radical polymerization initiator can be used. Since 2 or more radicals are generated from 1 molecule of the photo radical polymerization initiator by using such a photo radical polymerization initiator, good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is improved, precipitation with time is less likely to occur, and the stability of the curable composition with time can be improved. Specific examples of the 2-functional or 3-or more-functional photo radical polymerization initiator include dimers of oxime compounds described in Japanese patent application No. 2010-527339, Japanese patent application No. 2011-524436, International publication No. 2015/004565, Japanese patent application No. 2016-532675, paragraphs No. 0412 to 0417, and paragraphs No. 0039 to 0055 of International publication No. 2017/033680, the compound (E) and the compound (G) described in JP-A-2013-522445, Cmpd 1-7 described in International publication No. 2016/034963, the oxime ester photoinitiator described in JP-A-2017-523465, the photoinitiator described in JP-A-2017-0020-0033, and the photopolymerization initiator (A) described in JP-A-2017-151342-0017-0026.

The content of the photopolymerization initiator in the total solid content of the curable composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. In the curable composition of the present invention, only 1 kind of photopolymerization initiator may be used, or 2 or more kinds may be used. When 2 or more species are used, the total amount of these is preferably in the above range.

< other resins >

The curable composition of the present invention may further contain other resins. In the present invention, the compound corresponding to the above specific resin is not used as another resin. The other resin is blended, for example, for the purpose of dispersing particles such as a pigment in a curable composition or for the purpose of a binder. Among these, such use of other resins is an example, and the resin can be used for purposes other than this use.

The weight average molecular weight (Mw) of the other resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

Examples of the other resin include (meth) acrylic resins, olefin thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. These resins may be used alone in 1 kind or in combination of 2 or more kinds. Further, resins described in paragraphs 0041 to 0060 of Japanese patent application laid-open No. 2017-206689 and resins described in paragraphs 0022 to 0071 of Japanese patent application laid-open No. 2018-010856 can be used.

[ resin having acid group ]

The curable composition of the present invention preferably contains a resin having an acid group as another resin. According to this embodiment, the developability of the curable composition can be improved, and a pixel having excellent rectangularity can be easily formed. Preferable examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group. Resins having acid groups can be used as alkali-soluble resins, for example.

The resin having an acid group preferably contains a structural unit having an acid group in a side chain, and more preferably contains 5 to 70 mol% of the structural unit having an acid group in a side chain among all the structural units of the resin. The upper limit of the content of the structural unit having an acid group in a side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the structural unit having an acid group in a side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

In the present specification, when the content of the structural unit is expressed in mol%, the structural unit has the same meaning as the monomer unit.

The resin having an acid group also preferably contains a structural unit derived from a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer").

[ chemical formula 36]

In the formula (ED1), R¹And R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[ chemical formula 37]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1-30 carbon atoms. The details of the formula (ED2) can be found in japanese patent application laid-open No. 2010-168539, which is incorporated herein by reference.

As a specific example of the ether dimer, for example, reference can be made to the description of paragraph number 0317 of Japanese patent laid-open publication No. 2013-029760, and the contents thereof are incorporated in the present specification.

The resin used in the present invention also preferably contains a structural unit derived from a compound represented by the following formula (X).

[ chemical formula 38]

In the formula (X), R₁Represents a hydrogen atom or a methyl group, R₂Represents an alkylene group having 2 to 10 carbon atoms, R₃Represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. n represents an integer of 1 to 15.

As the resin having an acid group, reference can be made to the descriptions of Japanese patent application laid-open Nos. 0558 to 0571 (corresponding to U.S. patent application laid-open Nos. 0685 to 0700 of 2012/0235099) and the descriptions of Japanese patent application laid-open Nos. 2012 and 198408, paragraphs 0076 to 0099, which are incorporated herein. Further, commercially available resins having an acid group can also be used.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The upper limit is preferably 400mgKOH/g or less, more preferably 300mgKOH/g or less, and still more preferably 200mgKOH/g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

Examples of the resin having an acid group include resins having the following structures. In the following structures, the subscripts in parentheses indicate the content (mol%) of each structural unit.

[ chemical formula 39]

[ dispersant ]

The curable composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of the acid group is 70 mol% or more, and more preferably a resin substantially composed of only the acid group, when the total amount of the acid group and the basic group is 100 mol%. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 20 to 180mgKOH/g, more preferably 30 to 150mgKOH/g, and still more preferably 50 to 100 mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of basic groups than that of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a structural unit having an acid group. By the resin serving as the dispersant containing a structural unit having an acid group, generation of development residue can be more suppressed at the time of pattern formation by photolithography.

The resin used as a dispersant is also preferably a graft resin. The details of the graft resin can be found in paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012 and 255128, which are incorporated herein by reference.

The resin used as the dispersant is also preferably a polyimide-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimide-based dispersant preferably has a main chain having a partial structure with a functional group having a pKa of 14 or less, and a side chain having 40 to 10,000 atoms and having a basic nitrogen atom in at least one of the main chain and the side chain. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The polyimide-based dispersant can be described in Japanese patent laid-open Nos. 2012 and 255128, paragraphs 0102 to 0166, and the contents thereof are incorporated herein.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such a resin include a dendrimer (including a star polymer). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in the paragraphs 0196 to 0209 of Japanese patent laid-open publication No. 2013-043962.

Further, a resin having the above-mentioned acid group (alkali-soluble resin) can also be used as the dispersant.

Also, the resin used as the dispersant is preferably a resin containing a structural unit having an ethylenically unsaturated group in a side chain. The content of the structural unit having an ethylenically unsaturated group in a side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol% of all the structural units of the resin.

The dispersant may be obtained in the form of a commercially available product, and specific examples thereof include DISPERBYK series (for example, DISPERBYK-111, 161) manufactured by BYKChemie GmbH, SOLSPERSE series (for example, SOLSPERSE 76500) manufactured by Japan Lubrizol Corporation, and the like. Further, the pigment dispersants described in Japanese patent application laid-open Nos. 2014-130338, paragraphs 0041 to 0130 can be used and are incorporated in the present specification. The resin described as the dispersant can be used for applications other than dispersants. For example, it can also be used as an adhesive.

Resins having curable groups

As the dispersant used in the present invention, a resin having a curable group can be appropriately exemplified.

The curable group in the dispersant is preferably an ethylenically unsaturated group, more preferably at least one selected from the group consisting of a vinyl group, a vinylphenyl group, an allyl group, a (meth) acryloyl group, a (meth) acrylamido group, and a maleimido group, even more preferably a (meth) acryloyl group, and particularly preferably an acryloyl group.

The resin having a curable group preferably has a curable group in a side chain, and also preferably has a curable group at a molecular terminal of a side chain.

The preferable weight average molecular weight of the dispersant is 10,000 to 100,000.

The resin having a curable group includes a resin containing a structural unit represented by the above formula (D1), preferably a resin containing at least one selected from the group consisting of a structural unit represented by the above formula (D1), a structural unit represented by the above formula (D4), and a structural unit represented by the above formula (D5), and more preferably a resin containing a structural unit represented by the above formula (D1), a structural unit represented by the above formula (D4), and a structural unit represented by the above formula (D5).

The resin having a curable group is a resin that does not satisfy either of the conditions 1 and 2.

[ content ]

When the curable composition of the present invention contains another resin, the content of the other resin in the total solid content of the curable composition is preferably 0.5 to 50% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. The content of the resin having an acid group in the total solid content of the curable composition is preferably 0.5 to 50% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

< Compound having Cyclic Ether group >

The curable composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetane group. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include compounds having 1 or more epoxy groups in 1 molecule, and compounds having 2 or more epoxy groups are preferable. Preferably, the epoxy group has 1 to 100 epoxy groups in 1 molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more. As the compound having an epoxy group, compounds described in paragraphs 0034 to 0036 of Japanese patent application laid-open No. 2013-011869, paragraphs 0147 to 0156 of Japanese patent application laid-open No. 2014-043556, compounds described in paragraphs 0085 to 0092 of Japanese patent application laid-open No. 2014-089408, and compounds described in Japanese patent application laid-open No. 2017-179172 can be used. These are incorporated into the present specification.

The compound having an epoxy group may be a low molecular compound (for example, less than 2000 molecular weight, and further less than 1,000 molecular weight), or may be a high molecular compound (macromolecule) (for example, 1,000 or more molecular weight, and in the case of a polymer, 1,000 or more weight average molecular weight). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less.

As the compound having an epoxy group, an epoxy resin can be preferably used. Examples of the epoxy resin include epoxy resins which are glycidyl etherates of phenol compounds, epoxy resins which are glycidyl etherates of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having epoxy groups with silicon compounds other than these, copolymers of polymerizable unsaturated compounds having epoxy groups with polymerizable unsaturated compounds other than these, and the like. The epoxy equivalent of the epoxy resin is preferably 310 to 3,300g/eq, more preferably 310 to 1,700g/eq, and still more preferably 310 to 1,000 g/eq.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by DAICEL CORPORATION), EPICLON N-695 (manufactured by DIC CORPORATION), MarproofG-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (or more, a polymer containing an epoxy group manufactured by NOF CORATION).

When the curable composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the curable composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The number of the compounds having a cyclic ether group may be only 1, or may be 2 or more. When the number of these is 2 or more, the total amount of these is preferably in the above range.

< silane coupling agent >

The curable composition of the present invention may contain a silane coupling agent. According to this aspect, the adhesion to the support of the obtained film can be further improved. In the present invention, the silane coupling agent is a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a substituent capable of forming a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction by being directly bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a thioether group, an isocyanate group, and a phenyl group, and an amino group, a (meth) acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of Japanese patent application laid-open No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese patent application laid-open No. 2009-242604, and these contents are incorporated herein.

The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The number of silane coupling agents may be only 1, or may be 2 or more. When the number of the compounds is 2 or more, the total amount is preferably in the above range.

< solvent >

The curable composition of the present invention may contain a solvent. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the curable composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details of these, reference can be made to paragraph number 0223 of international publication No. 2015/166779, which is incorporated in the present specification. Also, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, 3-ethoxymethylpropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. Among them, from the viewpoint of environmental factors and the like, it is preferable that aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, and the like) as a solvent be reduced in some cases (for example, the amount may be 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less with respect to the total amount of the organic solvent).

In the present invention, it is preferable to use a solvent having a small metal content, and the metal content of the solvent is, for example, preferably 10 parts per billion (ppb) or less by mass. Solvents of the grade ppt (parts per trillion) in mass can be used as required, such high purity solvents being supplied, for example, by Toyo Gosei co., ltd. (journal of chemical industry, 11/13/2015).

Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, membrane distillation, or the like) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is polytetrafluoroethylene, preferably polyethylene or nylon.

The solvent may contain isomers (compounds having the same atomic number but different structures). The isomer may be contained in only 1 kind or in plural kinds.

In the present invention, the content of the peroxide in the organic solvent is preferably 0.8mmol/L or less, and more preferably, the organic solvent contains substantially no peroxide.

The content of the solvent in the curable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass.

In view of environmental control, it is preferable that the curable composition of the present invention contains substantially no environmental control substance. In the present invention, the substantial absence of the environmental control substance means that the content of the environmental control substance in the curable composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environment-controlling substance include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as environmental control substances based on the reach (registration Evaluation Authorization and recovery of Chemicals) regulation, the PRTR (pollution Release and Transfer register) regulation, the VOC (volatile Organic Compounds) regulation, and the like, and the amount of use and the treatment method are strictly controlled. These compounds may be used as a solvent in the production of each component used in the curable composition of the present invention, or may be mixed into the curable composition as a residual solvent. From the viewpoint of safety to the human body and environmental protection, it is preferable to reduce these substances as much as possible. As a method for reducing the environmental controlled substance, there is a method for reducing the environmental controlled substance by heating or reducing the pressure of the system to a boiling point of the environmental controlled substance or higher and distilling off the environmental controlled substance from the system. In addition, when a small amount of the environmental control substance is distilled off, it is also effective to azeotropically remove the solvent with a solvent having the same boiling point in order to improve efficiency. When a compound having radical polymerizability is contained, the compound can be removed by distillation under reduced pressure by adding a polymerization inhibitor or the like in order to suppress intermolecular crosslinking due to a radical polymerization reaction in the process of removal by distillation under reduced pressure. These distillation removal methods can be performed at any stage of the raw materials, the reaction product of the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the curable composition prepared by mixing these compounds.

< polymerization inhibitor >

The curable composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine salt (ammonium salt, cerium salt, and the like). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass in the total solid content of the curable composition.

< surfactant >

The curable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. As the surfactant, there can be mentioned paragraphs 0238 to 0245 of International publication No. 2015/166779, which is incorporated herein by reference.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By adding the fluorine-based surfactant to the curable composition, the liquid properties (particularly, fluidity) can be further improved, and the liquid saving properties can be further improved. Further, a film having small thickness unevenness can be formed.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the viewpoint of uniformity of the thickness of the coating film and liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective, and the solubility in the curable composition is also good.

Examples of the fluorine-based surfactant include surfactants described in, for example, Japanese patent application laid-open Nos. 0060 to 0064 (corresponding to Japanese patent application laid-open Nos. 0060 to 0064 of 2014/017669) of Japanese patent application laid-open No. 2014-041318, and surfactants described in Japanese patent application laid-open Nos. 0117 to 0132 of 2011-132503, and the contents of these are incorporated in the present specification. Commercially available fluorine-based surfactants include, for example, Megaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (produced by DIC CORPORATION), FluoradFC430, FC431, FC171 (produced by Sumitomo 3M Limited), SurflonS-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (produced by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (produced by OMNOVA Solutions Inc.), and the like.

Further, the fluorine-based surfactant can also preferably use an acrylic compound having a molecular structure with a functional group containing a fluorine atom, and when heated, a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such a fluorine-containing surfactant include Megaface DS series (chemical industry journal, 2016 (2/22) th day) (Nissan Industrial News, 2016 (2/23) th day), manufactured by DIC CORPORATION, for example, Megaface DS-21.

Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used. Such a fluorine-based surfactant can be referred to the disclosure of Japanese patent application laid-open No. 2016-216602, and the contents thereof are incorporated in the present specification.

As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in Japanese patent application laid-open No. 2011-089090 can be mentioned. The fluorine-containing surfactant can also preferably use a fluorine-containing polymer compound containing: a structural unit derived from a (meth) acrylate compound having a fluorine atom; and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[ chemical formula 40]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% representing the proportion of the structural unit is mol%.

Further, as the fluorine-containing surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used. Specific examples thereof include the compounds described in the paragraphs 0050 to 0090 and 0289 to 0295 of Japanese patent application laid-open No. 2010-164965, such as Megaface RS-101, RS-102 and RS-718K, RS-72-K manufactured by DIC CORPORATION. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese patent laid-open publication No. 2015-117327 can be used.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONICL10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), TETRONIC304, 701, 704, FAT 901, 904, 150R1 (manufactured by BASF Corporation), SOLSPERSE20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002(Wako Pure Industries, Ltd.), PinD-6112, D-6112-366315 (MOKEL & TAOIL & TO Co., Ltd.), ltd), OLFINE E1010, SURFYNOL104, 400, 440 (manufactured by Nissin Chemical Industry co., ltd), and the like.

Examples of the silicon-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., LTD.), BYK307, BYK323, and ChemK 330 (manufactured by BYK GmbH).

The content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The number of the surfactants may be only 1, or may be 2 or more. When the number of the compounds is 2 or more, the total amount is preferably in the above range.

< other colorants >

The curable composition of the present invention may contain a colorant other than the above-described pigment. Examples of the other colorant include dyes.

[ dye ]

The dye is not particularly limited, and a known dye can be used. The dye can be a color dye or a near infrared ray absorption dye. Examples of the color dye include pyrazole azo compounds, aniline azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrromethene compounds. Further, thiazole compounds described in Japanese patent laid-open No. 2012-158649, azo compounds described in Japanese patent laid-open No. 2011-184493, and azo compounds described in Japanese patent laid-open No. 2011-145540 can also be used. Further, as the yellow dye, quinoline yellow compounds described in paragraphs 0011 to 0034 of Japanese patent application laid-open No. 2013 and 054339, quinoline yellow compounds described in paragraphs 0013 to 0058 of Japanese patent application laid-open No. 2014 and 026228, and the like can be used. Examples of the near-infrared absorbing dye include a pyrrolopyrrole compound, a ranunculus compound, an oxonol compound, a squarylium compound, a cyanine compound, a ketanium compound, a phthalocyanine compound, a naphthalocyanine compound, a pyrylium compound, an Auzlenium compound, an indigo compound, and a pyrromethene compound. Further, squarylium compounds described in Japanese patent laid-open publication No. 2017-197437, squarylium compounds described in paragraph Nos. 0090-0107 of International publication No. 2017/213047, pyrrole-containing compounds described in paragraph Nos. 0019-0075 of Japanese patent laid-open publication No. 2018-054760, pyrrole-containing compounds described in paragraph Nos. 0078-0082 of Japanese patent laid-open publication No. 2018-040955, pyrrole-containing compounds described in paragraph Nos. 0043-0069 of Japanese patent laid-open publication No. 2018-002773, squarylium compounds having an aromatic ring at the amide α position described in paragraph Nos. 0024-0086 of Japanese patent laid-open publication No. 2018-041047, amide-linked squarylium compounds described in Japanese patent laid-open publication No. 2017-179131, compounds having a pyrrole-symmetric squarylium acid skeleton or ketonium skeleton described in Japanese patent laid-open publication No. 2017-141215, and the like compounds having a pyrrole-symmetric squarylium skeleton or a ketonium skeleton, Dihydrocarbazole symmetrical squaraine compounds described in Japanese patent laid-open publication No. 2017-082029, asymmetric compounds described in paragraphs 0027-0114 of Japanese patent laid-open publication No. 2017-068120, pyrrole ring-containing compounds (carbazole type) described in Japanese patent laid-open publication No. 2017-067963, phthalocyanine compounds described in Japanese patent laid-open publication No. 6251530, and the like.

Also, the curable composition of the present invention may contain a pigment multimer as another colorant. The pigment multimer is preferably a dye which is dissolved in a solvent and used, but the pigment multimer may be formed into particles, and when the pigment multimer is a particle, it may be used in a state of being dispersed in a solvent. The pigment multimer in a particle state can be obtained by, for example, emulsion polymerization, and specific examples thereof include the compounds and production methods described in Japanese patent laid-open No. 2015-214682. The dye multimer has 2 or more dye structures, preferably 3 or more dye structures, in one molecule. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or different dye structures. The pigment multimer preferably has a weight average molecular weight (Mw) of 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and still more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and still more preferably 20,000 or less. The dye multimer may be a compound described in Japanese patent application laid-open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, or International publication WO 2016/031442.

When the curable composition contains another colorant, the content of the other colorant in the total solid content of the curable composition is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

The content of the other colorant is preferably 5 to 50 parts by mass based on 100 parts by mass of the pigment. The upper limit is preferably 45 parts by mass or less, and more preferably 40 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.

The curable composition of the present invention may not substantially contain other coloring agents. When the curable composition of the present invention contains substantially no other colorant, the content of the other colorant in the total solid content of the curable composition of the present invention is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably no colorant.

< ultraviolet absorber >

The curable composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a salicylate compound, a diphenylketone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, and the like can be used. For details of these, reference can be made to the descriptions in paragraphs 0052 to 0072 of japanese patent application laid-open No. 2012 and 208374, paragraphs 0317 to 0334 of japanese patent application laid-open No. 2013 and 068814, and paragraphs 0061 to 0080 of japanese patent application laid-open No. 2016 and 162946, and these contents are incorporated in the present specification. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.). As the benzotriazole compound, the MYUA series (journal of chemical industry, 2016, 2 months and 1 day) manufactured by MIYOSHI & FAT co.

[ chemical formula 41]

The content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only 1 kind of the ultraviolet absorber may be used, or 2 or more kinds may be used. When 2 or more species are used, the total amount is preferably within the above range.

< antioxidant >

The curable composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol antioxidant can be used. Preferable examples of the phenol compound include hindered phenol compounds. Preferred are compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Further, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can be preferably used. Examples of the phosphorus-based antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, F ] [1,3,2] dioxaphosphorinan-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4,6,9, 11-tetra-t-butyldibenzo [ d, F ] [1,3,2] dioxaphosphorinan-2-yl ] oxy ] ethyl ] amine, and ethyl phosphite bis (2, 4-di-t-butyl-6-methylphenyl), and commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab-40, Adekastab-50, Adekastab AO-50F, Adekastab AO-60G, Adekastab AO-30, Adekastab-40, Adekastab AO-50F, Adekastab AO-60G, and the like, Adekastab AO-80, Adekastab AO-330 (above, ADEKA CORPORATION), and the like.

The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant may be used in 1 type or 2 or more types. When 2 or more species are used, the total amount is preferably within the above range.

< oxidant >

The curable composition of the present invention may contain an oxidizing agent.

The oxidizing agent may contain a compound that functions as the polymerization inhibitor.

Examples of the oxidizing agent include quinone compounds and quinodimethane. As the quinone compound, p-benzoquinone, naphthoquinone, anthraquinone, chloranil, dichlorodicyanobenzoquinone (DDQ), and the like can be used. Examples of the quinodimethane include 7,7,8, 8-Tetracyanoquinodimethane (TCNQ), 2-fluoro-7, 7,8, 8-tetracyanoquinodimethane (FTCNQ), 2, 5-difluoro-7, 7,8, 8-tetracyanoquinodimethane (F2TCNQ), and tetracyanoquinodimethane (F4 TCNQ).

The oxidizing agent is preferably below the Lowest Unoccupied Molecular Orbital (LUMO) containing the pigment or dye. The LUMO of the oxidizing agent is preferably-3.5 eV or less, more preferably-3.8 eV or less, and particularly preferably-4.0 eV or less.

The content of the oxidizing agent in the total solid content of the curable composition is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, most preferably 0.001 to 1% by mass. The oxidizing agent may be used in 1 kind or 2 or more kinds. When 2 or more species are used, the total amount is preferably within the above range.

< other ingredients >

The curable composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjuster, a chain transfer agent, etc.) as needed. By appropriately containing these components, properties such as physical properties of the film can be adjusted. For example, the components can be described in, for example, paragraph No. 0183 of japanese patent application laid-open No. 2012 and 003225 (corresponding to paragraph No. 0237 of the specification of U.S. patent application publication No. 2013/0034812), and in paragraphs nos. 0101 to 0104, 0107 to 0109 and the like of japanese patent application laid-open No. 2008 and 250074, and the contents of these can be incorporated in the present specification. The curable composition of the present invention may contain a latent antioxidant, if necessary. The potential antioxidant includes a compound in which a site functioning as an antioxidant is protected with a protecting group, and the compound is heated at 100 to 250 ℃ or at 80 to 200 ℃ in the presence of an acid/base catalyst to release the protecting group and function as an antioxidant. Examples of the potential antioxidant include compounds described in International publication Nos. 2014/021023, 2017/030005 and 2017-008219. Examples of commercially available potential antioxidants include ADEKA ARKLSGPA-5001 (manufactured by ADEKA CORPORATION) and the like.

Further, the curable composition of the present invention may contain a metal oxide to adjust the refractive index of the obtained film. The metal oxide may be TiO₂、ZrO₂、Al₂O₃、SiO₂And the like. The primary particle diameter of the metal oxide is preferably 1 to 100nm, more preferably 3 to 70nm, and further preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core portion may be hollow.

The curable composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraphs 0036 to 0037 of Japanese patent laid-open publication No. 2017-198787, compounds described in paragraphs 0029 to 0034 of Japanese patent laid-open publication No. 2017-146350, compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese patent laid-open publication No. 2017-129774, compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of Japanese patent laid-open publication No. 2017-129674, compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of Japanese patent laid-open publication No. 2017-122803, compounds described in paragraphs 0025 to 0039 of International publication No. 2017/164127, compounds described in paragraphs 0034 to 0047 of Japanese patent laid-open publication No. 2017-546, compounds described in paragraphs 0030019 to 0041 of Japanese patent laid-open publication No. 025116, and compounds described in paragraphs 0120101455 to 0045 to 012604 of Japanese patent laid-145604, The compounds described in the paragraphs 0018 to 0021 in Japanese patent laid-open No. 2012 and 103475, the compounds described in the paragraphs 0015 to 0018 in Japanese patent laid-open No. 2011 and 257591, the compounds described in the paragraphs 0017 to 0021 in Japanese patent laid-open No. 2011 and 191483, the compounds described in the paragraphs 0108 to 0116 in Japanese patent laid-open No. 2011 and 145668, the compounds described in the paragraphs 0103 to 0153 in Japanese patent laid-open No. 2011 and 253174, and the like.

The viscosity (25 ℃) of the curable composition of the present invention is preferably 1 to 100 mPas, for example, when a film is formed by coating. The lower limit is more preferably 0.1 mPas or more, and still more preferably 0.2 mPas or more. The upper limit is more preferably 10 mPas or less, still more preferably 5 mPas or less, particularly preferably 3 mPas or less.

The curable composition of the present invention preferably contains no free metal bonded or coordinated to a pigment or the like in an amount of 100ppm or less, more preferably 50ppm or less, still more preferably 10ppm or less, and particularly preferably substantially no free metal. In the present specification, ppm is based on mass. According to this embodiment, effects such as stabilization of pigment dispersibility (inhibition of polymerization), improvement of spectroscopic characteristics accompanying improvement of dispersibility, stabilization of curable components, suppression of variation in conductivity accompanying elution of metal atoms and metal ions, and improvement of display characteristics can be expected. Further, the effects described in Japanese patent laid-open Nos. 2012-153796, 2000-345085, 2005-200560, 08-043620, 2004-145078, 2014-119487, 2010-083997, 2017-090930, 2018-025612, 2018-025797, 2017-155228, 2018-036521 and the like can be obtained. Examples of the kind of the free metal include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, and Bi. In the curable composition of the present invention, the content of free halogen not bonded or coordinated to a pigment or the like is preferably 100ppm or less, more preferably 50ppm or less, further preferably 10ppm or less, and particularly preferably substantially none. Examples of the halogen include F, Cl, Br, I and anions thereof. Examples of the method for reducing the free metal or halogen in the curable composition include washing with ion-exchanged water, filtration, ultrafiltration, purification with an ion-exchange resin, and the like.

The curable composition of the present invention also preferably contains substantially no terephthalate.

< storage Container >

The container for the curable composition of the present invention is not particularly limited, and a known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the curable composition, it is also preferable to use a multilayer bottle having a container inner wall composed of 6 kinds of 6-layer resins or a bottle having a 7-layer structure of 6 kinds of resins as the container. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.

In addition, as a container for a composition used for producing the curable composition or the image sensor of the present invention, it is also preferable that the inner wall of the container is made of glass, stainless steel, or the like in order to prevent elution of metal from the inner wall of the container, to improve the storage stability of the composition, and to suppress component modification.

The storage conditions of the curable composition of the present invention are not particularly limited, and a previously known method can be used. Further, the method described in Japanese patent laid-open No. 2016-180058 can be used.

< method for producing curable composition >

The curable composition of the present invention can be prepared by mixing the above components. In the preparation of the curable composition, all the components may be dissolved and/or dispersed in a solvent at the same time to prepare the curable composition, or each component may be appropriately prepared as a solution or a dispersion of 2 or more, if necessary, and these may be mixed at the time of use (at the time of coating) to prepare the curable composition.

Also, in producing the curable composition, the preparation of a dispersed pigment is preferably involved. In the step of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, pressing, impact, shearing, cavitation and the like. Specific examples of these steps include bead milling, sand milling, roll milling, ball milling, paint mixer, microfluid, high-speed impeller, sand mixing, jet mixing, high-pressure wet granulation, ultrasonic dispersion, and the like. In addition, in the pulverization of the pigment by the sand grinding (bead grinding), it is preferable to perform the treatment under the conditions that the pulverization efficiency is improved by using the beads having a small diameter, making the filling ratio of the beads large, or the like. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Further, as the step of dispersing the pigment and the dispersing machine, the steps and dispersing machines described in "the dispersion technology university, johakiko co., ltd. release, 7/15/2005" and "the actual comprehensive data set of dispersion technology and industrial application centered on suspension (solid/liquid dispersion system), release by the department of business development, 10/1978", and paragraph No. 0022 of japanese patent laid-open No. 2015-157893 can be preferably used. In the step of dispersing the pigment, the particles may be refined in the salt milling step. For example, the raw materials, facilities, and treatment conditions used in the salt milling step can be described in japanese patent application laid-open nos. 2015-194521 and 2012-046629.

In the production of the curable composition, the curable composition is preferably filtered through a filter for the purpose of removing foreign matters, reducing defects, and the like. The filter is not particularly limited as long as it is a conventional filter used for filtration applications and the like. Examples of the filter include filters made of materials such as a fluororesin such as Polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (e.g., nylon-6, 6), a polyolefin resin (including a high-density, ultrahigh-molecular-weight polyolefin resin) such as Polyethylene and Polypropylene (PP), and the like. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 0.01 to 7.0. mu.m, more preferably 0.01 to 3.0. mu.m, and still more preferably 0.05 to 0.5. mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. With regard to the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. The filters can be any of the filters provided by NIHON PALL LTD. (DFA4201NIEY et al), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon micro liquid Co., Ltd.), and KITZMICROSFILTER CORPORATION et al.

Further, as the filter, a fibrous filter medium is also preferably used. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include ROKI techon co, SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by ltd.

When filters are used, different filters (e.g., a1 st filter and a 2 nd filter, etc.) may be combined. In this case, the filtration using each filter may be performed only 1 time, or may be performed 2 or more times. Further, filters having different pore sizes may be combined within the above range. And, may be as follows: the filtration using the 1 st filter was performed only for the dispersion, and after mixing other components, filtration was performed using the 2 nd filter.

(film)

The film of the present invention is a film formed from the curable composition of the present invention.

The film of the present invention is preferably a cured film obtained by curing the curable composition of the present invention. The film of the present invention is preferably a film formed from a cured product of the curable composition of the present invention.

The film of the present invention can be used for color filters, near-infrared transmission filters, near-infrared cut filters, black matrices, light-shielding films, refractive index adjusting films, and the like. For example, it can be preferably used as a coloring layer of a color filter.

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

(color Filter)

The color filter of the present invention is a color filter formed from the curable composition of the present invention. The color filter of the present invention preferably has the film of the present invention described above. When the film of the present invention is used for a color filter, a color pigment is preferably used as the pigment.

The film thickness of the color filter of the present invention is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.

The color filter of the present invention may comprise the film of the present invention and a protective layer. The protective layer may be in contact with the film of the present invention, may have another layer therebetween, or may have a space therebetween. The inclusion of the protective layer can impart various functions such as oxidation resistance, low reflection, hydrophilicity/hydrophobicity, and shielding of light having a specific wavelength (ultraviolet light, near infrared light, and the like). The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a resin composition dissolved in a solvent, a chemical vapor deposition method, and a method of bonding a resin to be molded with a bonding material. Examples of the component constituting the protective layer include (meth) acrylic resin, olefin thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, and polyvinylidene chloride resinMelamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine-based resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al₂O₃、Mo、SiO₂、Si₂N₄Etc., may contain 2 or more of these components. For example, in the case of a protective layer for the purpose of oxygen barrier, the protective layer preferably contains a polyol resin or SiO₂、Si₂N₄. In the case of a protective layer for the purpose of reducing reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.

When the protective layer is formed by applying the resin composition, a known method such as a spin coating method, a spray method, a screen printing method, an ink jet method, or the like can be used as a method for applying the resin composition. As the solvent contained in the resin composition, a known solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by a chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, or photochemical vapor deposition method) can be used as the chemical vapor deposition method.

The protective layer may contain additives such as organic particles, inorganic particles, absorbers of specific wavelengths (for example, ultraviolet rays, near infrared rays, and the like), refractive index modifiers, antioxidants, adhesives, and surfactants, as needed. Examples of the organic and inorganic particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, calcium carbonate, barium sulfate, and the like. As the absorber of a specific wavelength, a known absorber can be used. For example, as the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a salicylate compound, a diphenylketone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, and the like can be used. For details of these, reference can be made to the descriptions in paragraphs 0052 to 0072 of japanese patent application laid-open No. 2012 and 208374, paragraphs 0317 to 0334 of japanese patent application laid-open No. 2013 and 068814, and paragraphs 0061 to 0080 of japanese patent application laid-open No. 2016 and 162946, and these contents are incorporated in the present specification. Examples of the infrared absorber include cyclic tetrapyrrole pigments, carboxin pigments, cyanine pigments, quartilene pigments, naphthalocyanine pigments, nickel complex pigments, copper ion pigments, Iminium (Iminium) pigments, subphthalocyanine pigments, xanthene pigments, azo pigments, dipyrromethene pigments, and pyrrolopyrrole pigments. For details of these, reference can be made to the descriptions of japanese patent laid-open nos. 0020 to 0072, 2009 and 263614, and 2017/146092, which are incorporated in the present specification. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of japanese patent application laid-open No. 2017-151176 can be used.

< first mode of the method for manufacturing color Filter >

The method for manufacturing a color filter of the present invention comprises: a step of applying the curable composition to a support to form a composition layer (composition layer forming step); a step (exposure step) of exposing the composition layer to light in a pattern; and a step (developing step) of forming a colored pattern by removing the unexposed portion by development.

Hereinafter, each step will be explained.

[ composition layer Forming Process ]

In the step of forming the composition layer, the curable composition of the present invention is used to form the curable composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, and the like are preferable. Further, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix for isolating each pixel may be formed on the silicon substrate. Further, an undercoat layer for improving adhesion to the upper layer, preventing diffusion of a substance, or planarizing the substrate surface may be provided on the silicon substrate.

In the step of forming the curable composition layer, the curable composition is applied to the support.

As a method for applying the curable composition, a known method can be used. For example, a dropping method (drop casting); slit coating method; spraying; a roll coating method; spin coating (spin coating); tape casting coating method; slit spin coating; a prewet method (for example, the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as ink jet (for example, on-demand, piezoelectric, thermal), jet printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; nanoimprint method, and the like. The method of applying the inkjet is not particularly limited, and examples thereof include a method (especially from 115 to 133 pages) shown in "unlimited possibility in widely used inkjet-japanese patent publication-published under 2.2005", and s.b. reset co., ltd. ", and a method described in japanese patent laid-open nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1699325. Further, as for the method for applying the curable composition, reference can be made to the descriptions in international publication No. 2017/030174 and international publication No. 2017/018419, and these contents are incorporated in the present specification.

The curable composition layer formed on the support may be dried (prebaked). When the film is manufactured through a low-temperature process, pre-baking may not be performed. When the prebaking is performed, the temperature of the prebaking is preferably 150 ℃ or lower, more preferably 120 ℃ or lower, and further preferably 110 ℃ or lower. The lower limit may be, for example, 50 ℃ or higher, or 80 ℃ or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. The pre-baking can be performed using a hot plate, a baking oven, or the like.

[ Exposure procedure ]

Next, the curable composition layer is exposed to light in a pattern (exposure step). For example, the curable composition layer can be exposed to light in a pattern form by exposing the curable composition layer to light through a mask having a predetermined mask pattern using a stepper, a scanner, or the like. Thereby, the exposed portion can be cured.

As the radiation (light) that can be used in the exposure, g-rays, i-rays, and the like can be preferably used. Light having a wavelength of 300nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300nm or less include KrF rays (wavelength: 248nm), ArF rays (wavelength: 193nm), and the like, and KrF rays (wavelength: 248nm) are preferable. Further, a light source having a wavelength of 300nm or more can be used.

In the exposure, the exposure may be performed by continuously irradiating light, or may be performed by irradiating light in a pulse manner (pulse exposure). The pulse exposure is an exposure method of a system in which exposure is performed by repeating irradiation and stop of light in a short time (for example, millisecond order or less) cycle. In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 ns or less, and further preferably 30 ns or less. The lower limit of the pulse width is not particularly limited, and may be 1 femtosecond (fs) or more, or 10 femtoseconds or more. The frequency is preferably 1kHz or more, more preferably 2kHz or more, and further preferably 4kHz or more. The upper limit of the frequency is preferably 50kHz or less, more preferably 20kHz or less, and further preferably 10kHz or less. The maximum instantaneous illuminance is preferably 50,000,000W/m²Above, more preferably 100,000,000W/m²The above, more preferably 200,000,000W/m²The above. Also, the upper limit of the maximum instantaneous illuminance is preferably 1,000,000,000W/m²Hereinafter, 800,000,000W/m is more preferable²Hereinafter, 500,000,000W/m is more preferable²The following. The pulse width is a time during which light is irradiated in a pulse period. The frequency is the number of pulse periods per 1 second. The maximum instantaneous illuminance is an average illuminance over the time period in which light is irradiated in the pulse period. And isThe pulse period is a period in which the irradiation and stop of light in the pulse exposure are 1 cycle.

The dose (exposure) is preferably 0.03 to 2.5J/cm²More preferably 0.05 to 1.0J/cm². The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the atmospheric air, exposure may be performed in a low oxygen environment (for example, 15 vol%, 5 vol%, or substantially no oxygen) in which the oxygen concentration is 19 vol% or less, or exposure may be performed in a high oxygen environment (for example, 22 vol%, 30 vol%, or 50 vol%) in which the oxygen concentration is more than 21 vol%. Further, the exposure illuminance can be appropriately set, and usually can be set from 1,000W/m²～100,000W/m²(e.g., 5,000W/m²，15,000W/m²Or 35,000W/m²) Is selected. The oxygen concentration and the exposure illuminance may be appropriately combined, and for example, the illuminance can be set to 10,000W/m at an oxygen concentration of 10 vol%²The illuminance was set at 20,000W/m at an oxygen concentration of 35 vol%²And the like.

[ development Defect ]

Next, the unexposed portion of the curable composition layer is developed and removed to form a pattern (pixel). The unexposed portions of the curable composition layer can be removed by development using a developer. Accordingly, the curable composition layer in the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. The developer is preferably an organic alkali developer which does not cause a loss of a substrate element, a circuit, or the like. The temperature of the developing solution is preferably 20 to 30 ℃. The developing time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, the process of throwing off the developer every 60 seconds and supplying a new developer may be repeated several times.

The developer is preferably an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water. Examples of the alkali agent include organic basic compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo [5.4.0] -7-undecene, and inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight from the viewpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. The surfactant is preferably the above surfactant or a nonionic surfactant. The developer may be once produced as a concentrated solution from the viewpoint of convenience in transportation and storage, and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to perform washing (rinsing) with pure water after development. It is preferable that the support on which the developed curable composition layer is formed is rotated, and the rinse liquid is supplied to the developed curable composition layer to perform the rinsing. It is also preferable that the rinse liquid is discharged from a nozzle which moves from the center of the support to the peripheral edge of the support. In this case, the nozzle may be moved while gradually decreasing the moving speed of the nozzle when moving from the center portion to the peripheral portion of the support body of the nozzle. By performing flushing in this way, in-plane variations during flushing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the central portion to the peripheral portion of the support body.

After the development, it is preferable to perform additional exposure treatment and heating treatment (post-baking) after drying. The additional exposure treatment and the post-baking are curing treatments after development for complete curing, and the heating temperature is, for example, preferably 100 to 240 ℃, and more preferably 200 to 240 ℃. The post-baking can be performed in an intermittent manner or in a heating mechanism such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater so as to satisfy the above conditions.

When the additional exposure treatment is performed, the light used for the exposure is preferably light having a wavelength of 400nm or less. The additional exposure treatment can be performed by the method described in Korean laid-open patent publication No. 10-2017-0122130.

The pixel width is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less.

The Young's modulus of the pixel is preferably 0.5 to 20GPa, and more preferably 2.5 to 15 GPa.

The pixels preferably have a high degree of flatness. Specifically, the surface roughness Ra of the pixel is preferably 100nm or less, more preferably 40nm or less, and still more preferably 15nm or less. The lower limit is not particularly limited, but is preferably 0.1nm or more, for example. The measurement of the surface roughness can be performed using, for example, AFM (atomic force microscope) Dimension3100 manufactured by Veeco Instruments inc.

The contact angle of water on the pixel can be set to a preferable value as appropriate, and is typically in the range of 50 to 110 °. The contact angle can be measured using a contact angle meter CV-DT · a (manufactured by Kyowa Interface Science co., ltd.).

The volume resistance value of the pixel is desirably high. Specifically, the volume resistance value of the pixel is preferably 10⁹Omega cm or more, more preferably 10¹¹Omega cm or more. The upper limit is not specified, and for example, 10 is preferable¹⁴Omega cm or less. The volume resistance value of the pixel can be measured using, for example, an ultra high resistance meter 5410 (manufactured by Advantest Corporation).

The color filter composed of the desired color layer is formed by repeating the above-described composition layer forming step, exposure step, and development step (and further, additional exposure treatment or heating treatment as necessary) for the desired number of hues.

The above-described manufacturing method is a manufacturing method of pixels of a color filter, and according to the curable composition of the present invention, for example, a black matrix provided between pixels of a color filter can also be manufactured. For example, except for the mode of adding a black pigment as a pigment to the curable composition of the present invention, pattern exposure and development can be performed in the same manner as in the above-described method for manufacturing pixels, and if necessary, post baking can be performed to manufacture a black matrix.

(second mode of the method for manufacturing color Filter)

A second aspect of the method for manufacturing a color filter of the present invention includes: a step (cured layer forming step) of applying the curable composition of the present invention to a support to form a composition layer and curing the composition layer to form a cured layer; a step of forming a photoresist layer on the cured layer (photoresist layer forming step); a step of patterning the photoresist layer by exposure and development to obtain a resist pattern (resist pattern forming step); and a step (etching step) of etching the solidified layer using the resist pattern as an etching mask.

Hereinafter, each step will be explained.

< Process for Forming cured layer >

In the cured layer forming step, the curable composition of the present invention is applied to a support and cured to form a cured layer.

As the support, the support used in the composition layer forming step can be preferably used.

The method of applying the curable composition can be preferably applied in the composition film-forming step.

The method for curing the provided curable composition is not particularly limited, and curing by light or heat is preferable.

In the case of curing by light, the light may be appropriately selected according to the initiator contained in the curable composition, and for example, ultraviolet rays such as g-ray and i-ray may be preferably used. The exposure is preferably 5-1, 500mJ/cm²More preferably 10 to 1,000mJ/cm²More preferably 10 to 500mJ/cm²。

When the heat-based curing is performed, the heating temperature is preferably 120 to 250 ℃, more preferably 160 to 230 ℃. The heating time varies depending on the heating mechanism, and is preferably 3 to 30 minutes, for example, when heating is performed on a hot plate, and is preferably 30 to 90 minutes, for example, when heating is performed in an oven.

< Process for Forming Photoresist layer >

In the photoresist layer forming step, a photoresist layer is formed on the cured layer.

For the formation of the photoresist layer, for example, a known negative or positive photosensitive composition is used, and a positive photosensitive composition is preferred.

The photosensitive composition is applied to the cured layer and dried as necessary to obtain a photoresist layer.

The method for forming the photoresist layer is not particularly limited, and may be performed by a known method.

The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm.

< resist Pattern Forming Process >

In the resist pattern forming step, the photoresist layer is exposed to light in a pattern and developed to form a resist pattern.

The exposure and development are not particularly limited, and can be performed by a known method.

< etching Process >

In the etching step, the cured layer is etched with the resist pattern interposed therebetween.

The etching method is not particularly limited as long as it is performed by a known method, and for example, a method by dry etching is exemplified.

< Process for removing resist Pattern >

In the second aspect of the method for manufacturing a color filter according to the present invention, the etching step may further include a step of removing the resist pattern.

The method of stripping the resist pattern is not particularly limited, and a known method can be used.

(solid-state imaging element)

The solid-state imaging device of the present invention includes the film of the present invention or the color filter of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging element, and examples thereof include the following structures.

The structure is as follows: the substrate has a transfer electrode made of polysilicon or the like and a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD (charge coupled device) image sensor, a CMOS (complementary metal oxide semiconductor) image sensor, or the like), a light shielding film for opening only a light receiving portion of the photodiode is provided on the photodiode and the transfer electrode, an element protection film made of silicon nitride or the like and formed so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode is provided on the light shielding film, and a color filter is provided on the element protection film. Further, the light condensing means (for example, a microlens) may be provided below the color filter (on the side close to the substrate) on the element protective film, or the light condensing means may be provided on the color filter. The color filter may have a structure in which each of the colored pixels is embedded in a space partitioned into, for example, a grid shape by a partition plate. The spacer in this case is preferably low in refractive index for each colored pixel. Examples of imaging devices having such a configuration include those described in japanese patent laid-open nos. 2012 and 227478, 2014 and 179577, and 2018/043654. The imaging device including the solid-state imaging element according to the present invention can be used as a vehicle camera or a monitoring camera in addition to a digital camera or an electronic device (such as a mobile phone) having an imaging function.

(image display device)

The image display device of the present invention includes the film of the present invention or the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. The definition of the image display devices and the details of the respective image display devices are described in, for example, "display devices (published by yoko showa, Kogyo chess Publishing co., ltd., 1990)", "display devices (published by yo Tosho Publishing co., ltd. 1989)", and the like. The liquid crystal display device is described in, for example, "next generation liquid crystal display technology (edited by infiniband man, Kogyo Chosakai Publishing co., ltd., 1994)". The liquid crystal display device applicable to the present invention is not particularly limited, and can be applied to, for example, liquid crystal display devices of various types described in the above-mentioned "next generation liquid crystal display technology".

(Polymer Compound)

The polymer compound of the present invention contains at least one of the structural unit represented by the formula (a1) and the structural unit represented by the formula (B1).

The polymer compound of the present invention is the same as the specific resin in the curable composition of the present invention, and the preferred embodiment is the same.

Examples

The present invention will be described in more detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatment, the treatment steps, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.

< Synthesis of specific resin PA-1 >

Into a three-necked flask, a macromonomer B-1 solution described later was introduced as a monomer 2 at a concentration (solid content) of 50 mass%, and a monomer A-1 and PGMEA (propylene glycol 1-monomethyl ether 2-acetate) were introduced as a monomer 1 to obtain a mixture.

The mixture was stirred while blowing nitrogen gas. Subsequently, the mixture was heated to 75 ℃ while flowing nitrogen gas into the flask. Subsequently, dodecylmercaptan (0.82g) was added to the mixture, followed by 2, 2' -azobis (methyl 2-methylpropionate) (0.43g, hereinafter also referred to as "V-601"), and polymerization was started.

After the mixture was heated at 75 ℃ for 2 hours, V-601(0.43g) was further added to the mixture. After 2 hours, V-601(0.43g) was further added to the mixture.

After a further 2 hours of reaction, the mixture was warmed to 90 ℃ and stirred for 3 hours. The polymerization reaction was terminated by the above-mentioned operation.

After the reaction, dimethyldodecylamine (F-1) was added as an amine compound and 2,2,6,6, -tetramethylpiperidine 1-oxyl (Q-1, TEMPO) was added as a polymerization inhibitor under air, and 4-hydroxybutylacrylate glycidyl ether (monomer C-1) was added dropwise as a reactive compound.

After completion of the dropwise addition, after the reaction was continued for 24 hours under air at 90 ℃, completion of the reaction was confirmed by acid value measurement. To the obtained mixture was added PGMEA to make a 30 mass% solution, thereby obtaining a resin PA-1.

The amounts of the monomer B-1 (the amount of solid components in the solution), the monomer A-1, the monomer C-1, the monomer F-1 and the monomer Q-1 used are shown in Table 1 below.

The weight-average molecular weight of the obtained specific resin PA-1 was 17,200, and the acid value was 70 mgKOH/mg.

The specific resin PA-1 is a resin satisfying the above condition 1 and is a resin having a structural unit represented by the above formula (a 1).

Method for measuring weight average molecular weight-

The weight average molecular weight (Mw) of each macromonomer and resin is calculated by measurement by GPC (Gel Permeation Chromatography) under the following measurement conditions. The weight average molecular weight of the resin is set forth in table 1 or table 2.

The device comprises the following steps: HLC-8220GPC (manufactured by TOSOH CORPORATION)

A detector: differential refractometer (RI detector)

Pre-column (Pre column) TSKGUARDCOLUMN MP (XL)6mm × 40mm (manufactured by TOSOH CORPORATION)

Sample side column: directly bonded with the following 4 strips (all manufactured by TOSOH CORPORATION)

TSK-GEL Multipore-HXL-M 7.8mm×300mm

Reference side pipe column: same as the sample side pipe column

Temperature of the thermostatic bath: 40 deg.C

Mobile phase: tetrahydrofuran (THF)

Sample side mobile phase flow rate: 1.0mL/min

Reference side mobile phase flow rate: 0.3 mL/min

Sample concentration: 0.1% by mass

Sample injection amount: 100 μ L

Data acquisition time: 16-46 minutes after sample injection

Sampling interval: 300ms (millisecond)

Method for measuring acid value

The acid value of each resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the resin obtained was dissolved in a solvent to obtain a solution, a sodium hydroxide aqueous solution was titrated by a potentiometric method, the number of millimoles of acid contained in the solid content of 1g of the resin was calculated, and the value was multiplied by the molecular weight of potassium hydroxide (KOH) of 56.1 to obtain the product. The acid value of the resin is shown in the column of "acid value" in table 1 or table 2. In Table 1 or Table 2, the unit of the acid value is (mgKOH/g).

Method for measuring the valence of (C ═ C) of the olefinically unsaturated bond (valence)

The C ═ C value of each resin was measured by the following method.

The low-molecular component (a) having an ethylenically unsaturated group site (for example, acrylic acid in the case where the structural unit represented by formula D1 of the specific resin has an acryloyloxy group) is taken out from the specific resin by alkali treatment, the content thereof is measured by High Performance Liquid Chromatography (HPLC), and the valence (C ═ C valence) of the ethylenically unsaturated bond is calculated from the following formula based on the measured value.

Specifically, 0.1g of the specific resin was dissolved in a tetrahydrofuran/methanol mixture (50mL/15mL), 10mL of a 4mol/L aqueous sodium hydroxide solution was added, and the mixture was reacted at 40 ℃ for 2 hours. The reaction solution was neutralized with 10.2mL of a 4mol/L methanesulfonic acid aqueous solution, and then a mixture solution in which 5mL of ion exchange water and 2mL of methanol were added was pipetted into a 100mL volumetric flask, and HPLC measurement samples were prepared by fixing the volume with methanol and measured under the following conditions. In addition, the content of the low molecular component (a) was calculated from a calibration curve of the low molecular component (a) prepared separately, and the ethylenic unsaturated bond valence was calculated from the following formula. The C ═ C valency of a specific resin is shown in the column of "C ═ C valency" in table 1 or table 2. In table 1 or table 2, the unit of C ═ C valency is (mmol/g).

Calculation formula of olefinic unsaturated bond valence

Number of ethylenically unsaturated bonds (mmol/g) (content of low molecular component (a) (ppm)/molecular weight of low molecular component (a) (g/mol))/(weighed value of liquid for preparing polymer (g) × (solid content concentration of polymer liquid (%)/100) × 10)

HPLC measurement conditions

The measuring equipment comprises: agilent-1200 (manufactured by Agilent Technologies, Inc.)

Pipe column: synergi 4u Polar-RP 80A manufactured by Phenomenex corporation, 250 mm. times.4.60 mm (inner diameter) + protective column

Controlling the temperature: 40 deg.C

Analysis time: 15 minutes

Flow rate: 1.0mL/min (maximum liquid feed pressure: 182bar (18.2MPa))

Injection amount: 5 μ l

Detection wavelength: 210nm

Eluent: tetrahydrofuran (for HPLC without stabilizer)/buffer solution (ion-exchange aqueous solution containing 0.2 vol% of phosphoric acid and 0.2 vol% of triethylamine) ═ 55/45 (vol%)

In the present specification, the volume% is a value at 25 ℃.

Method for measuring amine value-

About 0.5g of a sample was accurately weighed, dissolved by adding 50mL of acetic acid, and titrated by a 0.1mol/L perchloric acid acetic acid solution using an automatic potentiometric titration apparatus (AT-710M; manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). Also, a blank test was performed in the same manner to perform correction.

Amine number a × 5.611/c

a: consumption of 0.1mol/L perchloric acid (mL)

c: amount of sample (g)

The amine number of the resin is shown in the column of "amine number" in Table 1 or Table 2. In Table 1 or Table 2, the unit of amine number is (mmol/g).

< Synthesis of specific resins PA-2 to PA-25 >

PA-2 to PA-22 were synthesized in the same manner as for PA-1, except that monomer 1, monomer 2, monomer 3, the reactive compound, the amine compound and the polymerization inhibitor used were changed to those shown in Table 1. When the monomer 3 is added, the monomer 3 is further added to a mixture of the monomer 1 and the monomer 2.

In table 1, the unit of the numerical value described in the column of "content" is "g". In table 1, the unused components are represented as "-".

PA-2 to PA-22 are resins satisfying the above condition 1, and are resins having a structural unit represented by the above formula (A1).

In table 1, the column of "structural unit a 1" represents a structural unit represented by any one of the above formulas (a1-1) to (a1-17) and represents a structural unit included in each resin.

< Synthesis of resin PZ-1 >

PZ-1 was synthesized in the same manner as PA-1 except that monomer 1, monomer 2, monomer 3, the reactive compound, the amine compound and the polymerization inhibitor used were changed to those shown in table 1.

The resin PZ-1 is a resin which is not capable of forming a structure in which a quaternary ammonium cationic structure using F-8 as an amine compound is linked to a radical polymerizable group, and which does not satisfy either of the above conditions 1 and 2.

[ Table 1]

The details of each component shown in table 1 are shown below.

[ monomer 1]

A-1: ARONIXM-5300, omega-carboxy-polycaprolactone monoacrylate (TOAGOSEI co., ltd., manufactured)

A-2: light ester HO-MS, 2-methacryloyloxyethylsuccinic acid (KYOEISHA CHEMICAL Co., LTD., Ltd.)

A-3: light ester HOA-HH, 2-Acryloxyethylhexahydrophthalic acid (KYOEISHA CHEMICAL Co., LTD., Ltd.)

A-4: β CEA, β -carboxyethylacrylate (manufactured by DAICEL-ALLNEX LTD.)

A-5: vinyl benzoic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

A-6: CB-12-methacryloyloxyethyl phthalic acid (Shin-Nakamura Chemical Co., Ltd.)

A-7: 12-Methacrylamidododecanoic acid (12-methacrylamido decanoic acid) (synthesized by a known method.)

A-8: 4- (4- (acryloyloxy) butoxy) benzoic acid (4- (4- (acryloyloxy) butoxy) benzoic acid) (synthetic product, synthesized by a known method.)

A-9: methacrylic acid

A-10: vinylsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

A-11: vinylphosphonic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

A-12: 10- (Phosphonoxy) decylmethacrylate (10- (phosphooxy) decylmethacrylate) (manufactured by Fujifilm Wako Pure Chemical Corporation)

[ monomer 2]

B-1: composition based on Synthesis example B1 described below

B-2: composition based on Synthesis example B2 described below

B-3: composition based on Synthesis example B3 described below

B-4: BLEMMER PSE1300 (manufactured by NOF CORPORATION), stearyloxypolyethyleneglycol monomethacrylate

B-5: BLEMMER 75ANEP-600 (manufactured by NOF CORPORATION) nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate

B-6: BLEMMER 50POEP800B (manufactured by NOF CORPORATION) octyloxypolyethylene glycol-polypropylene glycol monomethacrylate

The structural unit represented by the above formula (D5) is introduced into the specific resin by using at least one compound of B-1 to B-6 as the monomer 2.

Synthesis of (E) -B-1

Hereinafter, a method for synthesizing macromonomer B-1 (also referred to simply as "B-1") of monomer 2 containing a structural unit consisting of an oxyalkylene carbonyl group will be described.

To the flask, epsilon-caprolactone (1256.62 parts, corresponding to cyclic compounds) and 2-ethyl-1-hexanol (143.38 parts, corresponding to ring-opening polymerization initiator) were introduced to obtain a mixture. Subsequently, the mixture was stirred while blowing nitrogen gas.

Next, monobutyltin oxide (0.63 part) was added to the mixture, and the obtained mixture was heated to 90 ℃. After 6 hours use¹After H-NMR (Nuclear Magnetic Resonance) confirmed that the signal from 2-ethyl-1-hexanol in the mixture disappeared, the mixture was heated to 110 ℃. After a further 2 hours of polymerization at 110 ℃ under nitrogen, from¹After confirming the disappearance of the signal derived from epsilon-caprolactone by H-NMR, the temperature was reduced to 80 ℃ and 2, 6-di-tert-butyl-4-methylphenol (0.78 part) was added to the mixture containing the above-mentioned compound, and then 2-methacryloyloxyethyl isocyanate (174.15 parts) was added dropwise to the obtained mixture over 30 minutes. After 1 hour from the end of the dropwise addition, the reaction mixture was heated¹After confirming the disappearance of the signal from 2-methacryloyloxyethyl isocyanate (MOI) by H-NMR, Propylene Glycol Monomethyl Ether Acetate (PGMEA) (1575.57 parts) was added to the mixture to obtain a 50 mass% macromonomer B-1 solution. The structure of the macromonomer B-1 is represented by¹H-NMR. The weight-average molecular weight of the obtained macromonomer B-1 is 3,000.

[ chemical formula 42]

Synthesis of (E) -B-2

B-2 was synthesized in the same manner as in the synthesis of B-1, except that 2-ethyl-1-hexanol (143.38g) was changed to stearyl alcohol (297.88 g).

The structure of B-2 (shown in formula (B-2)) is represented by¹H-NMR was confirmed. The weight average molecular weight of the obtained B-2 was 3,400。

[ chemical formula 43]

Synthesis of (E) -B-3

Into the flask, epsilon-caprolactone (243.45 parts, cyclic compound), delta-valerolactone (60.86 parts, cyclic compound) and 2-ethyl-1-hexanol (35.69 parts, ring-opening polymerization initiator.) were introduced to obtain a mixture. Subsequently, the mixture was stirred while blowing nitrogen gas.

Next, monobutyltin oxide (0.156 part) was added to the mixture, and the obtained mixture was heated to 90 ℃. After 6 hours use¹H-NMR (Nuclear Magnetic Resonance) confirmed that the signal from 2-ethyl-1-hexanol in the mixture disappeared, and then the mixture was heated to 110 ℃. After a further polymerization at 110 ℃ for 12 hours under nitrogen, from¹After H-NMR confirmed the disappearance of the signals derived from ε -caprolactone and Δ -valerolactone, the temperature was reduced to 80 ℃ and 2, 6-di-tert-butyl-4-methylphenol (0.19 part) was added to the mixture containing the above compounds, and then 2-methacryloyloxyethyl isocyanate (42.52 parts) was added dropwise to the obtained mixture over 30 minutes. After 1 hour from the end of the dropwise addition, the reaction mixture was heated¹After confirming the disappearance of the signal from 2-methacryloyloxyethyl isocyanate (MOI) by H-NMR, Propylene Glycol Monomethyl Ether Acetate (PGMEA) (382.87 parts) was added to the mixture to obtain a 50 mass% macromonomer B-3 solution. The structure of the macromonomer B-3 is represented by¹H-NMR. The weight average molecular weight of the obtained macromonomer B-3 is 3,000.

[ chemical formula 44]

[ monomer 3]

E-1: benzyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

E-3: 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-4: ARONIXM120(TOAGOSEI co., ltd., manufactured) ethyl 2- (2- ((2-ethylhexyl) oxy) ethoxy) acrylate (2- (2- ((2-ethylhexyl) oxy) ethoxy) ethyl acrylate)

E-5: dicyclopentyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-6: 2-Methoxyacrylic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-7: 2- (methacryloyloxy) ethyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[ reactive Compound ]

C-1: 4HBAGE, 4-hydroxybutylacrylate glycidyl ether (manufactured by Nippon Kasei Chemical Company Limited)

C-2: 3, 4-epoxycyclohexylmethyl acrylate (manufactured by DAICEL CORPORATION)

C-3: glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

C-4: 9- (Oxiran-2-yl) nonyl acrylate (9- (oxaran-2-yl) nonyl acrylate) (the following composition)

C-5: 3- (Oxiran-2-ylmethoxy) -3-oxopropyl acrylate (3- (oxaran-2-ylmethoxy) -3-oxopropyl acrylate) (the following composition)

C-6: 2-methyl-2- (((oxiran-2-ylmethoxy) carbonyl) amino) propane-1,3-diyl diacrylate (2-methyl-2- (((oxaran-2-ylmethoxy) carbonyl) amino) propane-1,3-diyl diacrylate) (the following composition)

C-7: GMA, glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

C-8: allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

C-9: chloromethyl styrene (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

Synthesis of-C-4

While adding 200g of the solution10-undecen-1-ol (Tokyo Chemical Industry Co., Ltd.), 1,378g of DMAc: a flask of dimethylacetamide was ice-cooled, and 153.65g of 3-chloropropionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, followed by stirring for 1.5 hours under ice-cooling. By¹H-NMR confirmed the disappearance of the starting alcohol and the target product, and the stirring was stopped. Ethyl acetate (2,000 ml) was added, and washing with 3.5 mass% aqueous hydrochloric acid (2,000 ml) and 2 times with 5 mass% sodium bicarbonate (2,000 ml) was performed, and the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure, whereby 296g of an intermediate was obtained. 192g of this intermediate and 918g of methylene chloride were charged into a flask, and 200g of metachloroperbenzoic acid was added in portions at intervals of 1 hour 5 times under a water bath: mCPBA, and stir the final liquid.

By¹H-NMR confirmed the disappearance of the peak at the terminal double bond of the starting material, and 1,487g of 5 mass% sodium bicarbonate water was added to the reaction solution and stirred for 2 hours. Then, 500ml of ethyl acetate was added and extracted, 500ml of a 5 mass% aqueous sodium thiosulfate solution was added and stirred for 1 hour, the aqueous layer was discarded, and the organic layer was concentrated under reduced pressure, thereby obtaining 211.5g of an intermediate.

210g of the intermediate, 822g of methylene chloride and 182.3mg of p-methoxyphenol were added thereto and the mixture was dropwise added while keeping a temperature of a mixture of 231g of diazabicycloundecene and 441g of methylene chloride at 10 ℃ or lower under ice cooling.

By¹The product was confirmed by H-NMR, and the mixture was stirred at room temperature for 2 hours while maintaining a mixture of 91.1g of acetic acid and 147g of methylene chloride at 10 ℃ or lower.

Methylene chloride was concentrated under reduced pressure, and 1,050g of hexane was added, and water-washed with 420g of water and 420g of 5 mass% sodium bicarbonate water, to obtain C-4137.9 g as an object.

Synthesis of-C-5

23.3g of beta-carboxyethylacrylate, 87mg of p-methoxyphenol, 117g of chloroform, 16.8g of glycidol, and 1.98g N, N-dimethylaminopyridine were charged into a flask, and 37.26g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride was added in portions under ice-cooling, followed by stirring for 1 hour. Then, the mixture was washed with 150ml of a predetermined (0.1mol/L) aqueous hydrochloric acid solution (0.1 ml), and then with 150ml of water, and the organic layer was concentrated under reduced pressure to obtain C-520 g of the desired product.

Synthesis of-C-6

To the flask were added 5.0g of glycidol (manufactured by Aldrich), 53g of butyl acetate, 0.04g of p-methoxyphenol, 14.5g of Karenz BEI (manufactured by SHOWA DENKO k.k.), 0.04g of Neostan U600 (manufactured by NITTO KASEI co., ltd.), and the temperature was slowly raised to 60 ℃. After a further 4 hours of polymerization at 60 ℃ were carried out¹The disappearance of the signal from Karenz BEI was confirmed by H-NMR, and 50g of water was added and stirred. The organic layer obtained by liquid separation of the aqueous layer and disposal was washed again with 50g of water. To the washed organic layer was added 3g of magnesium sulfate, followed by filtration, and then 2, 6-di-tert-butyl-4-methylphenol (0.4g) was added and concentrated to obtain 12g of C-6.

[ amine Compound ]

F-1: dimethyldodecylamine (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

F-2: dimethylbutylamine (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

F-3: dimethylbenzylamino group (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

F-4: 2,4, 6-tris (dimethylaminomethyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

F-5: 2- (dimethylaminomethyl) phenol

F-6: n, N-dimethylpiperazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

F-7: triethylamine (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

F-8: TBAB (tetrabutylammonium bromide) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[ polymerization inhibitor ]

Q-1: TEMPO free radical (free radial): 2,2,6, 6-tetramethylpiperidine 1-oxyl

Q-2: 4-hydroxy-TEMPO free radical (4-hydroxy-TEMPO free radial): 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 2-oxyl

Q-3: p-methoxyphenol

< Synthesis of specific resin PA-26 >

A30 mass% 1-methoxy-2-propanol solution was prepared from 36.25 parts by mass of a 20 mass% solution of a chain transfer agent CTA-1 (structure described below) obtained by the synthesis method described in Japanese patent application laid-open No. 2007-277514, and a mixed solution of 18 parts by mass of methacrylic acid and 20 parts by mass of methyl methacrylate, and was heated to 75 ℃ under a nitrogen stream.

To this was added azobisisobutyronitrile (AIBN, manufactured by Wako Pure Chemical Industries, Ltd., initiator) 0.5 part by mass and heated for 3 hours, then AIBN 0.5 part was added again, and the mixture was reacted under a nitrogen stream at 90 ℃ for 3 hours. Then, after cooling to room temperature (25 ℃ C., the same applies hereinafter) and replacement with air, 20 parts by mass of 4-hydroxybutylacrylate glycidyl ether, 4.02 parts by mass of dimethyldodecylamine, and 0.023 parts by mass of TEMPO (2,2,6, 6-tetramethylpiperidine 1-oxyl) were added thereto, and the mixture was heated and stirred at 90 ℃ for 36 hours.

Then, it was cooled to room temperature and diluted with acetone. After reprecipitating with a large amount of methanol, vacuum drying was performed to obtain a polymer compound PA-26: 65.1 parts by mass of a solid (specific resin PA-26) having a polystyrene-equivalent weight-average molecular weight of 18,600, an acid value of 88.5mgKOH/g, a C value of 1.44mmol/g, and an amine value of 0.27 mmol/g.

PA-26 is a resin satisfying the above condition 1 and is a resin having a structural unit represented by the above formula (a 1).

[ chemical formula 45]

< Synthesis of specific resin PA-27 >

A30 mass% 1-methoxy-2-propanol solution was prepared from 24.17 parts by mass of a 30 mass% solution of a chain transfer agent CTA-15 (structure described below) obtained by the synthesis method described in Japanese patent application laid-open No. 2007-277514, and a mixed solution of 10 parts by mass of methacrylic acid and 29.59 parts by mass of methyl methacrylate, and the mixture was heated to 75 ℃ under a nitrogen stream.

V-6010.5 parts by mass was added thereto, and after heating for 3 hours, V-6010.5 parts by mass was added again, and allowed to react for 3 hours under a nitrogen stream at 90 ℃. Then, after cooling to room temperature and replacement with air, 14.21 parts by mass of glycidyl methacrylate, 4 parts by mass of dimethyldodecylamine, and 0.023 parts by mass of TEMPO were heated and stirred at 90 ℃ for 36 hours.

Then, it was cooled to room temperature and diluted with acetone. After reprecipitating with a large amount of methanol, vacuum drying was performed to obtain a polymer compound PA-27: polystyrene equivalent weight average molecular weight of 13,800, acid value of 21mgKOH/g, C ═ C value of 1.54mmol/g, amine value of 0.29mmol/g solid 51.5 parts by mass.

PA-27 is a resin satisfying the above condition 1 and is a resin having a structural unit represented by the above formula (a 1).

[ chemical formula 46]

< Synthesis of specific resin PB-2 >

Into a three-necked flask, a macromonomer B-1 solution having a concentration (solid content) of 50 mass% was introduced as a monomer 2, ω -carboxy-polycaprolactone monoacrylate was introduced as a monomer 1,2- (dimethylamino) ethyl acrylate and 171g of PGMEA were introduced as a monomer 4 to obtain a mixture.

The mixture was stirred while blowing nitrogen gas. Subsequently, the mixture was heated to 75 ℃ while flowing nitrogen gas into the flask. Next, 1.34g of dodecyl mercaptan was added to the mixture, followed by 0.7g V-601, and polymerization was started. After heating the mixture at 75 ℃ for 2 hours, 0.7g V-601 was further added to the mixture. After 2 hours, 0.7g V-601 was further added to the mixture.

After a further 2 hours of reaction, the mixture was warmed to 90 ℃ and stirred for 3 hours. The polymerization reaction was terminated by the above-mentioned operation.

After the reaction was completed, TEMPO (Q-1) was added under air, and 4-hydroxybutylacrylate glycidyl ether (C-1) was added dropwise.

After the end of the dropwise addition, the reaction was continued under air and at 90 ℃ for 24 hours. To the obtained mixture was added PGMEA to make a 30 mass% solution, thereby obtaining a resin PB-2.

The amounts of monomer 2 (the amount of solid components in the solution) and monomers 1,4, C-1 and Q-1 used are shown in Table 2 below.

The weight-average molecular weight of the obtained resin PB-2 was 17,800, the acid value was 75mgKOH/mg19,200, and the acid value was 60 mgKOH/mg.

The specific resin PB-2 is a resin satisfying the above condition 2 and has a structural unit represented by the above formula (B1).

< Synthesis of specific resins PB-1, PB-3 to PB-18 >

PB-1 and PB-3 to PB-18 were synthesized in the same manner as PA-1 except that monomer 1, monomer 2, monomer 3, monomer 4, the reactive compound and the polymerization inhibitor used were changed to those shown in Table 1. When the monomer 3 is added, the monomer 3 is further added with a mixture of the monomer 1, the monomer 2 and the monomer 4.

In table 2, the unit of the numerical value described in the column of "content" is "mass%". In Table 2, the unused components are represented by "-".

In Table 2, the column entitled "structural Unit B1" refers to a structural Unit represented by any one of the above formulae (B1-1) to (B1-12) and represents a structural Unit contained in each resin.

PB-1 and PB-3 to PB-18 are resins satisfying the above condition 2 and having a structural unit represented by the above formula (B1).

< Synthesis of resin PZ-2 >

PZ-2 was synthesized in the same manner as PB-2 except that monomer 1, monomer 2, monomer 3, monomer 4, the reactive compound and the polymerization inhibitor used were changed to those shown in Table 2.

Since the resin PZ-2 uses E-1 and E-7 as the monomer 4, it is a resin which does not have a structure in which a quaternary ammonium cation structure is linked to a radical polymerizable group and which does not satisfy any of the above conditions 1 and 2.

[ Table 2]

The following shows components other than those described above among the components described in table 2.

[ monomer 4]

D-1: 2- (dimethylamino) ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-2: 2- (diethylamino) ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-3: ethyl 2- (((2- (dimethylamino) ethoxy) carbonyl) amino) acrylate (2- (((2- (dimethylamino) ethoxy) carbonyl) amino) ethyl acrylate) (synthesized with reference to Bulletin of the Chemical Society of Japan, 2011, vol.84, #11, p.1215-1226.)

D-4: n, N-dimethyl-1- (4-vinylphenyl) methylamine (N, N-dimethyl-1- (4-vinylphenyl) methanamine) (synthesized in reference to Angewandte Chemie-International Edition, 2007, vol.46, #46, p.8869-8871.)

< Synthesis of specific resin PB-19 >

A mixed solution of 36.25 parts by mass of a 20 mass% solution of a chain transfer agent CTA-1 (the above-mentioned structure) obtained by the synthesis method described in Japanese patent application laid-open No. 2007-277514, 12 parts by mass of methacrylic acid, 5.46 parts by mass of 2- (dimethylamino) ethyl methacrylate, and 14 parts by mass of methyl methacrylate was prepared as a 30 mass% 1-methoxy-2-propanol solution, and the solution was heated at 75 ℃ under a nitrogen stream.

After 0.5 parts by mass of AIBN was added thereto and heated for 3 hours, 0.5 parts by mass of AIBN was added again and allowed to react for 3 hours under a nitrogen gas flow at 90 ℃. Then, after cooling to room temperature (25 ℃ C., the same applies hereinafter) and replacement with air, 15 parts by mass of 4-hydroxybutylacrylate glycidyl ether and 0.023 parts by mass of TEMPO were added thereto, and the mixture was heated and stirred at 90 ℃ for 36 hours.

Then, it was cooled to room temperature and diluted with acetone. After reprecipitating with a large amount of methanol, vacuum drying was carried out to obtain a polymer compound PB-19: polystyrene equivalent weight average molecular weight 14,600, acid value 67.4mgKOH/g, C ═ C value 1.39mmol/g, amine value 0.71mmol/g solid (special resin PB-19)62.9 parts by mass.

PB-19 is a resin satisfying the above condition 2 and has a structural unit represented by the above formula (B1).

< Synthesis of specific resin PB-20 >

A30 mass% solution of a chain transfer agent CTA-24 (structure shown below) obtained by the synthesis method described in Japanese patent application laid-open No. 2007-277514, which was a mixed solution of 24.17 parts by mass, 14.32 parts by mass of 2- (dimethylamino) ethyl methacrylate, and 6.51 parts by mass of 2-hydroxyethyl methacrylate, was prepared as a 30 mass% 1-methoxy-2-propanol solution, and the solution was heated at 75 ℃ under a nitrogen stream.

After adding V-6010.5 parts by mass and heating for 3 hours, V-6010.5 parts by mass was added again and allowed to react for 3 hours under a nitrogen stream at 90 ℃. Then, after cooling to room temperature (25 ℃ C., the same applies hereinafter) and replacement with air, 20.02 parts by mass of 4-hydroxybutylacrylate glycidyl ether and 0.023 parts by mass of TEMPO were added thereto, and the mixture was heated and stirred at 90 ℃ for 36 hours. Then, the mixture was cooled to room temperature and replaced with air, 11.96 parts by mass of Karenz BEI manufactured by SHOWA DENKO k.k., 11.96 parts by mass of NITTO KASEI co., Neostan U6000.61 parts by mass manufactured by ltd., and 0.023 part by mass of TEMPO were added, and the mixture was heated and stirred at 90 ℃ for 36 hours.

Then, it was cooled to room temperature and diluted with acetone. After reprecipitating with a large amount of methanol, vacuum drying was carried out to obtain a polymer compound PB-20: 57.4 parts by mass of a solid (specific resin PB-20) having a polystyrene-equivalent weight-average molecular weight of 19500, an acid value of 12.5mgKOH/g, a C value of 3.33mmol/g, and an amine value of 1.67 mmol/g.

PB-20 is a resin satisfying Condition 2 above and has a structural unit represented by formula (B1) above.

< preparation of pigment Dispersion >

After mixing the pigments described in tables 3 to 5 below, a dispersion aid (pigment derivative), a resin, a polymerization inhibitor, and a solvent, 230 parts by mass of zirconia beads having a diameter of 0.3mm were added, and a dispersion treatment was performed for 5 hours using a paint shaker, and the beads were filtered and separated to produce a dispersion. The numerical values of the contents shown in tables 3 to 5 below are expressed in parts by mass.

For example, PA-12/P1 in the column of "type of resin" in the pigment dispersion liquid R-12 is 1/1, and PA-12 and P1 are used as resins in a proportion of 1/1 (mass ratio), and the total amount is 4.2 parts by mass.

In tables 3 to 5, "-" indicates that no corresponding compound is contained.

[ Table 3]

[ Table 4]

[ Table 5]

Details of the raw materials shown in the above tables by abbreviations are as follows.

[ pigment ]

·PR254：C.I.Pigment Red 254

·PR264：C.I.Pigment Red 264

·PR272：C.I.Pigment Red 272

·PY139：C.I.Pigment Yellow 139

·PY150：C.I.Pigment Yellow 150

·PB15:6：C.I.Pigment Blue 15:6

·PV23：C.I.Pigment Violet 23

·PG58：C.I.Pigment Green 58

·PG36：C.I.Pigment Green 36

·PY185：C.I.Pigment Yellow 185

TiON: titanium oxynitride

TiN: titanium nitride

K1: a compound of the structure.

K2: a compound of the structure.

[ chemical formula 47]

[ dispersing aid (pigment derivative) ]

B1-B3: a compound of the structure

K3-K4: a compound of the structure

[ chemical formula 48]

[ resin (specific resin) ])

PA-1 to PA-27: the composition of the above synthesis example

PB-1 to PB-20: the composition of the above synthesis example

PZ-1 to PZ-2: the composition of the above synthesis example

[ polymerization inhibitor ]

Q1: TEMPO free radial: 2,2,6, 6-tetramethylpiperidine 1-oxyl

Q2: 4-hydroxy-TEMPO free radial: 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 2-oxyl

Q3: p-methoxyphenol

[ solvent ]

J1: PGMEA (propylene glycol monomethyl ether acetate)

J2: cyclohexanone

J3: cyclopentanone

J4: PGME (propylene glycol monomethyl ether)

(examples 1 to 76, comparative examples 1 to 2)

In each of examples and comparative examples, the raw materials described in tables 6 to 8 below were mixed to prepare a curable composition.

In tables 6 to 8, the expressions "R-1", "Y-1" and the like in the column of "pigment dispersion liquid 1" or "pigment dispersion liquid 2" indicate that the aforementioned "pigment dispersion liquid R-1", "pigment dispersion liquid Y-1" and the like are used.

For example, as described in "R-13/R-19 ═ 9/1" in the column of "pigment dispersion liquid 1", etc., 44.8 parts by mass of "R-13" and "R-19" in total are contained as the pigment dispersion liquid, and the content mass ratio of "R-13" and "R-19" is 9:1, etc.

In tables 6 to 8, "-" indicates that no corresponding compound is contained.

[ Table 6]

[ Table 7]

[ Table 8]

In tables 6 to 8, the details of the compounds shown by abbreviations other than the above are as follows.

[ other resins ]

P1: a resin having the following structure. The values indicated on the main chain are molar ratios. Mw 11,000.

P2: a resin having the following structure. The values indicated on the main chain are molar ratios. Mw is 30,000.

[ chemical formula 49]

[ photopolymerization initiator ]

I1: IRGACURE OXE02 (manufactured by BASF corporation)

I2: IRGACURE OXE03 (manufactured by BASF corporation)

I3: IRGACURE OXE04 (manufactured by BASF corporation)

I4: a compound having a structure represented by the following formula (I4)

I5: ADEKA ARKLSNCI-831 (manufactured by ADEKA CORPORATION)

I6: IRGACURE 369 (manufactured by BASF corporation)

[ chemical formula 50]

[ polymerizable Compound ]

M1: a compound represented by the following formula (M), a + b + c ═ 3

M2: a compound represented by the following formula (M), a + b + c ═ 4

M3: a compound represented by the following formula (M), a compound in which a + b + c is 5 and a compound in which a + b + c is 6 are mixed in a mass ratio of 1:3

M4: dipentaerythritol hexaacrylate (DPHA)

M5: a compound represented by the following formula (M5)

M6: a compound represented by the following formula (M6)

[ chemical formula 51]

[ surfactant ]

H1: megafacef F-781F (manufactured by DIC CORPORATION)

< evaluation of adhesion sensitivity (adhesion) >

The curable compositions obtained in each example or comparative example were applied to 8-inch (1 inch: 2.54cm) silicon wafers previously sprayed with hexamethyldisilazane by a spin coater so that the film thickness after drying became 0.8 μm, and prebaked at 100 ℃ for 120 seconds.

The coating film is passed through a mask having a 1.1 μm square island pattern at a wavelength of 365nm by using an i-ray stepper exposure apparatus FPA-i5+ (manufactured by Canon Inc.) for a coating substrate, and the thickness of the coating film is 50-1,700 mJ/cm²I-rays are irradiated with the exposure amount of (1). After exposure, development was carried out using an alkali developing solution CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 25 ℃ for 40 seconds. Then, after washing with running water for 30 seconds, spray drying was performed to obtain a colored pattern.

The colored pattern corresponds to a film formed using the curable composition.

The obtained colored pattern was observed from above using a scanning electron microscope (Hitachi, S-9220 manufactured by ltd.) and subjected to pattern size measurement. The adhesion was evaluated using an optical microscope. The pattern sizes when all the patterns were bonded were evaluated in 5 ranks according to the following evaluation standards. The evaluation results are shown in the columns of "adhesion sensitivity" in tables 6 to 8.

The closer to 5, the more excellent the adhesion to the support. The evaluation result is preferably 3,4 or 5, more preferably 4 or 5, most preferably 5.

[ evaluation criteria ]

5: the pattern size is more than 0.9 μm and less than 1.0 μm.

4: the pattern size is 1.0 μm or more and less than 1.05 μm.

3: the pattern size is 1.05 μm or more and less than 1.1 μm.

2: the pattern size is 1.1 μm or more and less than 1.2 μm.

1: if the non-pattern size is 1.2 μm or more, adhesion is not obtained.

< evaluation of Pattern shape >

The curable compositions obtained in the respective examples and comparative examples were used to form patterned cured products, and the edge shapes (pattern shapes) of the cured products were evaluated by the following methods.

The patterned cured product corresponds to a film formed using the curable composition.

[ procedure for Forming curable composition layer ]

A curable composition layer (composition film) was formed on a silicon wafer so that the thickness after drying became 0.9. mu.m. The curable composition layer was formed using spin coating. The spin speed was adjusted to the above film thickness. The silicon wafer was placed down on a hot plate and the coated curable composition layer was dried. The surface temperature of the hot plate was set to 100 ℃ and the drying time was set to 120 seconds.

[ Exposure procedure ]

The obtained curable composition layer was exposed to light under the following conditions.

The exposure was performed using an i-ray stepper (product name "FPA-3000 iS +", manufactured by Canon inc.). The curable composition film was coated with 400mJ/cm of a mask having a linear shape of 20 μm (width 20 μm, length 4mm)²The exposure amount (irradiation time 0.5 second) of (1) was irradiated with (exposed to) i-rays.

[ development Defect ]

The cured composition layer after curing was developed under the following conditions to obtain a patterned cured film.

The cured curable composition layer was repeatedly subjected to spin-immersion development using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ℃ for 5 times for 60 seconds to obtain a patterned cured product. Then, the patterned cured product was washed with a rotating shower and further washed with pure water.

[ post-baking step ]

The pattern-like cured product obtained above was heated at 220 ℃ for 300 seconds using a cleaning oven CLH-21CDH (manufactured by Koyo Thermo Systems Co., Ltd.).

The heated pattern-like cured product was placed on a hot plate having a surface temperature of 220 ℃ and heated for 300 seconds.

[ evaluation ]

The patterned cured product was photographed by a scanning electron microscope, and the edge shape of the 1.5 μm pattern cross section was evaluated according to the following criteria.

As shown in fig. 1, the length T of the notch at the bottom of the pattern edge 2 of the pattern-like cured product 1 formed on the wafer 4 was measured. In addition, in FIG. 1, L₁Corresponding to the exposure region, L₂Corresponding to the unexposed area. The evaluation was carried out according to the following criteria. The evaluation results are shown in the columns of "pattern shapes" in tables 6 to 8.

The smaller the undercut width, the more excellent the pattern shape. Among the evaluation results, A or AA is preferable, and AA is more preferable.

[ evaluation criteria ]

"AA": the undercut width (the length T) is greater than 0 μm and not greater than 0.05. mu.m.

"A": the undercut width is greater than 0.05 μm and less than 0.15 μm.

"B": the undercut width is greater than 0.15 μm and less than 0.25 μm.

"C": the undercut width is greater than 0.25 μm.

< evaluation of storage stability >

[ 1. Exposure sensitivity (initial) of curable composition ]

In each of examples and comparative examples, each curable composition was coated on a glass substrate by spin coating immediately after the preparation, and dried to form a curable composition layer having a film thickness of 1.0 μm. The spin coating conditions were first measured at a rotation speed: 300rpm (rotation per minute) for 5 seconds followed by 800rpm for 20 seconds. The drying was carried out at 100 ℃ for 80 seconds.

The coating film obtained above was exposed using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) through a pattern mask having lines and spaces of 1 μm and at a rate of 10 to 1,600mJ/cm²Exposure dose irradiation wavelength of 365nm and exposed. Subsequently, the cured composition film after exposure was developed with a 60% CD-2000 (manufactured by FUJIFILM Electronic materials co., ltd.) developer at 25 ℃ for 60 seconds to obtain a pattern-like cured film. Then, the patterned cured film was rinsed with running water for 20 seconds, and then air-dried.

The patterned cured film corresponds to a film formed using a curable composition.

In the above exposure, the exposure sensitivity is set to the minimum exposure amount at which the pattern line width of the region irradiated with light after development becomes 1.0 μm or more, and the exposure sensitivity is set to the initial exposure sensitivity.

[ 2] Exposure sensitivity of curable composition (after lapse of time: after lapse of 30 days at 45 ℃) ]

The curable composition just prepared was sealed in a closed container, and kept in a thermostat (EYELA/LTI-700) in which the temperature in the container was set to 45 ℃ and taken out after 30 days. Using the taken-out curable composition, the same test as that performed using the curable composition just prepared was performed to determine the exposure sensitivity. This was set as the exposure sensitivity after the lapse of time.

[ evaluation ]

The rate of change (%) of the exposure sensitivity obtained by the following equation was calculated from the initial exposure sensitivity and the exposure sensitivity after the lapse of time. The smaller the value of the fluctuation ratio (%) is, the more excellent the storage stability of the curable composition is.

(formula) rate of change [ (exposure sensitivity after elapse of time-initial exposure sensitivity)/initial exposure sensitivity ] × 100

The evaluation results are shown in the columns of "storage stability" in tables 6 to 8. The evaluation result is preferably 3,4 or 5, more preferably 4 or 5, most preferably 5.

[ evaluation criteria ]

"5": the variation rate is 0 to 3 percent.

"4": the fluctuation ratio is more than 3% and less than 6%.

"3": the fluctuation ratio is more than 6% and less than 10%.

"2": the fluctuation ratio is more than 10% and less than 15%.

"1": the rate of change is greater than 15%.

< evaluation of development residue (residue of unexposed portion) >

In the above test [ 1. exposure sensitivity (initial value) of the curable composition, a cured film obtained by exposure with a minimum exposure dose at which the pattern line width after the development becomes 1.0 μm or more was heated in an oven at 220 ℃ for 1 hour together with a glass substrate. After the film was cured by heating, the number of residues present in the unexposed area (unexposed area) was observed by SEM (Scanning Electron Microscope, magnification: 20,000 times) in the exposure step on the glass substrate, and the residue in the unexposed area was evaluated. The evaluation was performed according to the following criteria, and the results are shown in the columns of "development residue" in tables 6 to 8.

The smaller the number of residues, the more suppressed the development residue is. The evaluation result is preferably 3,4 or 5, more preferably 4 or 5, most preferably 5.

[ evaluation criteria ]

"5": no pattern was formed, and no residue was observed in the unexposed portion.

"4": no pattern was formed, and 1 to 3 residues were observed at 1.0 μm square of the unexposed portion.

"3": no pattern was formed, and 4 to 10 residues were observed at 1.0 μm square of the unexposed portion.

"2": no pattern was formed, and 11 or more residues were observed at 1.0 μm square of the unexposed portion.

"1": development was poor and no pattern was formed.

< evaluation of delayed Defect (Defect) >

The curable compositions of examples and comparative examples were applied to a glass substrate by a spin coating method so that the film thicknesses after drying became 0.9 μm, respectively, and then the glass substrate applied with the curable composition was heated at 100 ℃ for 2 minutes on a hot plate to obtain a coating film. After 24 hours, a patterned cured product was obtained through exposure, development, and post-baking steps under the same conditions as in the "evaluation of pattern shape".

The pattern-like cured product was observed with an optical microscope MT-3600LW (manufactured by FLOVEL), and the retardation defect (generation of foreign matter at the time) was evaluated. The less foreign matter, the better the storage stability, and the more the retardation defect is suppressed. The evaluation result is preferably 3,4 or 5, more preferably 4 or 5, most preferably 5.

[ evaluation criteria ]

"5": foreign matter was not found in the patterned cured product.

"4": less than 5 foreign matters are found on the patterned cured product.

"3": 5 to 10 foreign matters are found on the patterned cured product.

"2": 11 to 50 foreign matters are found on the patterned cured product.

"1": 51 to 100 foreign matters are found on the patterned cured product.

(examples 77 to 78, comparative examples 3 to 4)

In each of examples and comparative examples, the raw materials described in table 9 below were mixed to prepare a curable composition.

In Table 9, the expressions "R-1", "Y-1" and the like in the column of "pigment Dispersion 1" or "pigment Dispersion 2" indicate that the aforementioned "pigment Dispersion R-1", "pigment Dispersion Y-1" and the like were used.

In table 9, the expression "-" indicates that no corresponding compound is contained.

[ Table 9]

< evaluation of adhesion sensitivity (adhesion) of glass substrate >

[ production of glass substrate with undercoat ]

The glass substrate (Corning1737) was ultrasonically cleaned with a 0.5 mass% aqueous sodium hydroxide solution, and then washed with water and dehydrated and baked (200 ℃/20 minutes). Subsequently, the cleaned glass substrate was coated with a coating film so that the film thickness after drying became 0.1 μm by using a spin coater CT-4000 (manufactured by FUJIFILM Electronic Materials co., Ltd), and dried by heating at 220 ℃ for 1 hour using a hot plate, to prepare an undercoat-coated glass substrate.

[ evaluation of adhesion sensitivity ]

Except for using the glass substrate with a primer layer, evaluation was performed by the same method as the evaluation method described in the "evaluation of adhesion sensitivity (adhesion property)". The evaluation results are shown in the column of "glass substrate adhesion sensitivity" in table 9.

As described above, as shown in examples and comparative examples, films having excellent adhesion to the support were formed from the curable compositions of examples.

The curable composition in comparative example 1 does not contain a resin satisfying at least one of condition 1 or condition 2, and does not form a film having excellent adhesion to the support.

The curable composition in comparative example 2 does not contain a resin satisfying at least one of condition 1 or condition 2, and a film having excellent adhesion to a support is not formed.

(example 101 to example 164)

The film thickness of any of the Green composition, the Blue composition, and the Red composition was applied to 1.0 μm by spin coating so as not to overlap the color of the curable composition. For example, the color of the curable compositions of examples 1 to 50 is Red, the color of the curable compositions of examples 51 to 56 is Blue, and the color of the curable compositions of examples 57 to 64 is Green.

A total 3-color composition selected from 2 compositions of the Red composition, the Green composition and the Blue composition described below was prepared so that any one of the Red composition, the Green composition 57 to 64 and the Blue composition 51 to 56 in examples 1 to 50 and the composition described above did not overlap in color (the Red composition, the Green composition and the Blue composition, and the composition of any 1 color were the compositions in examples 1 to 64).

Next, the plate was heated at 100 ℃ for 2 minutes using a hot plate. Then, makeAn exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used with an i-ray stepper, which was set at 1,000mJ/cm²The exposure was performed through a mask having a dot pattern of 2 μm square. Then, spin-immersion development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, the film was washed with a rotary shower and further washed with pure water. Next, the Red composition, the Green composition, and the Blue composition were patterned by heating at 200 ℃ for 5 minutes using a hot plate, and Red, Green, and Blue colored patterns (Bayer patterns) were formed.

In addition, the Bayer pattern repeats a pattern of a 2 × 2 array of color filters having 1 Red (Red), 2 Green (Green), and 1 Blue (Blue) element, as disclosed in U.S. patent No. 3,971,065.

The obtained solid-state imaging device was subjected to image selection, and the image performance was evaluated. When any of the compositions obtained in examples 1 to 64 was used, an image could be clearly confirmed even in a low-light environment.

The Red composition, Green composition, Blue composition and composition for forming an infrared transmitting filter used in examples 101 to 164 were as follows.

-Red composition-

After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Pall Corporation) having a pore size of 0.45 μm to prepare a Red composition.

Red pigment dispersion liquid: 51.7 parts by mass

Resin 4(40 mass% PGMEA solution): 0.6 part by mass

Polymerizable compound 4: 0.6 part by mass

Photopolymerization initiator 1: 0.3 part by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 42.6 parts by mass

Green compositions

After mixing and stirring the following components, filtration was performed using a nylon filter (manufactured by Pall Corporation) having a pore size of 0.45 μm to prepare a Green composition.

Green pigment dispersion liquid: 73.7 parts by mass

Resin 4(40 mass% PGMEA solution): 0.3 part by mass

Polymerizable compound 1: 1.2 parts by mass

Photopolymerization initiator 1: 0.6 part by mass

Surfactant 1: 4.2 parts by mass

Ultraviolet absorber (UV-503, DAITO CHEMICAL co., ltd.): 0.5 part by mass

PGMEA: 19.5 parts by mass

Blue composition

The following components were mixed and stirred, and then filtered using a nylon filter (manufactured by Pall Corporation) having a pore size of 0.45 μm to prepare a Blue composition.

Blue pigment dispersion liquid: 44.9 parts by mass

Resin 4(40 mass% PGMEA solution): 2.1 parts by mass

Polymerizable compound 1: 1.5 parts by mass

Polymerizable compound 4: 0.7 part by mass

Photopolymerization initiator 1: 0.8 part by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 45.8 parts by mass

Composition for forming infrared transmission filter

The components of the following composition were mixed and stirred, and then filtered using a nylon filter (manufactured by Pall Corporation) having a pore size of 0.45 μm to prepare an infrared ray transmitting filter composition.

< composition 100 >

Pigment dispersion liquid 1-1: 46.5 parts by mass

Pigment dispersion liquid 1-2: 37.1 parts by mass

Polymerizable compound 5: 1.8 parts by mass

Resin 4: 1.1 parts by mass

Photopolymerization initiator 2: 0.9 parts by mass

Surfactant 1: 4.2 parts by mass

Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass

Silane coupling agent: 0.6 part by mass

PGMEA: 7.8 parts by mass

< composition 101 >

Pigment dispersion liquid 2-1: 1,000 parts by mass

Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass

Resin: 17 parts by mass

Photopolymerization initiator (1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyloxime)): 10 parts by mass

PGMEA: 179 parts by mass

Alkali-soluble polymer FA-1: 17 parts by mass (solid content concentration 35 parts by mass)

< Synthesis example of alkali-soluble Polymer FA-1 >

In a reaction vessel, 14 parts of benzyl methacrylate, 12 parts of N-phenylmaleimide, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene and 20 parts of methacrylic acid were dissolved in 200 parts of propylene glycol monomethyl ether acetate, and 3 parts of 2, 2' -azoisobutyronitrile and 5 parts of α -methylstyrene dimer were charged. After the inside of the reaction vessel was purged with nitrogen, the reaction vessel was heated at 80 ℃ for 5 hours while stirring and blowing nitrogen, to obtain a solution containing the alkali-soluble polymer FA-1 (solid content concentration 35 mass%). The polymer had a polystyrene-reduced weight-average molecular weight of 9,700, a number-average molecular weight of 5,700, and Mw/Mn of 1.70.

< pigment Dispersion 2-1 >

60 parts of c.i. pigment black 32, 20 parts of c.i. pigment blue 15:6, 20 parts of c.i. pigment yellow 139, 80 parts of SOLSPERSE76500 (solid content concentration 50 mass%) manufactured by Japan Lubrizol Corporation, 120 parts of a solution containing the alkali-soluble polymer F-1 (solid content concentration 35 mass%), 700 parts of propylene glycol monomethyl ether acetate were mixed and dispersed for 8 hours using a paint stirrer, and a colorant dispersion liquid 2-1 was obtained.

The raw materials used for the Red composition, Green composition, Blue composition and composition for forming an infrared transmission filter are as follows.

Red pigment dispersion

A mixed liquid composed of 9.6 parts by mass of c.i.pigment Red 254, 4.3 parts by mass of c.i.pigment Yellow 139, 6.8 parts by mass of a dispersant (manufactured by Disperbyk-161, BYKChemie GmbH), and 79.3 parts by mass of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3mm in diameter) for 3 hours to prepare a pigment dispersion liquid. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reducing mechanism was further used at 2,000kg/cm³Was subjected to dispersion treatment at a flow rate of 500g/min under the pressure of (1). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

Green pigment Dispersion

A mixed solution composed of 6.4 parts by mass of c.i.pigment Green 36, 5.3 parts by mass of c.i.pigment Yellow 150, 5.2 parts by mass of a dispersant (manufactured by Disperbyk-161, BYKChemie GmbH), and 83.1 parts by mass of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3mm in diameter) for 3 hours to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reducing mechanism was further used at 2,000kg/cm³Was subjected to dispersion treatment at a flow rate of 500g/min under the pressure of (1). This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

Blue pigment dispersion

A mixed liquid composed of 9.7 parts by mass of c.i.pigment Blue 15:6, 2.4 parts by mass of c.i.pigment Violet 23, 5.5 parts of a dispersant (manufactured by Disperbyk-161, BYKChemie GmbH) and 82.4 parts of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3mm in diameter) for 3 hours to prepare a pigment dispersion liquid. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reducing mechanism was further used at 2,000kg/cm³Was subjected to dispersion treatment at a flow rate of 500g/min under the pressure of (1). This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

Pigment Dispersion 1-1

The mixed liquid having the following composition was mixed and dispersed for 3 hours using zirconia beads having a diameter of 0.3mm and a bead mill (high pressure disperser NANO-3000-10(Nippon BEE co., ltd.) with a pressure reducing mechanism) to prepare pigment dispersion liquid 1-1.

A mixed pigment composed of a Red pigment (c.i. pigment Red 254) and a Yellow pigment (c.i. pigment Yellow 139): 11.8 parts by mass

Resin (Disperbyk-111, manufactured by BYKChemie GmbH): 9.1 parts by mass

PGMEA: 79.1 parts by mass

Pigment Dispersion 1-2

The mixed liquid having the following composition was mixed and dispersed for 3 hours using zirconia beads having a diameter of 0.3mm and a bead mill (high pressure disperser NANO-3000-10(Nippon BEE co., ltd.) with a pressure reducing mechanism) to prepare pigment dispersion liquid 1-2.

Mixed pigments consisting of Blue pigment (c.i. pigment Blue 15: 6) and Violet pigment (c.i. pigment Violet 23): 12.6 parts by mass

Resin (Disperbyk-111, manufactured by BYKChemie GmbH): 2.0 parts by mass

Resin A: 3.3 parts by mass

Cyclohexanone: 31.2 parts by mass

PGMEA: 50.9 parts by mass

Resin A: the following structure (Mw: 14,000, molar ratio of each structural unit.)

[ chemical formula 52]

Polymerizable compound 1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol penta (meth) acrylate, manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound 4: the following structure

[ chemical formula 53]

Polymerizable compound 5: the following structure (mixture of the left compound and the right compound in a molar ratio of 7: 3)

[ chemical formula 54]

Resin 4: the following structure (acid value: 70mgKOH/g, Mw: 11,000, molar ratio in each structural unit.)

[ chemical formula 55]

Photopolymerization initiator 1: IRGACURE-OXE01(1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyl oxime), manufactured by BASF corporation)

Photopolymerization initiator 2: the following structure

[ chemical formula 56]

Surfactant 1: a1 mass% PGMEA solution of the following mixture (Mw ═ 14,000). In the following formula, the unit of% (62% and 38%) indicating the proportion of the structural unit is mass%.

[ chemical formula 57]

Silane coupling agent: a compound of the structure. In the following structural formulae, Et represents an ethyl group.

[ chemical formula 58]

Description of the symbols

1-cured product, 2-pattern edge part of cured product, 4-support (wafer), L₁-an exposure area, L₂Unexposed areas, T-cut length of the bottom in the pattern edge of the cured object.