阅读说明：本技术 着色组合物、固化膜的形成方法、滤色器的制造方法及显示装置的制造方法 (Coloring composition, method for forming cured film, method for manufacturing color filter, and method for manufacturing display device ) 是由 泷下大贵 山本启之 于 2019-09-20 设计创作，主要内容包括：在含有着色剂、自由基聚合性单体及光自由基聚合引发剂的着色组合物中,着色组合物的总固体成分中的光自由基聚合引发剂的含量为3质量％以上,着色组合物用于使用具有大于350nm且为380nm以下的波长的光以200mJ/cm～2以上的曝光量进行曝光且在整个工序中在150℃以下的温度下形成固化膜。并且,本发明涉及一种使用该着色组合物而成的固化膜的形成方法、滤色器的制造方法及显示装置的制造方法。(A coloring composition containing a coloring agent, a radical polymerizable monomer and a photo-radical polymerization initiator, wherein the content of the photo-radical polymerization initiator in the total solid content of the coloring composition is 3% by mass or more, and the coloring composition is used for using light with a wavelength of more than 350nm and 380nm or less at 200mJ/cm 2 The exposure is performed with the exposure amount above, and a cured film is formed at a temperature of 150 ℃ or less in the whole process. The present invention also relates to a method for forming a cured film using the colored composition, a method for producing a color filter, and a method for producing a display device.)

1. A coloring composition comprising a coloring agent, a radical polymerizable monomer and a photo radical polymerization initiator,

the content of the photo radical polymerization initiator in the total solid content of the coloring composition is 3 mass% or more,

the coloring composition is used for using light with a wavelength of more than 350nm and 380nm or less to achieve 200mJ/cm²The exposure is performed with the exposure amount above, and a cured film is formed at a temperature of 150 ℃ or less in the whole process.

2. The coloring composition according to claim 1,

the content of the photo radical polymerization initiator is 9 mass% or more.

3. The coloring composition according to claim 1 or 2,

the ratio M/I of the content M of the radical polymerizable monomer to the content I of the photo radical polymerization initiator in the total solid content of the coloring composition is 20 or less in mass ratio.

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

the photo radical polymerization initiator includes an oxime compound.

5. The coloring composition according to claim 4,

the content of the oxime compound is 10% by mass or more.

6. The coloring composition according to any one of claims 1 to 5,

the photo radical polymerization initiator includes: a photopolymerization initiator A1 having an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol³more than mL/gcm; and a photopolymerization initiator A2, having an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol²mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10³mL/gcm or higher.

7. The coloring composition according to claim 6,

the content of the photopolymerization initiator a1 is 10% by mass or more.

8. The coloring composition according to claim 6 or 7,

a content M of the radical polymerizable monomer and the content I of the photopolymerization initiator A1 in the total solid content of the coloring composition_A1Ratio M/I_A1The mass ratio is 20 or less.

9. The coloring composition according to any one of claims 6 to 8,

the photopolymerization initiator a1 contains an oxime compound containing a fluorine atom.

10. The coloring composition according to any one of claims 6 to 9,

the photopolymerization initiator a2 contains a hydroxyalkyl phenone compound.

11. The coloring composition according to claim 10,

the hydroxyalkyl phenone compound is a compound represented by the following formula (V),

formula (V):

in the formula, Rv¹Represents a substituent group, Rv²And Rv³Each independently represents a hydrogen atom or a substituent, optionally Rv²And Rv³Are bonded to each other to form a ring, and m represents an integer of 0 to 5.

12. The coloring composition according to any one of claims 6 to 11,

the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the coloring composition is 5 to 15% by mass.

13. The coloring composition according to any one of claims 1 to 12,

the coloring composition further contains a resin containing a repeating unit derived from a compound represented by the following formula (I),

in the formula, X¹Represents O or NH, and is selected from the group consisting of,

R¹represents a hydrogen atom or a methyl group,

L¹represents a linking group having a valence of 2,

R¹⁰represents a substituent group, and a pharmaceutically acceptable salt thereof,

m represents an integer of 0 to 2,

p represents an integer of 0 or more.

14. The coloring composition according to any one of claims 1 to 13, further containing a compound containing a furyl group.

15. The coloring composition according to claim 14,

the compound containing the furyl group is at least one selected from the group consisting of a compound represented by the following formula (fur-1) and a resin containing a repeating unit derived from the compound represented by the following formula (fur-1),

formula (fur-1):

in the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf²Represents a 2-valent linking group.

16. A method for forming a cured film, comprising:

a step of applying the color composition according to any one of claims 1 to 15 to a support to form a color composition layer; and

at 200mJ/cm²An exposure step of irradiating the colored composition layer with light having a wavelength of more than 350nm and 380nm or less at the above exposure amount to expose the colored composition layer,

in the whole process, a cured film, which is a film obtained by curing the colored composition layer, is obtained at a temperature of 150 ℃.

17. The method for forming a cured film according to claim 16,

the exposure amount in the exposure step is 1J/cm²The above.

18. The method for forming a cured film according to claim 16 or 17,

the exposure illumination in the exposure process is 1000mW/cm²The above.

19. The method of forming a cured film according to any one of claims 16 to 18,

the cured film is obtained at a temperature of 100 ℃ or less throughout the process.

20. A method of manufacturing a color filter, comprising the method of forming a cured film according to any one of claims 16 to 19.

21. A manufacturing method of a display device, comprising the method of forming a cured film according to any one of claims 16 to 19.

Technical Field

The present invention relates to a coloring composition, a method for forming a cured film, a method for manufacturing a color filter, and a method for manufacturing a display device.

Background

Conventionally, color filters have been used in various display devices and solid-state imaging devices to colorize a display image. Such a color filter is generally manufactured by forming a coating film of a curable coloring composition containing a resin and a colorant and curing the coating film in a pattern.

In recent years, studies have been made on the use of organic semiconductor materials and plastic members as raw materials for a part of the above-described display devices and the like, and it is desired that color filters can also be manufactured at a temperature of 150 ℃. For example, patent document 1 describes the following: a color filter imparting chemical resistance is produced at a low curing temperature of 150 ℃ or lower by using a composition containing: an alkali-soluble resin (A) containing 45 wt% or more of a specific constituent unit in all constituent units; a photopolymerizable monomer (B) composed of a specific compound; a photopolymerization initiator (C); and a colorant (D).

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-091940

Disclosure of Invention

Technical problem to be solved by the invention

However, it was found that the cured film (color filter) of patent document 1 is likely to have variations in spectral characteristics in a high-temperature and high-humidity test.

The present invention has been made in view of the above problems, and an object thereof is to provide a coloring composition capable of forming a cured film having excellent stability of spectral characteristics at low temperature.

Another object of the present invention is to provide a method for forming a cured film using the colored composition, a method for manufacturing a color filter, and a method for manufacturing a display device.

Means for solving the technical problem

The above problems can be solved by increasing the content of the photo radical polymerization initiator in the coloring composition as compared with the conventional one and by generating more photo radicals in the composition than the conventional one at the time of exposure. Specifically, the above problems are solved by the following means < 1 >, preferably < 2 > - < 21 >.

＜1＞

A coloring composition comprising a coloring agent, a radical polymerizable monomer and a photo radical polymerization initiator,

the content of the photo-radical polymerization initiator in the total solid content of the coloring composition is 3% by mass or more,

the coloring composition is used for using light with wavelength of more than 350nm and 380nm or less at 200mJ/cm²The exposure is performed with the exposure amount above, and a cured film is formed at a temperature of 150 ℃ or less in the whole process.

＜2＞

The coloring composition according to < 1 >, wherein,

the content of the photo radical polymerization initiator is 9% by mass or more.

＜3＞

The coloring composition according to < 1 > or < 2 >, wherein,

the ratio M/I of the content M of the radical polymerizable monomer to the content I of the photo radical polymerization initiator in the total solid content of the coloring composition is 20 or less in mass ratio.

＜4＞

The coloring composition according to any one of < 1 > to < 3 >, wherein,

the photo radical polymerization initiator contains an oxime compound.

＜5＞

The coloring composition according to < 4 >, wherein,

the content of the oxime compound is 10% by mass or more.

＜6＞

The coloring composition according to any one of < 1 > to < 5 >, wherein,

the photo radical polymerization initiator comprises: a photopolymerization initiator A1 having an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol³more than mL/gcm; and a photopolymerization initiator A2, having an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol²mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10³mL/gcm or higher.

＜7＞

The coloring composition according to < 6 >, wherein,

the content of the photopolymerization initiator a1 is 10% by mass or more.

＜8＞

The coloring composition according to < 6 > or < 7 >, wherein,

the content M of the radical polymerizable monomer in the total solid content of the coloring composition and the content I of the photopolymerization initiator A1_A1Ratio M/I_A1The mass ratio is 20 or less.

＜9＞

The coloring composition according to any one of < 6 > to < 8 >, wherein,

the photopolymerization initiator a1 contains an oxime compound containing a fluorine atom.

＜10＞

The coloring composition according to any one of < 6 > to < 9 >, wherein,

the photopolymerization initiator a2 contains a hydroxyalkyl phenone compound.

＜11＞

The coloring composition according to < 10 > wherein,

the hydroxyalkyl phenone compound is a compound represented by the following formula (V),

formula (V):

[ chemical formula 1]

In the formula, Rv¹Represents a substituent group, Rv²And Rv³Each independently represents a hydrogen atom or a substituent, optionally Rv²And Rv³Are bonded to each other to form a ring, and m represents an integer of 0 to 5.

＜12＞

The photosensitive coloring composition according to any one of < 6 > to < 11 >, wherein,

the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the colored composition is 5-15% by mass.

＜13＞

The coloring composition according to any one of < 1 > to < 12 >, wherein,

the coloring composition further contains a resin containing a repeating unit derived from a compound represented by the following formula (I),

[ chemical formula 2]

In the formula, X¹Represents O or NH, and is selected from the group consisting of,

R¹represents a hydrogen atom or a methyl group,

L¹represents a linking group having a valence of 2,

R¹⁰represents a substituent group, and a pharmaceutically acceptable salt thereof,

m represents an integer of 0 to 2,

p represents an integer of 0 or more.

＜14＞

The coloring composition according to any one of < 1 > to < 13 > further containing a compound containing a furyl group.

＜15＞

The coloring composition according to < 14 >, wherein,

the compound containing a furyl group is at least one selected from the group consisting of a compound represented by the following formula (fur-1) and a resin containing a repeating unit derived from the compound represented by the following formula (fur-1),

formula (fur-1):

[ chemical formula 3]

In the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf²Represents a 2-valent linking group.

＜16＞

A method of forming a cured film, comprising:

a step of applying the coloring composition described in any one of < 1 > to < 15 > to a support to form a coloring composition layer; and

at 200mJ/cm²An exposure step of exposing the colored composition layer with light having a wavelength of more than 350nm and 380nm or less,

the cured film is obtained as a film obtained by curing the colored composition layer at a temperature of 150 ℃ or lower in the whole process.

＜17＞

The method of forming a cured film according to < 16 >, wherein,

the exposure amount in the exposure step was 1J/cm²The above.

＜18＞

The method of forming a cured film according to < 16 > or < 17 >, wherein,

the exposure illuminance in the exposure step was 1000mW/cm²The above.

＜19＞

The method of forming a cured film according to any one of < 16 > to < 18 >, wherein,

the cured film is obtained at a temperature of 100 ℃ or lower throughout the process.

＜20＞

A method for manufacturing a color filter, comprising the method for forming a cured film of any one of < 16 > to < 19 >.

＜21＞

A method for manufacturing a display device, comprising the method for forming a cured film of any one of < 16 > to < 19 >.

Effects of the invention

The colored composition of the present invention can form a cured film having excellent stability of spectroscopic characteristics at low temperatures. Further, the colored composition of the present invention can provide a method for forming a cured film, a method for producing a color filter, and a method for producing a display device of the present invention.

Detailed Description

Hereinafter, a main embodiment of the present invention will be described. However, the invention is not limited to the embodiments that have been set forth.

In the present specification, a numerical range denoted by a "to" symbol means a range including numerical values before and after the "to" as a lower limit value and an upper limit value.

The term "step" in the present specification includes not only an independent step but also a step which cannot be clearly distinguished from other steps as long as the desired action of the step can be achieved.

In the labeling of the group (atomic group) in the present specification, the label not labeled with substitution and unsubstituted includes a group (atomic group) having no substituent and also includes a group (atomic group) having a substituent. For example, when only "alkyl group" is recited, it means that both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group) are included.

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, the concentration of the total solid content in the composition is represented by mass percentage of other components than the solvent with respect to the total mass of the composition.

In this specification, unless otherwise specified, the temperature is set to 23 ℃.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are expressed as polystyrene conversion values according to gel permeation chromatography (GPC measurement). The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220 (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns, for example. Also, unless otherwise specified, THF (tetrahydrofuran) was used as an eluent for measurement. And, unless otherwise specified, a 254nm wavelength detector of UV rays (ultraviolet rays) is used for detection in GPC measurement.

In the present specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that another layer is present above or below the reference layer among the plurality of layers of interest. That is, the 3 rd layer or the element may be further interposed between the layer serving as the reference and the other layer, and the layer serving as the reference does not need to be in contact with the other layer. Also, unless otherwise specified, a direction in which layers are stacked on a substrate is referred to as "upper", or a direction from the substrate toward the photosensitive layer when the photosensitive layer is present is referred to as "upper", and a direction opposite thereto is referred to as "lower". In the present specification, such a vertical direction is set for convenience, and in an actual mode, the "up" direction in the present specification may be different from the vertical up direction.

In this specification, the term "light" is also used for convenience with respect to electromagnetic waves other than the visible region, and the meaning of "light" is the same as that of "electromagnetic waves" with respect to electromagnetic waves other than the visible region.

< coloring composition >

The coloring composition of the present invention contains a colorant, a radical polymerizable monomer (hereinafter, also simply referred to as "polymerizable monomer"), and a photo radical polymerization initiator (hereinafter, also simply referred to as "photopolymerization initiator"). In the colored composition of the present invention, the content of the photopolymerization initiator in the total solid content of the colored composition is 3% by mass or more. Further, the coloring composition is used for using light having a wavelength of more than 350nm and 380nm or less at 200mJ/cm²The exposure amount is above and a cured film is formed at a temperature of 150 ℃ or less in the whole process, and the cured film can be used as a color filter used in a display device or the like.

The coloring composition of the present invention is used for forming a cured film at a temperature of 150 ℃ or lower throughout the entire process, and preferably used for forming a cured film at a temperature of 120 ℃ or lower throughout the entire process. In the present specification, the term "forming a cured film at a temperature of 150 ℃ or lower throughout the entire process" means performing a series of entire processes of forming a cured film on a support using a coloring composition and a support at a support temperature of 150 ℃ or lower and at an ambient temperature. For example, the step of forming a cured film and a patterned cured film using a coloring composition and a support includes a step of applying the coloring composition to the support, a step of drying a coating film containing the composition, a step of exposing the dried film, a step of developing the exposed film, and a step of heating the support after exposure or development (so-called post-baking). The post-baking may be performed as needed or may not be performed.

The coloring composition of the present invention preferably has a solid content concentration of 5 to 25% by mass. The upper limit is preferably 22.5% by mass or less, more preferably 20% by mass or less, and still more preferably 18% by mass or less. When the solid content concentration is within the above range, a film having excellent flatness can be formed even when a cured film is formed at a temperature of 150 ℃ or lower (preferably, 120 ℃ or lower) in the entire process.

In the colored composition of the present invention, the content of the photopolymerization initiator in the colored composition is set to be 3% by mass or more and higher than the conventional content, and the content of the photopolymerization initiator in the colored composition is set to be 200mJ/cm²The exposure amount is higher than the conventional exposure amount. Thus, a cured film having excellent stability of spectroscopic characteristics can be formed at a low temperature without performing a heat curing treatment at a temperature of, for example, more than 150 ℃. This is considered to be because the same number of photo radicals are generated by the photopolymerization initiator more than ever and the exposure amount more than ever, as in the case of the heat curing treatment at a high temperature (for example, more than 150 ℃) after the development. That is, in the present invention, it is considered that a dense crosslinked state similar to the crosslinked state generated by the heat curing treatment at a high temperature can be realized by exposure generating a large amount of photo radicals.

In the present invention, in particular, when the photopolymerization initiator includes a compound having an aromatic ring as described later, and the resin contains the resin b1 described later, or the coloring composition contains a compound having a furan group as described later, it is considered that a decomposed product of the photo radical polymerization initiator generating a radical is concentrated around the aromatic ring of the resin and fills a gap of the resin. As a result, the cured film becomes denser in film quality, and the moisture resistance and the like are improved, contributing to the stability of spectral characteristics.

The colored composition of the present invention is, for example, a colored composition for forming a pixel (a cured film in a pattern) constituting a color filter for a display device. The color filter generally includes pixels corresponding to 3 colors, i.e., red (R), green (G), and blue (B), and is manufactured by patterning a cured film formed of a coloring composition corresponding to each color. The type of the display device is not particularly limited, but the colored composition of the present invention is particularly effective in the case of a display device in which a color filter is formed on a support having low heat resistance, such as a support containing an organic semiconductor layer. Examples of such a display device include a display device having an organic semiconductor element as a light source, such as an organic electroluminescence display device.

The thickness of the cured film and the pixel formed from the colored composition of the present invention is preferably 0.5 to 3.0. mu.m. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less.

The line width (pattern size) of the pixel formed from the colored composition of the present invention is preferably 2.0 to 10.0. mu.m. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and still more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and further preferably 2.75 μm or more. When the line width (pattern size) of the pixel is within the above range, the usability of the present invention is large.

Hereinafter, each component that can constitute the coloring composition will be described.

Coloring agent

The coloring composition of the present invention contains a colorant. Examples of the colorant include color colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a violet colorant, and an orange colorant. In the present invention, the colorant may be a pigment or a dye. Pigments and dyes may also be used in combination. The pigment may be any of an inorganic pigment and an organic pigment. In addition, a material obtained by substituting a part of an inorganic pigment or an organic-inorganic pigment with an organic chromophore can be used as the pigment. By substituting a part of the inorganic pigment or organic-inorganic pigment with an organic chromophore, the hue can be easily designed.

The colorant used in the present invention preferably contains a pigment. The content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Also, the colorant may be only a pigment. Examples of the pigment include those described below.

Color index (C.I.) pigment yellow 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, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 199, 215, 231, 213, 234, 199, 233, and 234, 142, 234, 18, 234, 142, 234, 23, 234, 23, 234, 23, 160, 23, 235 (amino ketone), 236 (amino ketone), etc. (the above is a yellow pigment, and hereinafter, it is also referred to as "PY 1" or the like).

C.i. pigment orange 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 pigment). Hereinafter, it is also referred to simply as "PO 2" or the like. ).

C.i. pigment red 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, 246, 254, 255, 264, 269, 270, 272, 279, 294 (xanthene series, Organo Ultramarine, bluired), 296 (monoazo series), 296 (diazo series), 297 (aminoketone series), etc. (referred to above for short as Red pigment PR1, etc.).

C.i. pigment green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine series), 65 (phthalocyanine series), 66 (phthalocyanine series), etc. (the above is a green pigment, and hereinafter, also simply referred to as "PG 7", etc.).

C.i. pigment violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (the above is a violet pigment, hereinafter, also simply referred to as "PV 1", etc.).

C.i. pigment blue 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 system), etc. (the above is a blue pigment, and hereinafter, also simply referred to as "PB 1", etc.).

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 on average in 1 molecule. Specific examples thereof include the compounds described in International publication No. 2015/118720. Further, as the green pigment, a compound described in the specification of the chinese patent application publication No. 106909027, a phthalocyanine compound having a phosphate ester described in the international publication No. 2012/102395 as a ligand, a phthalocyanine compound described in the japanese patent application laid-open No. 2019-008014, a phthalocyanine compound described in the japanese patent application laid-open No. 2018-02318058, a compound described in the japanese patent application laid-open No. 2019-038958, and the like can be used.

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.

Further, as the yellow pigment, a compound described in Japanese patent laid-open publication No. 2017-201003, a compound described in Japanese patent laid-open publication No. 2017-197719, compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese patent laid-open publication No. 2017-171912, compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese patent laid-open publication No. 2017-171913, compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of Japanese patent laid-open publication No. 2017-171914, compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of Japanese patent laid-open publication No. 2017-171914, quinophthalone compounds described in paragraphs 0011 to 0034 of Japanese patent laid-open publication No. 2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 and phthalein compounds described in Japanese patent laid-open publication No. 2014-026228, and quinophthalone compounds described in paragraphs 0013 to 0058 of Japanese patent laid-open publication No. 2018, The quinophthalone compound described in Japanese patent laid-open publication No. 2018-203798, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-062578, the quinophthalone compound described in Japanese patent laid-open publication No. 6432076, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-155881, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-111757, the quinophthalone compound described in Japanese patent laid-open publication No. 2018-040835, the quinophthalone compound described in Japanese patent laid-open publication No. 2017-197640, the quinophthalone compound described in Japanese patent laid-open publication No. 2016-145282, the quinophthalone compound described in Japanese patent laid-open publication No. 2014-085565, the quinophthalone compound described in Japanese patent laid-open publication No. 2014-021139, the quinophthalone compound described in Japanese patent laid-open publication No. 2092013-209614, The quinophthalone compound described in Japanese patent application laid-open No. 2013-209435, the quinophthalone compound described in Japanese patent application laid-open No. 2013-181015, the quinophthalone compound described in Japanese patent application laid-open No. 2013-061622, the quinophthalone compound described in Japanese patent application laid-open No. 2013-032486, the quinophthalone compound described in Japanese patent application laid-open No. 2012-226110, the quinophthalone compound described in Japanese patent application laid-open No. 2008-074987, the quinophthalone compound described in Japanese patent application laid-open No. 2008-open No. 081565, the quinophthalone compound described in Japanese patent application laid-open No. 2008-open No. 074986, the quinophthalone compound described in Japanese patent application laid-open No. 2008-open No. 074985, the quinophthalone compound described in Japanese patent application laid-open No. 2008-open No. 050420, the quinophthalone compound described in Japanese patent application laid, A quinophthalone compound described in Japanese patent publication No. 48-032765, a quinophthalone compound described in Japanese patent application laid-open No. 2019-008014, a compound represented by the following formula (QP1), and a compound represented by the following formula (QP 2).

[ chemical formula 4]

In formula (QP1), X¹～X¹⁶Each independently represents a hydrogen atom or a halogen atom, Z¹To representAn alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph 0016 of japanese patent No. 6443711.

[ chemical formula 5]

In formula (QP2), Y¹～Y³Each independently represents a halogen atom. n and m are integers of 0 to 6, and p is an integer of 0 to 5. (n + m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese patent No. 6432077.

As the red pigment, a diketopyrrolopyrrole compound substituted with at least one bromine atom in the structure described in japanese patent application laid-open No. 2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of japanese patent No. 6248838, a diketopyrrolopyrrole compound described in international publication No. 2012/102399, a diketopyrrolopyrrole compound described in international publication No. 2012/117965, a naphthol azo compound described in japanese patent application laid-open No. 2012-229344, a red color material described in japanese patent No. 6516119, a red color material described in japanese patent No. 6525101, 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 having an oxygen atom, a sulfur atom, or a nitrogen atom bonded thereto is bonded to a diketopyrrolopyrrole skeleton can be used.

The dye is not particularly limited, and a known dye can be used. Examples thereof include dyes of pyrazolazine, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole, pyridone azo, cyanine, phenothiazine, pyrrolopyrazolylmethyleneimine, xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene. Furthermore, thiazole compounds described in Japanese patent laid-open No. 2012 and 158649, azo compounds described in Japanese patent laid-open No. 2011 and 184493, azo compounds described in Japanese patent laid-open No. 2011 and 145540, and intramolecular imide type xanthene dyes described in Japanese patent laid-open No. 2018 and 012863 can also be preferably used. Further, as the yellow dye, a quinophthalone (quinophthalone) compound described in paragraphs 0011 to 0034 of Japanese patent application laid-open No. 2013-054339, a quinophthalone compound described in paragraphs 0013 to 0058 of Japanese patent application laid-open No. 2014-026228, and the like can be used.

As the yellow colorant, pigments described in international publication No. 2012/128233 and japanese patent application laid-open publication No. 2017-201003 can be used. As the red colorant, pigments described in international publication nos. 2012/102399, 2012/117965, and jp 2012-229344 a can be used. As the green colorant, a pigment described in international publication No. 2012/102395 can be used. In addition, a salt-forming dye described in International publication No. 2011/037195 can also be used.

In the present invention, a pigment multimer can also be used as the colorant. The pigment multimer is preferably a dye that is dissolved in a solvent and used, but the pigment multimer can form particles, and when the pigment multimer is a particle, it is usually 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, and may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and still more preferably 6000 or more. The upper limit is more preferably 30000 or less, and still more preferably 20000 or less.

The dye structure of the dye multimer includes a structure derived from a dye compound having absorption in the visible region (preferably, in the wavelength range of 400 to 700nm, more preferably, in the wavelength range of 400 to 650 nm). Examples of the dye include triarylmethane dye structures, xanthene dye structures, anthraquinone dye structures, cyanine dye structures, squarylium dye structures, quinophthalone dye structures, phthalocyanine dye structures, subphthalocyanine dye structures, azo dye structures, pyrazolotriazole dye structures, dipyrromethene dye structures, isoindoline dye structures, thiazole dye structures, benzimidazole dye structures, perinone dye structures, diketopyrrolopyrrole dye structures, diimine dye structures, naphthalocyanine dye structures, frizzle dye structures, dibenzofuranone dye structures, merocyanine dye structures, ketanium dye structures, oxonol dye structures, and the like.

The pigment multimer is preferably a pigment multimer having a repeating unit represented by formula (A), a pigment multimer having a repeating unit represented by formula (B), a pigment multimer having a repeating unit represented by formula (C), and a pigment multimer represented by formula (D), and more preferably a pigment multimer having a repeating unit represented by formula (A) and a pigment multimer represented by formula (D).

[ chemical formula 6]

In the formula (A), X¹Denotes the main chain of the repeating unit, L¹Represents a single bond or a 2-valent linking group, D¹Represents a pigment structure. For details of the formula (A), reference can be made to paragraphs 0138 to 0152 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference.

In the formula (B), X²Denotes the main chain of the repeating unit, L²Represents a single bond or a 2-valent linking group, D²Is represented by having the ability to react with Y²Dye structure of an ionically or coordinatively bonded group, Y²Is represented by being able to react with D²A group that undergoes ionic bonding or coordinate bonding. For details of the formula (B), reference can be made to paragraphs 0156 to 0161 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference.

In the formula (C), L³Represents a single bond or a 2-valent linking group, D³Represents a pigment structure, and m represents 0 or 1. For details of the formula (C), reference can be made to paragraphs 0165 to 0167 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference.

In the formula (D), L⁴A linking group representing a valence of (n + k), L⁴¹And L⁴²Each independently represents a single bond or a 2-valent linking group, D⁴Represents a pigment structure, P⁴Represents a substituent; n is 2 to 15, k is 0 to 13, and n + k is 2 to 15. When n is 2 or more, a plurality of D⁴May or may not be different from each other. When k is 2 or more, a plurality of P⁴May or may not be different from each other. As L⁴Examples of the (n + k) -valent linking group include those described in paragraphs 0071 to 0072 of Japanese patent application laid-open No. 2008-222950, and those described in paragraphs 0176 of Japanese patent application laid-open No. 2013-029760. P⁴Examples of the substituent include an acid group and a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group (group having an ethylenically unsaturated bond), an epoxy group, an oxazoline, and a methylol group. Examples of the ethylenically unsaturated group include a vinyl group, (meth) allyl group, and (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. P⁴The substituents represented may be 1-valent polymer chains having repeating units. The polymer chain having a valence of 1 of the repeating unit preferably has a polymer chain having a valence of 1 of the repeating unit derived from the vinyl compound.

The dye multimer can also be a compound described in Japanese patent application laid-open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, and International publication No. 2016/031442.

The content of the colorant is preferably 5 to 70% by mass of the total solid content of the coloring composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.

In the coloring composition of the present invention, the content of each of the red colorant and the green colorant in the total solid content of the coloring composition may be 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. In particular, the content of the blue colorant that readily absorbs light in the ultraviolet region may be 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, of the total solid content of the coloring composition. If the content of the colorant is set to a high concentration, the thickness of the color filter can be reduced. On the other hand, as described above, when the content of the colorant is high, light during exposure hardly reaches the deep layer portion of the film, and curing of the deep layer portion of the film may be insufficient. However, in the present invention, since a sufficient exposure amount is secured to the extent that sufficient light reaches the film deep layer portion, even if the content of the colorant reaches a high concentration, curing can be performed more sufficiently than in the past. In particular, the present invention is highly useful when the content of the blue colorant which easily absorbs light in the ultraviolet region and hardly reaches the deep layer portion of the film is set to a high concentration.

The coloring composition of the present invention particularly preferably contains, as a colorant, at least one of PR177, PG7, PG36, PY139, PY150, and PY185, and more preferably contains at least one of PR177, PG7, and PY 150. In particular, the red-colored composition preferably contains at least PR177 and PY139 as the coloring agent. In addition, in the coloring composition for green, it is preferable that the colorant contains at least PG7, a combination of PG36 and PY139, a combination of PG7, a combination of PG36 and PY150, or a combination of PG36, PY150 and PY 185.

In the red-based coloring composition, the content of PR177 is preferably 0 to 60% by mass in the total solid content of the coloring composition. The upper limit of the numerical range is more preferably 55% by mass or less, and still more preferably 50% by mass or less. The lower limit of the numerical range is more preferably 10% by mass or more, and still more preferably 20% by mass or more. In the green-based coloring composition, the content of PG7 is preferably 0 to 50 mass% in the total solid content of the coloring composition. The upper limit of the numerical range is more preferably 40% by mass or less, and still more preferably 30% by mass or less. The lower limit of the numerical range is more preferably 5% by mass or more, and still more preferably 10% by mass or more. In the green-based coloring composition, the content of PY150 is preferably 0 to 30% by mass in the total solid content of the coloring composition. The upper limit of the numerical range is more preferably 25% by mass or less, and still more preferably 20% by mass or less. The lower limit of the numerical range is more preferably 5% by mass or more, and still more preferably 10% by mass or more.

Free radical polymerizable monomer

The coloring composition of the present invention contains a radical polymerizable monomer as a compound capable of radical polymerization. Examples of the polymerizable monomer include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, (meth) allyl group, and (meth) acryloyl group.

The molecular weight of the polymerizable monomer is preferably 100 to 2000. The upper limit is less than 2000, more preferably 1500 or less, still more preferably 1000 or less, and particularly preferably less than 1000. The lower limit is more preferably 150 or more, and still more preferably 250 or more.

The polymerizable monomer preferably has an ethylenically unsaturated group value (hereinafter referred to as C value) of 2 to 14mmol/g from the viewpoint of the stability of the composition over time. The lower limit is preferably 3mmol/g or more, more preferably 4mmol/g or more, and still more preferably 5mmol/g or more. The upper limit is preferably 12mmol/g or less, more preferably 10mmol/g or less, and still more preferably 8mmol/g or less. The value of C ═ C of the polymerizable monomer was calculated by dividing the number of ethylenically unsaturated groups contained in 1 molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated groups, and more preferably a compound containing 4 or more ethylenically unsaturated groups. In this manner, the curing properties of the colored composition by exposure are good. From the viewpoint of the stability of the composition over time, the upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. The polymerizable monomer is preferably a trifunctional or higher (meth) acrylate compound, more preferably a 3-15 functional (meth) acrylate compound, still more preferably a 3-10 functional (meth) acrylate compound, and particularly preferably a 3-6 functional (meth) acrylate compound.

The polymerizable monomer is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group. Such polymerizable monomers have high flexibility and are easy to move the ethylenically unsaturated group, and therefore the polymerizable monomers are easy to react with each other during exposure, and a cured film having excellent adhesion to a support or the like can be formed. Further, when a hydroxyalkyl phenone compound is used as the photopolymerization initiator, it is presumed that the polymerizable monomer is brought close to the photopolymerization initiator and the initiator generates radicals in the vicinity of the polymerizable monomer to enable the polymerizable monomer to react more efficiently, and a cured film having more excellent adhesion and solvent resistance is easily formed.

The number of alkyleneoxy groups contained in 1 molecule of the polymerizable monomer is preferably 3 or more, and more preferably 4 or more. From the viewpoint of the stability of the composition over time, the upper limit is preferably 20 or less.

The SP value (Solubility Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition. The upper limit is preferably 10.75 or less, more preferably 10.5 or less. The lower limit is preferably 9.25 or more, and more preferably 9.5 or more. In the present specification, the SP value is calculated by the Fedors method.

Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include compounds represented by the following formula (M-1).

Formula (M-1)

[ chemical formula 7]

Wherein A1 represents an ethylenically unsaturated group, L¹Represents a single bond or a 2-valent linking group, R¹Represents an alkylene group, m represents an integer of 1 to 30, n represents an integer of 3 or more,L²represents a linking group having a valence of n.

As A¹Examples of the ethylenically unsaturated group include a vinyl group, (meth) allyl group, and (meth) acryloyl group, and a (meth) acryloyl group is preferable.

As L¹The 2-valent linking group may be an alkylene group, an arylene group, -O-, -CO-, -CO O-, -OCO-, -NH-, or a combination of two or more thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10.

R¹The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2. R¹The alkylene group is preferably a straight chain or a branched chain, and more preferably a straight chain. R¹Specific examples of the alkylene group include an ethylene group, a linear or branched propylene group and the like, and an ethylene group is preferable.

m represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 5.

n represents an integer of 3 or more, preferably an integer of 4 or more. The upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and still more preferably an integer of 6 or less.

As L²Examples of the n-valent linking group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a group including a combination of these groups, and a group in which at least one member selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group is combined with at least one member selected from the group consisting of-O-, -CO-, -COO-, -OCO-, and-NH-. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Structure of the organizationExamples of the hetero atom forming the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring. L is²The n-valent linking group represented is also preferably derived from a polyfunctional alcohol group.

The compound having an ethylenically unsaturated group and an alkyleneoxy group is more preferably a compound represented by the following formula (M-2).

Formula (M-2)

[ chemical formula 8]

In the formula R²Represents a hydrogen atom or a methyl group, R¹Represents an alkylene group, m represents an integer of 1 to 30, n represents an integer of 3 or more, L²Represents a linking group having a valence of n. R of the formula (M-2)¹、L²M, n and R of formula (M-1)¹、L²M and n have the same meanings, and the preferable ranges are also the same.

Commercially available products of the polymerizable monomer having an ethylenically unsaturated group and an alkyleneoxy group include KAYARAD T-1420(T), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330; NIPPON KAYAKU co., ltd., product), dipentaerythritol tetraacrylate (KAYARAD D-320; NIPPON KAYAKU co., product ltd., product D.), dipentaerythritol penta (meth) acrylate (KAYARAD D-310; NIPPON KAYAKU co., product D.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; NIPPON KAYAKU co., product D-DPH-12E; product f-NAKAMURA chemcal co., product D.), and a compound having a structure in which a (meth) acryloyl group thereof is bonded to a residue of ethylene glycol and/or propylene glycol (for example, SR454, inc. SR499, product sarter Company, product c.).

Further, as the polymerizable monomer, ARONIX M-402(TOAGOSEI co., ltd., product of the publication, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) is preferably used.

As the polymerizable monomer, a trifunctional (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, trimethylolpropane-propylene oxide-modified tri (meth) acrylate, trimethylolpropane-ethylene oxide-modified tri (meth) acrylate, isocyanuric acid-ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like can be used. Commercially available trifunctional (meth) acrylate compounds include ARONIX M-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 Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., manufactured by Ltd.) and THE like.

As the polymerizable monomer, a polymerizable monomer having an acid group is also preferably used. By using a polymerizable monomer having an acid group, the colored composition layer in the unexposed portion 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 sulfonic acid group, and a phosphoric acid group, and a carboxyl group is preferable. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Commercially available products of polymerizable monomers having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349(TOAGOSEI CO., LTD., Ltd.). The acid value of the polymerizable monomer 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 monomer is 0.1mgKOH/g or more, the solubility in a developer is good, and when it is 40mgKOH/g or less, it is advantageous in production or handling.

The polymerizable monomer is also preferably a compound having a caprolactone structure. Polymerizable monomers having a caprolactone structure are commercially available as KAYARAD DPCA series from, for example, NIPPON KAYAKU CO., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60 and DPCA-120.

As the polymerizable monomer, compounds described in Japanese patent laid-open Nos. 2017-048367, 6057891, 6031807, 2017-194662, 8UH-1006, 8UH-1012 (above, Taisei Fine Chemical Co., Ltd., manufactured by Ltd.), and Light-Acrylate POB-A0(KYOEISHA CHEMICAL Co., manufactured by LTD.) are preferably used.

The content of the polymerizable monomer is preferably 5.0 to 35% by mass in the total solid content of the coloring composition. The upper limit is more preferably 30% by mass or less, and still more preferably 25% by mass or less. The lower limit is more preferably 7.5% by mass or more, and still more preferably 10% by mass or more. The polymerizable monomer may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

Photo-radical polymerization initiator

The coloring composition of the present invention contains 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, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole compounds and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, and benzoylformate compounds. As specific examples of the photopolymerization initiator, mention may be made of, for example, paragraphs 0265 to 0268 of Japanese patent laid-open publication No. 2013-029760 and Japanese patent laid-open publication No. 6301489, which are incorporated herein by reference.

Examples of the benzoylformate compound include methyl benzoylformate. The commercially available product may be DAROCUR-MBF (manufactured by BASF corporation).

Examples of the aminoalkyl phenone compound include the aminoalkyl phenone compounds described in Japanese patent application laid-open No. 10-291969. Also, IRGACURE-907, IRGACURE-369 and IRGACURE-379 (both manufactured by BASF) can be used as the aminoalkyl phenone compound.

The acylphosphine compound may be an acylphosphine compound described in japanese patent No. 4225898. Specific examples thereof include bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and the like. As the acylphosphine compound, IRGACURE-819 or DAROCUR-TPO (both manufactured by BASF) can be used.

Examples of the hydroxyalkyl phenone compound include compounds represented by the following formula (V).

Formula (V)

[ chemical formula 9]

In the formula Rv¹Represents a substituent group, Rv²And Rv³Each independently represents a hydrogen atom or a substituent, Rv²And Rv³Or may be bonded to each other to form a ring, and m represents an integer of 0 to 5.

As Rv¹Examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably straight-chain or branched, and more preferably straight-chain. Rv¹The alkyl group and the alkoxy group may be unsubstituted or substituted. Examples of the substituent include a hydroxyl group and a group having a hydroxyalkyl phenone structure. As the group having a hydroxyalkyl phenone structure, there can be mentioned Rv represented by the formula (V)¹The bound benzene ring or from Rv¹Groups of structure which remove 1 hydrogen atom.

Rv²And Rv³Each independently represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). And, Rv²And Rv³May be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably straight-chain or branched, more preferably straight-chain.

Specific examples of the compound represented by the formula (V) include the following compounds.

[ chemical formula 10]

As the hydroxyalkyl phenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: manufactured by BASF) can also be used.

Examples of oxime compounds include compounds described in Japanese patent laid-open Nos. 2001-233842, 2000-080068, 2006-342166, J.C.S.Perkin II (1979, pp.1653-1660), J.C.S.Perkin II (1979, pp.156-162), Journal of Photopharmaceuticals Science and Technology (1995, pp.202-232), 2000-066385, 2000-080068, 2004-534797, 2006-342166, 2017-01978, 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 0025 to 0038 of International publication No. 2017/164127, 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) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (BASF CORPORATION), TR-PBG-304(Changzhou Tronly New Electronic Materials CO., LTD. Co.), Adeka Optomer N-1919 (photopolymerization initiator 2 described in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052).

Further, as the oxime compound, a compound described in japanese patent application laid-open No. 2009-519904 in which oxime is linked to the N-position of the carbazole ring, a compound described in U.S. Pat. No. 7626957 in which a hetero substituent is introduced into a diphenylketone site, a compound described in japanese patent application laid-open No. 2010-015025 and U.S. Pat. application laid-open No. 2009/0292039 in which a nitro group is introduced into a dye site, a ketoxime compound described in international publication No. 2009/131189, a compound described in U.S. Pat. No. 7556910 in which a triazine skeleton and an oxime skeleton are contained in the same molecule, a compound described in japanese patent laid-open No. 2009-51221114 in which the absorption is maximum at 405nm and which has good sensitivity to a g-ray source, and the like can be used. Reference can preferably be made to paragraphs 0274 to 0306 of Japanese patent application laid-open No. 2013-029760, which are incorporated herein by reference.

The oxime compound is preferably an oxime compound containing a fluorine atom from the viewpoint of efficiently generating radical active species. The oxime compound containing a fluorine atom preferably has a group containing a fluorine atom. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing alkyl group) or a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group). As fluorine-containing group, it is preferably selected from-OR^F1、-SR^F1、-COR^F1、-COOR^F1、-OCOR^F1、-NR^F1R^F2、-NHCOR^F1、-CONR^F1R^F2、-NHCONR^F1R^F2、-NHCOOR^F1、-SO₂R^F1、-SO₂OR^F1and-NHSO₂R^F1At least one of (1). R^F1Represents a fluorine-containing alkyl group, R^F2Represents a hydrogen atom, an alkyl group, a fluoroalkyl group, an aryl group or a heterocyclic group. The fluorine-containing group is preferably-OR^F1。

The alkyl group and the fluoroalkyl group preferably have 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4 carbon atoms. The alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, and are preferably linear or branched. In the fluoroalkyl group, the substitution rate of fluorine atoms is preferably 40 to 100%, more preferably 50 to 100%, and further preferably 60 to 100%. The substitution rate of fluorine atoms means the ratio (%) of the number substituted with fluorine atoms to the number of all hydrogen atoms of the alkyl group.

The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of fusion is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and still more preferably 3 to 20. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

The group containing a fluorine atom preferably has a terminal structure represented by formula (1) or (2). Wherein denotes a bond.

*-CHF₂(1)

*-CF₃(2)

The number of all fluorine atoms in the oxime compound containing a fluorine atom is preferably 3 or more, and more preferably 4 to 10.

The oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).

(OX-1)

[ chemical formula 11]

In the formula (OX-1), Ar¹And Ar²Each independently represents an optionally substituted aromatic hydrocarbon ring, R¹Represents an aryl group having a group containing a fluorine atom, R²And R³Each independently represents an alkyl group or an aryl group.

Ar¹And Ar²Each independently represents an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms in the ring constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring. Among them, Ar is preferred¹And Ar²At least one of them is a benzene ring, more preferably Ar¹Is a benzene ring. Ar (Ar)²Preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

As Ar¹And Ar²Examples of the substituent which may be present include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR^X1、-SR^X1、-COR^X1、-COOR^X1、-OCOR^X1、-NR^X1R^X2、-NHCOR^X1、-CONR^X1R^X2、-NHCONR^X1R^X2、-NHCOOR^X1、-SO₂R^X1、-SO₂OR^X1、-NHSO₂R^X1And the like. R^X1And R^X2Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. Alkyl as a substituent and R^X1And R^X2The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. In the alkyl group, a part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom). In the alkyl group, a part or all of the hydrogen atoms may be substituted by the above-mentioned substituent. Aryl as a substituent and R^X1And R^X2The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. In the aryl group, a part or all of the hydrogen atoms may be substituted by the above-mentioned substituent. Heterocyclic group as substituent and R^X1And R^X2The heterocyclic group represented is preferably a 5-or 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, a part or all of the hydrogen atoms may be substituted by the above-mentioned substituentAnd (4) generation.

Ar¹The aromatic hydrocarbon rings represented are preferably unsubstituted. Ar (Ar)²The aromatic hydrocarbon ring may be unsubstituted or substituted. Preferably with substituents. As the substituent, preferred is-COR^X1。R^X1Preferably an alkyl, aryl or heterocyclic group, more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

R¹Represents an aryl group having a group containing a fluorine atom. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The group containing a fluorine atom preferably includes an alkyl group having a fluorine atom (a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (a fluorine-containing group). The group containing a fluorine atom has the same meaning as the above range, and the preferable range is also the same.

R²Represents an alkyl or aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or substituted. As the substituent, the above-mentioned Ar is mentioned¹And Ar²The substituents which may be present are the substituents mentioned above. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

R³Represents an alkyl or aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or substituted. As the substituent, the above-mentioned Ar is mentioned¹And Ar²The substituents which may be present are the substituents mentioned above. R³The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. R³The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese patent application laid-open No. 2010-262028, compounds 24, 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and compounds (C-3) described in Japanese patent application laid-open No. 2013-164471.

As the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include those described in Japanese patent application laid-open No. 2014-137466. This content is incorporated in the present specification.

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

Further, an oxime compound having a skeleton in which at least 1 benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include the compound of International publication No. 2013/083505.

As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can be used. Examples of such photopolymerization initiators include compounds described in international publication No. 2019/088055.

Further, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. 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 paragraphs 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, and compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071.

Specific examples of oxime compounds are shown below, but the present invention is not limited thereto.

[ chemical formula 12]

[ chemical formula 13]

In the present invention, it is preferable that the photopolymerization initiator is used in combination with methanol so that the absorption coefficient at 365nm in methanol is 1.0X 10³A photopolymerization initiator A1 having a light absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol and mL/gcm or more²mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10³A photopolymerization initiator A2 having a concentration of mL/gcm or more. According to this aspect, the composition can be sufficiently cured by exposure, and a cured film having excellent adhesion, solvent resistance, flatness, and rectangularity of pattern can be formed in a low-temperature process (for example, at a temperature of 150 ℃ or lower, preferably 120 ℃ or lower throughout the entire process). The photopolymerization initiator a1 and the photopolymerization initiator a2 are preferably selected from the above compounds and used as compounds having the above absorption coefficient.

In the present invention, the absorption coefficient at the above wavelength of the photopolymerization initiator is a value measured as follows. That is, a measurement solution was prepared by dissolving a photopolymerization initiator in methanol, and the absorbance of the measurement solution was measured and calculated. Specifically, the measurement solution was placed on a glass dish having a width of 1cm, and absorbance was measured by using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, and the absorbance was substituted into the following formula to calculate the absorption coefficients (mL/gcm) at a wavelength of 365nm and a wavelength of 254 nm.

[ numerical formula 1]

In the above formula,. epsilon.represents an absorption coefficient (mL/gcm), A represents an absorbance, c represents a concentration (g/mL) of a photopolymerization initiator, and l represents an optical path length (cm).

The photopolymerization initiator A1 had an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol³mL/gcm or more, preferably 1.0X 10⁴mL/gcm or more, more preferably 1.1X 10⁴mL/gcm or more, and more preferably 1.2X 10⁴～1.0×10⁵mL/gcm, more preferably 1.3X 10⁴～5.0×10⁴mL/gcm, particularly preferably 1.5X 10⁴～3.0×10⁴mL/gcm。

The photopolymerization initiator A1 preferably has an absorption coefficient of 1.0X 10 for light having a wavelength of 254nm in methanol⁴～1.0×10⁵mL/gcm, more preferably 1.5X 10⁴～9.5×10⁴mL/gcm, more preferably 3.0X 10⁴～8.0×10⁴mL/gcm。

The photopolymerization initiator a1 is preferably an oxime compound, an aminoalkylphenone compound, or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, still more preferably an oxime compound, and particularly preferably an oxime compound containing a fluorine atom, from the viewpoint of compatibility with other components contained in the composition. As the oxime compound containing a fluorine atom, a compound represented by the above formula (OX-1) is preferable. Specific examples of the photopolymerization initiator A1 include 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ] (commercially available products such as IRGACURE-OXE01 and BASF corporation), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) (commercially available products such as IRGACURE-OXE02 and BASF corporation), bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (commercially available products such as IRGACURE-819 and BASF corporation), and (C-13) and (C-14) shown as specific examples of the oxime compound.

The photopolymerization initiator A2 has an absorption coefficient of 1.0X 10 for light having a wavelength of 365nm in methanol²mL/gcm or less, preferably 10 to 1.0X 10²mL/gcm, more preferably 20 to 1.0X 10²mL/gcm. The difference between the absorption coefficient of the photopolymerization initiator A1 for light having a wavelength of 365nm in methanol and the absorption coefficient of the photopolymerization initiator A2 for light having a wavelength of 365nm in methanol was 9.0X 10²mL/gcm or more, preferably 1.0X 10³mL/gcm or more, more preferably 5.0X 10³～3.0×10⁴mL/gcm, more preferably 1.0X 10⁴～2.0×10⁴mL/gcm. The photopolymerization initiator A2 had an absorption coefficient of 1.0X 10 for light having a wavelength of 254nm in methanol³mL/gcm or more, preferably 1.0X 10³～1.0×10⁶mL/gcm, more preferably 5.0X 10³～1.0×10⁵mL/gcm。

The photopolymerization initiator a2 is preferably a hydroxyalkyl phenone compound, a benzoyl formate compound, an aminoalkyl phenone compound, or an acylphosphine compound, more preferably a hydroxyalkyl phenone compound or a benzoyl formate compound, and still more preferably a hydroxyalkyl phenone compound. The hydroxyalkyl phenone compound is preferably a compound represented by the above formula (V). Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF corporation), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF corporation), and the like.

The combination of the photopolymerization initiator a1 and the photopolymerization initiator a2 is preferably a combination in which the photopolymerization initiator a1 is an oxime compound and the photopolymerization initiator a2 is a hydroxyalkyl phenone compound, more preferably a combination in which the photopolymerization initiator a1 is an oxime compound and the photopolymerization initiator a2 is a compound represented by the above formula (V), and particularly preferably a combination in which the photopolymerization initiator a1 is an oxime compound containing a fluorine atom and the photopolymerization initiator a2 is a compound represented by the above formula (V).

The content of the photopolymerization initiator is preferably 3 to 25% by mass in the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and still more preferably 15% by mass or less. The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

In the colored composition of the present invention, the ratio M/I of the content M of the polymerizable monomer in the total solid content to the content I of the photopolymerization initiator in the total solid content is preferably 20 or less in mass%. The upper limit is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 2 or less. The lower limit is preferably 0.1 or more, and more preferably 0.5 or more. In this manner, the stability of the spectroscopic characteristics is improved. When two or more polymerizable monomers and photopolymerization initiators are used in combination, the total amount of each is preferably satisfied as described above.

In the coloring composition of the present invention, when the oxime compound is used as a photopolymerization initiator, the content of the oxime compound is preferably 3 to 25% by mass in the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and still more preferably 15% by mass or less. Since the content of the oxime compound is within the above range, the adhesion between the cured film after development and the support is improved, and the miniaturization of the pattern becomes easy. The oxime compound may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

In the coloring composition of the present invention, the content M of the polymerizable monomer in the total solid content and the content I of the oxime compound in the total solid content are expressed in mass%_ORatio M/I_OPreferably 20 or less. The upper limit is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 2 or less. The lower limit is preferably 0.1 or more, and more preferably 0.5 or more. In this manner, the stability of the spectroscopic characteristics is further improved. When two or more polymerizable monomers and an oxime compound are used in combination, the total amount of each is preferably satisfied as described above.

In the colored composition of the present invention, when the photopolymerization initiator a1 is used as a photopolymerization initiator, the content of the photopolymerization initiator a1 is preferably 3 to 25% by mass based on the total solid content of the colored composition. The lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and still more preferably 15% by mass or less. Since the content of the photopolymerization initiator a1 is within the above range, the adhesion between the cured film after development and the support is improved, and the miniaturization of the pattern becomes easy. The photopolymerization initiator a1 may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

In the colored composition of the present invention, the content M of the polymerizable monomer in the total solid content and the content I of the photopolymerization initiator a1 in the total solid content are expressed in mass%_A1Ratio M/I_A1Preferably 20 or less. The upper limit is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 2 or less. The lower limit is preferably 0.1 or more, and more preferably 0.5 or more. In this manner, the stability of the spectroscopic characteristics is further improved. When two or more polymerizable monomers and the photopolymerization initiator a1 are used in combination, the total amount of each is preferably satisfied as described above.

In the colored composition of the present invention, when the photopolymerization initiator a2 is used as a photopolymerization initiator, the content of the photopolymerization initiator a2 is preferably 0.1 to 10.0% by mass in the total solid content of the colored composition. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass or more. The upper limit is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, and still more preferably 7.0% by mass or less. Since the content of the photopolymerization initiator a2 is in the above range, the solvent resistance of the cured film after development is improved, and the miniaturization of the pattern becomes easy. The photopolymerization initiator a2 may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

In the colored composition of the present invention, when the photopolymerization initiator a1 and the photopolymerization initiator a2 are used as photopolymerization initiators, the colored composition of the present invention preferably contains 50 to 200 parts by mass of the photopolymerization initiator a2 per 100 parts by mass of the photopolymerization initiator a 1. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. In this manner, a cured film having excellent properties such as solvent resistance can be formed in a low-temperature process (e.g., a process at a temperature of 150 ℃ or lower, preferably 120 ℃ or lower throughout the entire process). When two or more kinds of photopolymerization initiator a1 and photopolymerization initiator a2 are used in combination, the total amount of each preferably satisfies the above requirements.

In the colored composition of the present invention, when the photopolymerization initiator a1 and the photopolymerization initiator a2 are used as photopolymerization initiators, the total content of the photopolymerization initiator a1 and the photopolymerization initiator a2 in the total solid content of the colored composition is preferably 3.1 to 25% by mass. The lower limit is preferably 3.1% by mass or more, preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and still more preferably 15% by mass or less. When two or more kinds of photopolymerization initiators and photopolymerization initiator a2 are used in combination, the total amount of each preferably satisfies the above requirements.

The colored composition of the present invention may contain a photopolymerization initiator (hereinafter, also referred to as another photopolymerization initiator) other than the photopolymerization initiator a1 and the photopolymerization initiator a2 as a photopolymerization initiator, but it is preferable that the composition does not substantially contain another photopolymerization initiator. The case where the other photopolymerization initiator is not substantially contained means that the content of the other photopolymerization initiator is 1 part by mass or less, more preferably 0.5 part by mass or less, further preferably 0.1 part by mass or less, and still further preferably not containing the other photopolymerization initiator with respect to 100 parts by mass of the total of the photopolymerization initiator a1 and the photopolymerization initiator a 2.

Resin

The coloring composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as a pigment in the composition and for the purpose of a binder. The resin mainly used for dispersing particles and the like in the composition is also referred to as a dispersant. However, these uses of the resin are examples, and the resin may be used for purposes other than these uses.

The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more.

Examples of the resin include (meth) acrylic resins, (meth) acrylamide resins, epoxy 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, styrene resins, and silicone resins.

The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins or dispersants.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more. The upper limit is more preferably 400mgKOH/g or less, still more preferably 200mgKOH/g or less, particularly preferably 150mgKOH/g or less, and most preferably 120mgKOH/g or less.

As the resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Examples thereof include copolymers having repeating units derived from monomers such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, and partial esterified maleic acid, alkali-soluble phenol resins such as novolak type resins, acidic cellulose derivatives having a carboxyl group in a side chain, and polymers obtained by adding a polymer having a hydroxyl group to an acid anhydride. In particular, a copolymer of (meth) acrylic acid with other monomers copolymerizable therewith is preferred. Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate. Examples of the vinyl compound include styrene, α -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidinone, polystyrene macromonomers, and polymethyl methacrylate macromonomers. The other monomer copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

The resin having an acid group may have a repeating unit derived from a maleimide compound. As the maleimide compound, N-alkyl maleimide, N-aryl maleimide and the like can be mentioned. As the repeating unit derived from the maleimide compound, a repeating unit represented by the formula (C-mi) can be mentioned.

[ chemical formula 14]

In formula (C-mi), Rmi represents an alkyl group or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 20. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. Preferably, Rmi is aryl.

The resin having an acid group is also preferably a resin containing a repeating unit derived from 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 15]

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 16]

As a specific example of the formula (ED2), reference can be made to the description of Japanese patent laid-open No. 2010-168539.

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

Examples of the resin containing a repeating unit derived from an ether dimer include polymers having the following structures. In the following structural formula, Me represents a methyl group.

[ chemical formula 17]

The resin used in the present invention may have a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups such as a vinyl group, (meth) allyl group, and (meth) acryloyl group. Commercially available products of resins having a polymerizable group include DIANAL NR series (LTD. manufactured by MITSUBASHI RAYON CO., LTD.), Photomer 6173 (urethane acrylate oligomer having a carboxyl group, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS RESIST 106 (manufactured by OSAKA ORGANIC CHEMICAL LTD., LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (manufactured by Daicel Corporation), Ebecry l3800(DAICEL UCB CO., LTD. manufactured by LTD., LTD.), ACURE RD-F8(NIPPON SHOKUI CO., LTD. manufactured by UBD., UBDP 1305-351305-1305 (FUJIFILM fibers Co., Ltd.), and the like.

The resin used in the present invention preferably contains resin b1 containing a repeating unit derived from a compound represented by formula (I) (hereinafter, also referred to as repeating unit b 1-1). By using a resin having the repeating unit b1-1, low-temperature curability and transparency are excellent. When the resin contains the resin b1 and the photopolymerization initiator contains at least one of the above-mentioned hydroxyalkylphenone compound and the oxime compound represented by the formula (OX-1), the decomposed product of the photopolymerization initiator which generates radicals is likely to be accumulated around the aromatic ring of the resin b1 by pi-pi interaction between the aromatic rings. As a result, the gaps between the resins are filled with the decomposed product, the film quality of the cured film becomes denser, and the stability of the spectroscopic characteristics is further improved.

[ chemical formula 18]

X¹Represents O or NH, preferably O.

R¹Represents a hydrogen atom or a methyl group.

L¹Represents a 2-valent linking group. As the linking group having a valence of 2, there may be mentioned hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO₂-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of two or more thereof. Examples of the hydrocarbon group include an alkyl group and an aryl group. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, and a halogen atom.

R¹⁰Represents a substituent. As R¹⁰The substituent represented by the formula (I) includes substituent T shown below, preferably a hydrocarbon group, and more preferably a hydrocarbon groupAn alkyl group having an aryl group as a substituent.

m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.

p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 or 1, and particularly preferably 1.

(substituent T)

Examples of the substituent T include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group and an-ORt group¹、-CORt¹、-COORt¹、-OCORt¹、-NRt¹Rt²、-NHCORt¹、-CONRt¹Rt²、-NHCONRt¹Rt²、-NHCOORt¹、-SRt¹、-SO₂Rt¹、-SO₂ORt¹、-NHSO₂Rt¹or-SO₂NRt¹Rt²。Rt¹And Rt²Each independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rt¹And Rt²May be bonded to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably branched.

The number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.

The number of carbon atoms of the alkynyl group is preferably 2 to 30, more preferably 2 to 25. The alkynyl group may be any of linear, branched and cyclic, and is preferably linear or branched.

The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.

The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of hetero atoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above for the substituent T.

The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).

[ chemical formula 19]

X¹Represents O or NH, preferably O.

R¹Represents a hydrogen atom or a methyl group.

R²、R³And R¹¹Each independently represents a hydrocarbon group.

R²And R³The hydrocarbon group represented is preferably an alkylene group or an arylene group, and more preferably an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. R³The hydrocarbon group represented is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. The number of carbon atoms of an alkyl group when the alkyl group has an aryl group as a substituent means the number of carbon atoms of the alkyl moiety.

R¹²Represents a substituent. As R¹²The substituent represented by the formula (I) includes the substituent (T).

n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 to 1, and particularly preferably 0.

q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

The compound represented by the formula (I) is preferably a compound represented by the following formula (III).

[ chemical formula 20]

In the formula, R¹Represents a hydrogen atom or a methyl group, R²¹And R²²Each independently represents an alkylene group, and n represents an integer of 0 to 15. R²¹And R²²The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

Examples of the compound represented by the formula (I) include ethylene oxide-or propylene oxide-modified (meth) acrylates of p-cumylphenol. As a commercially available product, ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.) and the like can be mentioned.

In the resin b1, the proportion of the repeating unit derived from the compound represented by the formula (I) (preferably the formula (III)) among all the repeating units is preferably 1 to 99 mol%. The lower limit is more preferably 3 mol% or more, and still more preferably 5 mol% or more. The upper limit is more preferably 95 mol% or less, and still more preferably 90 mol% or less.

Resin b1 may further contain a repeating unit other than the repeating unit derived from the compound represented by formula (I). For example, the resin b1 can preferably contain a repeating unit derived from a (meth) acrylate ester, and contain a repeating unit derived from an alkyl (meth) acrylate ester. The alkyl (meth) acrylate preferably has 3 to 10 carbon atoms in the alkyl portion, more preferably 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms in the alkyl portion. Preferable specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate and the like. Also, for example, the resin b1 preferably further contains a repeating unit having an acid group. Further, for example, the resin b1 preferably also contains a repeating unit derived from a (meth) acrylate having an acid group.

The coloring composition of the present invention can 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. When the total amount of the acid group and the basic group is 100 mol%, the acid dispersant (acidic resin) is preferably a resin in which the acid group accounts for 70 mol% or more, and more preferably a resin substantially containing only the acid group. 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 10 to 105 mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of basic groups than that of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups is more than 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

Examples of the dispersant include a polymer dispersant [ e.g., polyamide and a salt thereof, polycarboxylic acid and a salt thereof, a high-molecular-weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic acid-based copolymer, naphthalenesulfonic acid formalin condensate ], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and alkanolamine. The polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers from their structures. The polymeric dispersant functions to prevent reagglomeration by adsorbing on the surface of particles such as pigments. Therefore, a terminal-modified polymer, a graft polymer, or a block polymer having a fixed site on the surface of a particle such as a pigment can be exemplified as a preferable structure. Further, the dispersants described in paragraphs 0028 to 0124 of Japanese patent application laid-open No. 2011-070156 and the dispersants described in Japanese patent application laid-open No. 2007-277514 may be preferably used. These are incorporated in the present specification.

In the present invention, a graft copolymer can also be used in the dispersant. Details of the graft copolymer can be found in paragraphs 0131 to 0160 of Japanese patent application laid-open Nos. 2012 and 137564, which are incorporated herein by reference. In the present invention, an oligoimine-based copolymer containing a nitrogen atom in at least one of the main chain and the side chain can also be used as the dispersant. Regarding the oligoimine-based copolymer, reference can be made to the descriptions in paragraphs 0102 to 0174 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference.

The dispersant is also commercially available, and examples thereof include Disperbyk series (for example, Disperbyk-111, 2001, etc.) manufactured by BYK Chemie, SOLSPERSE series (for example, SOLSPERSE20000, 76500, etc.) manufactured by Lubrizol Japan Ltd., Ajinomoto Fine-Techno Co., Inc., AJISPER series manufactured by Inc. Further, the dispersant may be a product described in paragraph 0129 of Japanese patent laid-open Nos. 2012 and 137564 and 0235 of Japanese patent laid-open Nos. 2017 and 194662.

The resins described in paragraphs 0041 to 0060 of Japanese patent application laid-open No. 2017-206689 can also be suitably used.

The content of the resin is preferably 5 to 50% by mass of the total solid content of the coloring composition. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The content of the resin is preferably 25 to 500 parts by mass per 100 parts by mass of the polymerizable monomer. The upper limit is preferably 250 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 50 parts by mass or more, and more preferably 75 parts by mass or more. The resin may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

The content of the resin b1 (including the repeating unit derived from the compound represented by formula (III)) in the total amount of resins contained in the coloring composition of the present invention is preferably 0.1 to 100% by mass, and more preferably 5 to 100% by mass. The upper limit may be 90 mass% or less, may be 80 mass% or less, and may be 70 mass% or less. The content of the resin b1 is preferably 5 to 50% by mass based on the total solid content of the coloring composition. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 12.5% by mass or more. The resin b1 may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

< Compounds containing furyl group >)

The coloring composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). In this mode, the furyl group and the ethylenically unsaturated group of the polymerizable monomer form a bond even at a low temperature of 150 ℃ or lower by the Diels-Alder reaction, and thus the low-temperature curing is excellent. When the coloring composition contains a compound having a furyl group and the photopolymerization initiator contains at least one of the hydroxyalkyl phenone compound and the oxime compound represented by the formula (OX-1), decomposition products of the photopolymerization initiator which generate radicals tend to aggregate around the aromatic ring of the compound having a furyl group by pi-pi interaction between the aromatic rings. As a result, the gaps between the resins are filled with the decomposed product, the film quality of the cured film becomes denser, and the stability of the spectroscopic characteristics is further improved.

The compound having a furyl group is not particularly limited in structure as long as it contains a furyl group (a group obtained by removing 1 hydrogen atom from furan). As the compound having a furyl group, the compounds described in paragraphs 0049 to 0089 of Japanese patent laid-open publication No. 2017-194662 can be used. Further, compounds described in Japanese patent laid-open Nos. 2000-233581, 1994-271558, 1994-293830, 1996-239421, 1998-508655, 2000-001529, 2003-183348, 2006-193628, 2007-186684, 2010-265377, 2011-170170069, and the like can be used.

The compound containing a furyl group may be a monomer, an oligomer or a polymer. From the viewpoint of easily improving the durability of the obtained film, a polymer is preferable. When the polymer is used, the weight average molecular weight is preferably 2000 to 70000. The upper limit is preferably 60000 or less, and more preferably 50000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more. When it is a monomer, the weight average molecular weight is preferably less than 2000. The upper limit is preferably 1800 or less, and more preferably 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 175 or more. The polymer type furyl group-containing compound also corresponds to a component of the resin in the coloring composition of the present invention, and the radical polymerizable monomer type furyl group-containing compound also corresponds to a component of the polymerizable monomer in the coloring composition of the present invention.

As the monomer type furyl group-containing compound (hereinafter, also referred to as furyl group-containing monomer), a compound represented by the following formula (fur-1) can be exemplified. The compound is a compound having a radical polymerizable group in addition to a furyl group.

Formula (fur-1)

[ chemical formula 21]

In the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf²Represents a 2-valent linking group.

As Rf²The 2-valent linking group may be an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, or a combination of two or more thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and the arylene group may have a substituent. As a substitutionExamples of the group include a hydroxyl group.

The furyl group-containing monomer is preferably a compound represented by the following formula (fur-2).

Formula (fur-2)

[ chemical formula 22]

In the formula, Rf¹Represents a hydrogen atom or a methyl group, Rf¹¹represents-O-or-NH-, Rf¹²Represents a single bond or a 2-valent linking group. As Rf¹²The 2-valent linking group may be an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, or a combination of two or more thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.

Specific examples of the furyl group-containing monomer include compounds having the following structures. In the following structural formula, Rf¹Represents a hydrogen atom or a methyl group.

[ chemical formula 23]

The furyl group-containing compound (hereinafter, also referred to as a furyl group-containing polymer) as a polymer type is preferably a resin containing a repeating unit containing a furyl group, and more preferably a resin containing a repeating unit derived from a compound represented by the above formula (fur-1). In the polymer containing a furyl group, the proportion of repeating units containing a furyl group in all repeating units is preferably 30 to 70% by mass. The lower limit is more preferably 35% by mass or more, and still more preferably 40% by mass or more. The upper limit is more preferably 65% by mass or less, and still more preferably 60% by mass or less. The concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0mmol, more preferably 1.0 to 4.0mmol, per 1g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5mmol or more, preferably 1.0mmol or more, a more excellent pixel is easily formed due to solvent resistance or the like. When the concentration of the furyl group is 6.0mmol or less, preferably 4.0mmol or less, the coloring composition is more excellent in stability with time.

The polymer containing a furyl group may contain, in addition to the repeating unit having a furyl group, a repeating unit having an acid group and/or a repeating unit having a polymerizable group. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, and a phenolic hydroxyl group. Examples of the polymerizable group include ethylenically unsaturated groups such as a vinyl group, (meth) allyl group, and (meth) acryloyl group. When the polymer having a furyl group contains a repeating unit having an acid group, the acid value thereof is preferably 10 to 200mgKOH/g, more preferably 40 to 130 mgKOH/g. In the polymer containing a furyl group, the proportion of the repeating unit having an acid group in all the repeating units is preferably 2 to 25% by mass. The lower limit is more preferably 4% by mass or more, and still more preferably 5% by mass or more. The upper limit is more preferably 20% by mass or less, and still more preferably 15% by mass or less. On the other hand, in the polymer containing a furyl group, the proportion of the repeating unit having a polymerizable group in all the repeating units is preferably 20 to 60% by mass. The lower limit is more preferably 25% by mass or more, and still more preferably 30% by mass or more. The upper limit is more preferably 55% by mass or less, and still more preferably 50% by mass or less. When the polymer containing a furyl group includes a repeating unit having a polymerizable group, a cured film having more excellent solvent resistance and the like can be easily formed.

The furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of Japanese patent application laid-open No. 2017-194662.

The content of the furyl group-containing compound is preferably 0.1 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and further preferably 7.5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. When a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer in the resin contained in the coloring composition is preferably 0.1 to 100% 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 90% by mass or less, and more preferably 80% by mass or less.

Further, when the resin used in the colored composition of the present invention contains the above-mentioned resin b1 and a polymer containing a furyl group is used as the compound containing a furyl group, the content of the polymer containing a furyl group is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the resin b 1. The upper limit is preferably 175 parts by mass or less, and preferably 150 parts by mass or less. The lower limit is preferably 25 parts by mass or more, and preferably 150 parts by mass or more. By using the resin b1 and the furan group-containing polymer in combination, an effect of excellent low-temperature curability and transparency can be expected. In addition, when the ratio of the two is within the above range, an effect of further improving the durability of the obtained film can be expected.

The compound having a furyl group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

< Compound having Cyclic Ether group >

The coloring composition of the present invention can 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.

As the compound having an epoxy group, a compound having two or more epoxy groups in 1 molecule is preferable. More preferably, the epoxy group has 2 to 100 epoxy groups in 1 molecule. The upper limit may be set to, for example, 10 or less, or may be set to 5 or less. The epoxy equivalent of the compound having an epoxy group (the molecular weight of the compound having an epoxy group/the number of epoxy groups) is preferably 500g/eq or less, more preferably 100 to 400g/eq, and still more preferably 100 to 300 g/eq. The compound having an epoxy group may be a low molecular compound (for example, a molecular weight of less than 1000) or any high molecular compound (macromolecule) (for example, in the case of a polymer having a molecular weight of 1000 or more, the weight average molecular weight is 1000 or more). The molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably 200 to 100000, more preferably 500 to 50000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.

Examples of the compound having an epoxy group include those 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, 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. Further, as the compound having an oxetanyl group, for example, the compounds described in Japanese patent laid-open publication No. 2019-133052 can be used. These are incorporated in the present specification.

When the coloring composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group is preferably 0.1 to 40% by mass in the total solid content of the coloring composition. 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 30% by mass or less, and still more preferably 20% by mass or less. The cyclic ether group-containing compound may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

In the case where the coloring composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass in the total solid content of the coloring composition. 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 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

Solvent

The coloring composition of the present invention preferably contains a solvent. The solvent may be an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring 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 0223 of international publication No. 2015/166779, which is incorporated into the present specification. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 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 (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be reduced to be preferable for environmental reasons, etc. (for example, the aromatic hydrocarbons may be set to 50 mass ppm (parts per million) or less, may be set to 10 mass ppm or less, and may be set to 1 mass ppm or less with respect to the total amount of the organic solvent).

In the present invention, the solvent is preferably an organic solvent having a boiling point of 160 ℃ or less from the viewpoint of effectively utilizing the solvent. The boiling point of the organic solvent is more preferably 140 ℃ or lower, and still more preferably 130 ℃ or lower. The lower limit of the boiling point is not particularly limited, and is, for example, 100 ℃ or higher in practice. Examples of such organic solvents include butyl acetate, PGME, PGMEA, cyclohexanone, and ethyl lactate, and particularly, butyl acetate, PGME, and PGMEA are preferable.

In the present invention, a solvent having a small metal content is preferably used, and for example, the metal content of the solvent is preferably 10 parts per billion (ppb) by mass or less. Solvents of quality ppt (parts per trillion) grade, such as those provided by Toyo Gosei Kogyo co., ltd. (journal of chemical industry, 11/13/2015), may also be used as desired.

Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, membrane distillation, etc.) 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 preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same atomic number but different structures). The isomer may include only one kind or a plurality of 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 does not substantially contain a peroxide.

The content of the solvent in the coloring composition is preferably 60 to 95% by mass. The upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and further preferably 85% by mass or less. The lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more. The solvent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

Further, from the viewpoint of environmental regulations, the coloring composition of the present invention preferably contains substantially no environmental regulation substance. In the present invention, the substantial absence of the environmental regulation substance means that the content of the environmental regulation substance in the coloring 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 environmental regulation substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as environmental regulations under 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 amounts of use and treatment methods are strictly regulated. These compounds are sometimes used as a solvent in the production of each component or the like used in the coloring composition of the present invention, and mixed into the coloring composition as a residual solvent. From the viewpoint of safety to humans and environmental considerations, it is preferable to reduce these substances as much as possible. As a method for reducing the environmental regulation substance, there is a method in which the inside of the system is heated and depressurized to a boiling point of the environmental regulation substance or higher, and the environmental regulation substance is distilled off from the system and reduced. In addition, in the case of removing a small amount of environmental regulation substances by distillation, it is also useful to azeotropically distill with a solvent having the same boiling point as the solvent in order to improve efficiency. When the compound having radical polymerizability is contained, in order to suppress intermolecular crosslinking due to the progress of radical polymerization reaction in the removal by distillation under reduced pressure, the removal by distillation under reduced pressure may be performed after the addition of a polymerization inhibitor. These distillation removal methods can be performed in any of the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution and the polyfunctional monomer solution after polymerization), and the stage of the coloring composition prepared by mixing these compounds.

Pigment derivatives

The coloring composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Examples of the chromophore constituting the pigment derivative 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 skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a styrene skeleton, and a metal complex skeleton, and the quinoline skeleton, the benzimidazolone skeleton, the diketopyrrolopyrrole skeleton, the azo skeleton, the quinophthalone skeleton, the isoindoline skeleton, and the phthalocyanine skeleton are preferable, and the azo skeleton and the benzimidazolone skeleton are more preferable. 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 of the pigment derivative is preferably an amino group, and more preferably a tertiary amino group. As a specific example of the pigment derivative, reference can be made to the descriptions in paragraphs 0162 to 0183 of Japanese patent application laid-open No. 2011-252065, the contents of which are incorporated in the present specification.

Specific examples of the pigment derivative include Japanese patent application laid-open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-045662, 04-285669, 06-145546, 06-212088, 06-240158, 10-030063, 10-195326, 0086-0098 of International publication No. 2011/024896, 0063-0094 of International publication No. 2012/102399, 0082 of International publication No. 2017/038252, and 0171 of 2015-151530, The compounds described in paragraphs 0162 to 0183 of Japanese patent laid-open publication No. 2011-252065, Japanese patent laid-open publication No. 2003-081972, Japanese patent laid-open publication No. 5299151, Japanese patent laid-open publication No. 2015-172732, Japanese patent laid-open publication No. 2014-199308, Japanese patent laid-open publication No. 2014-085562, Japanese patent laid-open publication No. 2014-035351, Japanese patent laid-open publication No. 2008-565 081, Japanese patent laid-open publication No. 2019-109512, and Japanese patent laid-open publication No. 2019-133154.

The content of the pigment derivative is preferably 0.1 to 30 parts by mass per 100 parts by mass of the pigment. The lower limit of this range is more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and still more preferably 1 part by mass or more. The upper limit of the range is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. Since the content of the pigment derivative is within the above range, the stability with time is further improved. The pigment derivative may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount of these is preferably within the above range.

(curing accelerator)

The coloring composition of the present invention may further contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable monomer or lowering the curing temperature. Examples of the curing accelerator include a polyfunctional thiol compound having 2 or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkyl thiol, and more preferably a compound represented by the formula (T1).

Formula (T1)

[ chemical formula 24]

In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group having a valence of 2 to 4. In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and more preferably n is 2, and L is an alkylene group having 2 to 12 carbon atoms.

Furthermore, as the curing accelerator, a methylol compound (e.g., a compound exemplified as a crosslinking agent in the 0246 paragraph of Japanese patent laid-open No. 2015-034963), an amine, a phosphonium salt, an amidine salt, and an amide compound (e.g., the curing agent described in the 0186 paragraph of Japanese patent laid-open No. 2013-041165) can be used, examples of the base generating agent include an alkali generating agent (for example, an ionic compound described in Japanese patent laid-open publication No. 2014-055114), a cyanate ester compound (for example, a compound described in paragraph 0071 of Japanese patent laid-open publication No. 2012-150180), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in Japanese patent laid-open publication No. 2011-253054), an onium salt compound (for example, a compound described as an acid generating agent in paragraph 0216 of Japanese patent laid-open publication No. 2015-034963, and a compound described in Japanese patent laid-open publication No. 2009-941809).

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass, based on the total solid content of the coloring composition.

Silane coupling agent

The coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two functional groups different in reactivity in one molecule is preferable. The silane coupling agent is preferably a silane compound having at least one group selected from a vinyl group, an epoxy group, a styryl group, a methacrylic group, an amino group, an isocyanurate group, a urea group, a mercapto group, a sulfide group, and an isocyanate group, and having an alkoxy group or the like. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3- γ -aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-602), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-603), 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by Ltd., KBM-503), and 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by Shin-Etsu Co., manufactured by KBM-503), ltd. system, KBM-403), and the like. For details of the silane coupling agent, reference can be made to the descriptions in paragraphs 0155 to 0158 of japanese patent application laid-open No. 2013-254047, which is incorporated herein by reference. When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass. The coloring composition of the present invention may contain only one or two or more silane coupling agents. When two or more are contained, the total amount of these is preferably within the above range.

Polymerization inhibitor

The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosodiamine salt (ammonium salt, first cerium salt, etc.). When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the coloring composition. The coloring composition of the present invention may contain only one kind of polymerization inhibitor or two or more kinds of polymerization inhibitors. When two or more are contained, the total amount of these is preferably within the above range.

Ultraviolet absorbent

The coloring composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used. For details of these, reference may be made to the descriptions in paragraphs 0052 to 0072 of japanese patent application laid-open No. 2012-208374, paragraphs 0317 to 0334 of japanese patent application laid-open No. 2013-068814, and paragraphs 0061 to 0080 of japanese patent application laid-open No. 2016-162946, which are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.). Examples of the benzotriazole compound include MIYOSHI OIL & FAT co, MYUA series manufactured by ltd. (journal of chemical industry, 2016, 2 months and 1 day). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese patent No. 6268967 can be used. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. One or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount of these is preferably within the above range.

Surface active agent

The coloring composition of the present invention can 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 silicone-based surfactant can be used. Regarding the surfactant, reference can be made to 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 coloring composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. Further, a film with less 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. The fluorine-based surfactant having a fluorine content within the above range is effective in terms of uniformity of thickness of a coating film and liquid saving, and has good solubility in the coloring composition.

Examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of Japanese patent application laid-open No. 2014-041318 (paragraphs 0060 to 0064 of corresponding International publication No. 2014/017669), and surfactants described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, which are incorporated herein by reference. Commercially available fluorine-based surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781F, EXP, MFS-330 (manufactured by Corporation), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3 MLimited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTION INC).

Further, the fluorine-based surfactant can also preferably use an acrylic compound which has a molecular structure having a functional group containing a fluorine atom, and in which a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized when heated. Examples of the fluorine-based surfactant include MEGAFACE DS series (chemical industry journal, 2016, 2, 22 days) (sunrise industry news, 2016, 2, 23 days), manufactured by DIC Corporation, for example, MEGAFACE DS-21.

Further, as the fluorine-based surfactant, it is also preferable to use 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. Such a fluorine-based surfactant can be referred to the disclosure of Japanese patent laid-open No. 2016-216602, and the contents thereof are incorporated in the present specification.

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

[ chemical formula 25]

The weight average molecular weight of the above compound is preferably 3000 to 50000, for example 14000. In the above compounds,% representing the proportion of the repeating 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 compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese patent application laid-open No. 2010-164965, for example, 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 glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol 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, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Co., Ltd.), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Co., Ltd.), SOLSPERSE20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (FUFILLM Wako Pure Co., Ltd.), PIONIN D-6112, D-6112-W, D-6115 (Takeco & Okel Chemical Co., Ltd.), ltd), OLFIN E1010, Surfynol 104, 400, 440(Nissin Chemical co., ltd), and the like.

Examples of the Silicone 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 Inc.), KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and Chemie 330 (manufactured by BYK GmbH, manufactured by BYK).

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be one kind only, or two or more kinds. When the number of these is two or more, the total amount of these is preferably within the above range.

Other additives

Various additives such as fillers, adhesion promoters, antioxidants, anti-agglomeration agents and the like can be blended in the coloring composition of the present invention as needed. As such additives, the additives described in paragraphs 0155 to 0156 of Japanese patent application laid-open No. 2004-295116 can be cited, and the contents are incorporated in the present specification. Examples of the antioxidant include phenolic compounds, phosphorus compounds (e.g., compounds described in paragraph 0042 of jp 2011-a-090147), and thioether compounds. Examples of commercially available products include the Adekastab series (AO-20, AO-30, AO-40, AO-50F, AO-60, AO-60G, AO-80, AO-330, etc.) manufactured by ADEKA CORPORATION. Further, as the antioxidant, a polyfunctional hindered amine antioxidant described in international publication No. 2017/006600, an antioxidant described in international publication No. 2017/164024, and an antioxidant described in paragraphs 0023 to 0048 of japanese patent No. 6268967 can be used. The antioxidant may be used alone or in combination of two or more. The coloring composition of the present invention may further contain a latent antioxidant, if necessary. The latent antioxidant includes a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protecting group is released by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst to function as an antioxidant. Specific examples of latent antioxidants include compounds described in International publication Nos. 2014/021023 and 2017/030005 and Japanese patent application laid-open Nos. 2017 and 008219. Examples of commercially available products include ADEKAARKLS GPA-5001 (manufactured by ADEKA CORPORATION). The colored composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of Japanese patent application laid-open No. 2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of Japanese patent application laid-open No. 2004-295116, and a storage stabilizer described in paragraph 0242 of Japanese patent application laid-open No. 2018-091940.

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

Further, the coloring composition of the present invention may contain a light fastness improver. Examples of the light resistance improver include compounds described in paragraphs 0036 to 0037 of Japanese patent application laid-open No. 2017-198787, compounds described in paragraphs 0029 to 0034 of Japanese patent application laid-open No. 2017-146350, compounds described in paragraphs 0036 to 0037 of Japanese patent application laid-open No. 2017-129774, compounds described in paragraphs 0049 to 0052, compounds described in paragraphs 0031 to 0034 of Japanese patent application laid-open No. 2017-129674, compounds described in paragraphs 0058 to 0059, compounds described in paragraphs 20156 to 0037 of Japanese patent application laid-open No. 122803, compounds described in paragraphs 0051 to 0054, compounds described in paragraphs 0025 to 0039 of International publication No. 002 2017/164127, compounds described in paragraphs 0034 to 0047 of Japanese patent application laid-open No. 2017-004546, compounds described in paragraphs 0129 to 0041 of Japanese patent application laid-open No. 2012 025116, compounds described in paragraphs 0121 to 0045, and 012604 of Japanese patent application laid-open No. 2011, The compounds described in paragraphs 0018 to 0021 in Japanese patent laid-open No. 2012 and 103475, the compounds described in paragraphs 0015 to 0018 in Japanese patent laid-open No. 2011 and 257591, the compounds described in paragraphs 0017 to 0021 in Japanese patent laid-open No. 2011 and 191483, the compounds described in paragraphs 0108 to 0116 in Japanese patent laid-open No. 2011 and 145668, the compounds described in paragraphs 0103 to 0153 in Japanese patent laid-open No. 2011 and 253174, and the like.

In the coloring composition of the present invention, the content of free metal not bonded or coordinated to the pigment or the like is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less, and particularly preferably substantially not contained. This embodiment can expect effects such as stabilization of pigment dispersibility (inhibition of aggregation), improvement of spectroscopic characteristics accompanying improvement of dispersibility, stabilization of curable components, inhibition of conductivity fluctuation accompanying elution of metal atoms and metal ions, and improvement of display characteristics. 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, Fe, Co, Mg, Al, Ti, Sn, Zn, Zr, Ga, Ge, Ag, Au, Pt, Cs, and Bi. In the coloring composition of the present invention, the content of free halogen not bonded or coordinated to the pigment or the like is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less, and particularly preferably substantially not contained. Examples of the method for reducing the amount of free metal or halogen in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

The coloring composition of the present invention also preferably contains substantially no terephthalate. Here, "substantially not contained" means that the content of the terephthalate ester is 1000 mass ppb or less, more preferably 100 mass ppb or less, and particularly preferably 0 in the total solid content of the composition.

< storage Container >

The container for the coloring 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 coloring composition, it is preferable to use a multilayer bottle in which the inner wall of the container is made of 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins have a 7-layer structure. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351. In addition, the inner wall of the storage container is preferably made of glass or stainless steel from the viewpoints of preventing elution of metal from the inner wall of the container, improving the storage stability of the composition, and suppressing the deterioration of components.

< method for producing coloring composition >

The coloring composition of the present invention can be produced by mixing the aforementioned components. In the production of the coloring composition, the coloring composition may be produced by dissolving and/or dispersing all the components in a solvent at the same time, or the composition may be produced by mixing the components as a solution or dispersion of two or more kinds as needed and at the time of use (at the time of coating).

Further, the production of the coloring composition may include a step of dispersing particles such as a pigment. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, pressing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills (sand mills), roll mills, ball mills, paint mixers (paint shakers), microfluidizers (microfluidizers), high-speed impellers, sand mills, jet mixers (flowjet mixers), high-pressure wet atomization, ultrasonic dispersion, and the like. In addition, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to perform the treatment under the conditions that the pulverization efficiency is improved by using beads having a small diameter, increasing the packing ratio of the beads, or the like. After the pulverization treatment, it is preferable to remove coarse particles by filtration, centrifugation, or the like. The procedure and the dispersing machine for dispersing the pigment can be preferably those described in "the general term of dispersion technology, johaokiko co., ltd, release 7/15/2005" or "the actual data set of dispersion technology and industrial application centered on suspension (solid/liquid dispersion system), release by the ministry of business development, 10/1978" and paragraph 0022 of japanese patent application laid-open No. 2015-157893 ". In the process of dispersing the pigment, the fine particle size can be obtained by a salt milling (salt milling) step. Materials, equipment, processing conditions, and the like used in the salt milling step can be described in, for example, japanese patent application laid-open nos. 2015-194521 and 2012-046629.

In the production of the coloring composition, the coloring composition is preferably filtered by a filter for the purpose of removing foreign matter, reducing defects, and the like. The filter is not particularly limited and may be used as long as it is a filter that has been used for filtration purposes and the like. Examples of the filter include filters using a fluororesin such as Polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, 6), a polyolefin resin such as polyethylene or polypropylene (PP) (including a high-density and ultrahigh-molecular-weight polyolefin resin), and the like. Among these 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 reliably removed. For the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. The filters can be various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegr is K.K. (for merly Nippon Mykrolis Corporation), and KITZ MICROFILTER CO RPORATION, etc.

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

When a filter is used, different filters (for example, the 1 st filter and the 2 nd filter) may be combined. In this case, the filtration in each filter may be performed only once, or may be performed twice or more. Also, filters of different pore sizes may be combined within the above range. The filtration in the 1 st filter may be performed only on the dispersion, or the filtration may be performed in the 2 nd filter after mixing other components.

< method for forming cured film and pixel >

The method for forming a cured film of the present invention includes a step of applying the color composition of the present invention to a support to form a color composition layer and a step of exposing the color composition layer to light. In particular, the method for forming the pixels (patterned cured film) further includes: in the step of exposure, the colored composition layer is exposed in a pattern and then developed. The present invention is characterized in that the reaction is carried out at a temperature of 150 ℃ or lower throughout the entire process. In the present invention, "performed at a temperature of 150 ℃ or lower throughout the entire process" means that the entire process of forming a pixel using a coloring composition is performed at a temperature of 150 ℃ or lower. When a further heating step is provided after the color composition layer after exposure is developed, this heating step is also performed at a temperature of 150 ℃. Hereinafter, each step will be described in detail.

In the step of forming the colored composition layer, the colored composition of the present invention is applied to a support to form the colored composition layer. Examples of the support include a glass substrate and a resin substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide-imide substrate, and a polyimide substrate. An organic light emitting layer may be formed on these substrates. The substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of a substance, or planarizing the surface.

As a method for applying the coloring composition, a known method can be used. Examples thereof include a dropping method (drop casting); slit coating method; spraying; a roll coating method; spin coating (spin coating); tape casting coating method; slit and spin coating; a prewet method (for example, the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as an ink jet method (for example, a drop-on-demand method, a piezoelectric method, a thermal method), discharge printing such as nozzle spraying, 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 application method by the inkjet is not particularly limited, and examples thereof include "spreading, usable inkjet-unlimited possibility in the patent, release in 2.2005, and methods shown in SB Techno-Research co., ltd." (especially, pages 115 to 133), and methods described in japanese patent laid-open publication nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1699325. Further, as for the method of applying the coloring composition, reference can be made to the descriptions of international publication No. 2017/030174 and international publication No. 2017/018419, which are incorporated in the present specification.

The colored composition layer formed on the support may be dried (prebaked). When the prebaking is performed, the prebaking temperature is preferably 80 ℃ or lower, more preferably 70 ℃ or lower, still more preferably 60 ℃ or lower, and particularly preferably 50 ℃ or lower. The lower limit can be set to 40 ℃ or higher, for example. The pre-baking time is preferably 10-3600 seconds. The prebaking can be performed by a hot plate, an oven, or the like.

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

Examples of the light that can be used for exposure include ultraviolet rays such as g-rays (wavelength: 436nm) and i-rays (wavelength: 365 nm). As described in korean laid-open patent No. 1020170122130, exposure using i-rays may be performed while cutting light having a wavelength shorter than that of the i-rays. 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) and ArF rays (wavelength: 193nm), and KrF rays (wavelength: 248nm) are preferable. Further, a light source of a long 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 pulse irradiation (pulse exposure). The pulse exposure is an exposure method of repeating irradiation and suspension of light in a short time (for example, millisecond order or less) cycle to perform exposure. In the 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 still more 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 illumination intensity is preferably 5000W/cm²More preferably 10000W/cm or more²The above is more preferably 20000W/cm²The above. Further, the upper limit of the maximum instantaneous illuminance is preferably 100000W/cm²Hereinafter, more preferably 80000W/cm²Hereinafter, 50000W/cm is more preferable²The following. In addition, the pulse width refers to the time during which light is irradiated in the pulse period.And, the frequency means the number of pulse periods per one second. The maximum instantaneous illuminance is an average illuminance over the time period during which light is irradiated in the pulse period. The pulse period refers to a period in which irradiation and suspension of light in pulse exposure are performed as one cycle.

In the method for forming a cured film of the present invention, the exposure amount (irradiation dose) is 200mJ/cm²The above. In this way, by performing exposure with a larger exposure amount than ever, a large amount of photoradicals are generated, and curing of the composition is promoted in the same manner as in the heat curing treatment at a high temperature of more than 150 ℃. The lower limit of the exposure amount is preferably 800mJ/cm²Above, more preferably 1J/cm²The above. The upper limit of the exposure amount is preferably 2.5J/cm²Hereinafter, more preferably 2.0J/cm²Hereinafter, more preferably 1.5J/cm²The following. The exposure illuminance can be set as appropriate, and is preferably 50mW/cm, for example²～10W/cm². Further, the lower limit of the exposure illuminance is preferably 500mW/cm²Above, more preferably 800mW/cm²More preferably 1000mW/cm²The above. Further, the upper limit of the exposure illuminance is preferably 10W/cm²Below, more preferably 7W/cm²Hereinafter, it is more preferably 5W/cm²The following.

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%. The oxygen concentration and the exposure illuminance may be appropriately combined, and may be set to an illuminance of 1W/cm at an oxygen concentration of 10 vol%²The illuminance is set to 2W/cm at an oxygen concentration of 35 vol%²And the like.

Next, the color composition layer after exposure is developed. That is, the unexposed portions of the colored composition layer are removed by development, and the cured film is formed in a pattern to form pixels. The unexposed portions of the colored composition layer can be removed by development using a developer. In this way, the colored composition layer in the unexposed portion in the exposure step is dissolved in the developer, and only the photocured portion remains. The developing solution includes an organic solvent, an alkali developing solution, and the like, and is preferably an alkali developing solution. 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 following steps may be repeated several times: the developer was thrown off every 60 seconds, and the developer was further resupplied.

The alkaline developer is preferably an alkaline aqueous solution 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. As for the alkaline agent, a compound having a large molecular weight is preferably used in terms 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. Also, the developing solution may further include a surfactant. The surfactant includes the above-mentioned surfactants, and preferably a nonionic surfactant. From the viewpoint of convenience in transportation and storage, the developer may be once prepared as a concentrated solution or diluted to a concentration required for 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 cleaning (rinsing) with pure water after development. The rinsing is preferably performed by supplying a rinsing liquid to the colored composition layer after development while rotating the support on which the colored composition layer after development is formed. It is also preferable that the rinse liquid is discharged by moving a nozzle 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 in 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 also preferable to perform additional exposure treatment and heating treatment (post-baking) after drying. The additional exposure treatment and the post-baking are post-development curing treatments for completing curing.

When the post-baking is performed, the heating temperature is preferably 150 ℃ or lower. The upper limit of the heating temperature is more preferably 120 ℃ or lower, and still more preferably 100 ℃ or lower. The lower limit of the heating temperature is not particularly limited as long as the curing of the composition can be accelerated, and is more preferably 50 ℃ or higher, and still more preferably 75 ℃ or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 10 minutes or more. The upper limit is not particularly limited, and is preferably 20 minutes or less from the viewpoint of productivity. The post-baking is also preferably performed in an inert gas environment. This method enables thermal polymerization to be performed with very high efficiency without being hindered by oxygen, and enables production of a pixel having good flatness and excellent properties such as solvent resistance even when the pixel is produced at a temperature of 120 ℃. The inert gas includes nitrogen, argon, helium, and the like, and nitrogen is preferable. The oxygen concentration at the time of post-baking is preferably 100ppm or less.

When performing the additional exposure treatment, it is preferable to perform the exposure by irradiating light having a wavelength of 254 to 350 nm. More preferably, in the step of exposing the colored composition layer in a pattern (exposure before development), the colored composition layer is exposed by irradiating the colored composition layer with light having a wavelength of more than 350nm and not more than 380nm (preferably, light having a wavelength of 355 to 370nm, more preferably i-ray), and in the additional exposure treatment (exposure after development), the colored composition layer after development is exposed by irradiating the colored composition layer with light having a wavelength of 254 to 350nm (preferably, light having a wavelength of 254 nm). In this manner, the colored composition layer can be appropriately cured by the first exposure (exposure before development), and the entire colored composition layer can be substantially completely cured by the next exposure (exposure after development), and therefore, as a result, the colored composition layer can be cured even under low temperature conditionsThe colored composition layer can be sufficiently cured, and a pixel having excellent characteristics such as solvent resistance, adhesiveness, and rectangularity of a pattern can be formed. When the exposure is carried out in two stages as such, the coloring composition preferably contains, as a photopolymerization initiator: the absorption coefficient at 365nm wavelength in methanol was 1.0X 10³A photopolymerization initiator A1 of mL/gcm or more; and an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol²mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10³A photopolymerization initiator A2 having a concentration of mL/gcm or more.

The exposure after development can be performed using, for example, an ultraviolet resist curing apparatus. Light having a wavelength of 254 to 350nm and other light (i-ray, for example) may be irradiated from the ultraviolet resist curing apparatus.

The exposure amount (irradiation amount) after development under exposure is preferably 30 to 4000mJ/cm²More preferably 50 to 3500mJ/cm². The difference between the wavelength of light used for exposure before development and the wavelength of light used for exposure after development is preferably 200nm or less, and more preferably 100 to 150 nm.

< method for manufacturing color filter >

The method for manufacturing a color filter of the present invention includes the method for forming the cured film of the present invention described above, and particularly includes a method for forming a pixel.

When the color filter has pixels of a plurality of colors, the above-described pixel formation method is performed for each color pixel, whereby a color filter having pixels of a plurality of colors can be formed. Examples of the color filter include filters having colored pixels of one or more colors, such as a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, and a yellow pixel. Specific examples of the color filter include a filter having at least a red pixel, a blue pixel, and a green pixel, and a filter having at least a cyan pixel, a magenta pixel, and a yellow pixel. The color filter may have the following structure: the structure is such that each colored pixel is embedded in a space partitioned by a partition wall, for example, in a lattice shape. The partition walls in this case preferably have a low refractive index for each colored pixel. The partition wall may be formed in the structure described in U.S. patent application publication No. 2018/0040656.

< method for manufacturing display device >

The method for manufacturing a display device of the present invention includes the method for forming a pixel of the present invention.

Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. The definition of the display device and the details of each image display device are described in, for example, "electronic display device (published by gazozu shoff, Kogyo Chosakai Publishing co., ltd.1990)", "display device (published by yibushu, Sangyo-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 to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various types described in the "next generation liquid crystal display technology" described above.

The organic electroluminescent display device may have a light source composed of a white organic electroluminescent element. The white organic electroluminescent element is preferably of a tandem structure. The tandem structure of organic electroluminescent elements is described in japanese patent application laid-open No. 2003-045676, the third best practice, "the most advanced line of organic EL technology development-high brightness, high precision, long lifetime, skill set-", Technical Information Institute co., ltd., page 326-page 328, and 2008, for example. The spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in the blue region (430nm-485nm), green region (530nm-580nm), and yellow region (580nm-620 nm). It is more preferable that the emission peak has a maximum emission peak in a red region (650nm to 700nm) in addition to these emission peaks.

Also, the organic electroluminescent display device may have a lens on the color filter. As the shape of the lens, various shapes derived by optical system design can be adopted, and examples thereof include a convex shape, a concave shape, and the like. For example, the light condensing property can be easily improved by using a concave shape (concave lens). Such a lens is used by being disposed on the optical path of light passing through a color filter of a display device having the color filter. The lens of the present invention may be provided on the side where light is incident on the color filter, or on the side where light is emitted from the color filter. When the light source is disposed on the side of the color filter where light is incident, the amount of light condensed on the color filter can be increased. Further, when the light is emitted from the color filter, the amount of light condensed on the display can be increased. The lens may be in direct contact with the color filter, or another layer such as an adhesion layer or a planarization layer may be provided between the lens and the color filter. The lens may be arranged and used as described in international publication No. 2018/135189.

Examples

The present invention will be described more specifically below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the process procedures, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are on a mass basis.

< preparation of pigment Dispersion >

(pigment Dispersion liquid P-R)

After uniformly stirring and mixing a mixture of the following composition, it was dispersed for 5 hours using 1mm diameter zirconia beads, Eiger Motor Mill ("EIGER CO., Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-R.

C.i. pigment red 2548.96 parts by mass

C.i. pigment red 1771.42 parts by mass

C.i. pigment yellow 1501.16 parts by mass

2.29 parts by mass of a dispersant (SOLSPERSE 20000 manufactured by The Lubrizol Corporation)

2.69 parts by mass of a pigment derivative (pigment derivative 1 having the following structure)

27.66 parts by mass of alkali-soluble resin solution D

75.82 parts by mass of Cyclohexanone

Pigment derivative 1:

[ chemical formula 26]

The alkali-soluble resin solution D2 was produced by the following method.

In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas inlet tube, 90.0 parts by mass of cyclohexanone was placed, and while nitrogen gas was injected into the vessel, the vessel was heated to 60 ℃ to drop a mixture of 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate, and 2.5 parts by mass of 2,2' -azobisisobutyronitrile at the same temperature over 2 hours, and a polymerization reaction was performed. After completion of the dropwise addition, the mixture was further reacted at 60 ℃ for 1 hour, and then 0.5 part by mass of 2,2' -azobisisobutyronitrile was dissolved in 10.0 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and stirred at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with cyclohexanone, whereby an alkali-soluble resin solution D2 having a solid content concentration of 20% was obtained. Weight average molecular weight 30000.

(pigment Dispersion liquid P-G)

After uniformly stirring and mixing a mixture of the following composition, using zirconia beads having a diameter of 1mm, dispersion was carried out for 5 hours using an Eiger Motor Mill ("EIGER CO., manufactured by Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-G.

587.53 parts by mass of C.I. pigment Green

C.i. pigment yellow 1504.14 parts by mass

6.09 parts by mass of a dispersant (Disperbyk-2001, BYK Chemie., Ltd., solid content concentration 46% by mass)

Alkali-soluble resin solution D25.53 parts by mass

76.71 parts by mass of PGMEA

(pigment Dispersion liquid P-B)

After uniformly stirring and mixing a mixture of the following composition, using zirconia beads having a diameter of 1mm, dispersion was carried out for 5 hours using an Eiger Motor Mill ("EIGER CO., manufactured by Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-B.

C.I. pigment blue 15: 612.88 parts by mass

5.62 parts by mass of a dispersant (SOLSPERSE 20000 manufactured by The Lubrizol Corporation)

Alkali-soluble resin solution D21.50 parts by mass

80.00 parts by mass of Cyclohexanone

(pigment Dispersion liquid P-X)

After uniformly stirring and mixing a mixture of the following composition, using zirconia beads having a diameter of 1mm, dispersion was carried out for 5 hours using an Eiger Motor Mill ("EIGER CO., manufactured by Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-X.

C.i. pigment red 25413.33 parts by mass

1.67 parts by mass of a pigment derivative (pigment derivative 2A having the following structure)

1 st dispersant (resin K having the following structure) 2.50 parts by mass

2.50 parts by mass of the No. 2 dispersant (resin PA-1 synthesized by the following method)

80.00 parts by mass of PGMEA

Pigment derivative 2A:

[ chemical formula 27]

Resin K: a compound having the structure. The number attached to the brackets of the main chain represents the molar ratio of each repeating unit, and the number attached to the brackets of the side chain represents the number of repetitions of each repeating unit. The weight average molecular weight is 20000.

[ chemical formula 28]

Resin PA-1:

method for synthesizing resin PA-1

The following raw materials were introduced into a three-necked flask, thereby obtaining a mixture.

Subsequently, the mixture was stirred while blowing nitrogen gas, and then the temperature of the mixture was raised to 75 ℃ while flowing nitrogen gas into the flask. Subsequently, dodecylmercaptan (0.82g) and 0.43g of 2,2' -azobis (methyl 2-methylpropionate) (hereinafter, also referred to as "V-601") were added to the mixture to start a polymerization reaction. 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 completion of the reaction, dimethyldodecylamine (9.6g) as an amine compound and 2,2,6,6, -tetramethylpiperidine 1-oxyl (0.3g) as a polymerization inhibitor were added to air, and then 4-hydroxybutyl acrylate glycidyl ether (9.01g) was added dropwise as a reactive compound. After the completion of the dropwise addition, the reaction was continued in the air at 90 ℃ for 24 hours. The completion of the reaction was confirmed by measuring the acid value. PGMEA was added to the obtained mixture to be a 30 mass% solution to obtain a resin PA-1. The obtained resin PA-1 had a weight average molecular weight of 17,200 and an acid value of 70 mgKOH/mg.

Raw materials for the resin PA-1

A monomer B-1 solution (solid content: 50% by mass) prepared by the following method

60.78g

50.99g of a polymerizable monomer (omega-carboxy-polycaprolactone monoacrylate, ARONIX M-5300, TOAGOSEI CO., LTD., manufactured by Ltd.)

·PGMEA 159.5g

The acid value of the resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the following method is used to obtain: the obtained resin was dissolved in a solvent to obtain a solution, which was titrated with an aqueous sodium hydroxide solution by a potentiometric method to calculate the number of millimoles of acid contained in 1g of the solid content of the resin, and this value was multiplied by the molecular weight of potassium hydroxide (KOH) of 56.1.

Preparation of a solution of the monomer B-1

In a three-necked flask, epsilon-caprolactone (1256.62 parts, corresponding to a cyclic compound) and 2-ethyl-1-hexanol (143.38 parts, corresponding to a ring-opening polymerization initiator) were introduced to obtain a mixture. Subsequently, the mixture was stirred while blowing nitrogen gas. Next, monobutyl tin oxide (0.63 part) was added to the mixture, and the resulting mixture was heated to 90 ℃. After 6 hours while maintaining at 90 deg.C, the mixture was used¹H-NMR (nuclear magnetic resonance) confirmed that the signal derived from 2-ethyl-1-hexanol in the mixture disappeared. The mixture was then heated to 110 ℃ and polymerization continued for 2 hours at 110 ℃ under nitrogen. By using¹H-NMR confirmed the disappearance of the signal originating from epsilon-caprolactone and the mixture was cooled to 80 ℃. Then, 2, 6-di-tert-butyl-4-methylphenol (0.78 part) was added to the above mixture, and 2-methacryloyloxyethyl isocyanate (MOI, 174.15 parts) was further added dropwise to the obtained mixture over 30 minutes. After 1 hour from the completion of the dropwise addition, it was confirmed by 1H-NMR that the signal derived from the MOI disappeared. Then, PGMEA (1575.57 parts) was added to the mixture to obtain a monomer B-1 solution having a solid content of 50 mass%. Can pass through¹H-NMR confirmed the structure of the monomer B-1, as shown in the following formula (B-1). The weight-average molecular weight of the obtained monomer B-1 was 3000.

[ chemical formula 29]

(B-1)

(pigment Dispersion liquid P-Y)

After uniformly stirring and mixing a mixture of the following composition, it was dispersed for 5 hours using 1mm diameter zirconia beads, Eiger Motor Mill ("EIGER CO., Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-Y.

C.i. pigment red 25413.33 parts by mass

1.67 parts by mass of a pigment derivative (pigment derivative 2A having the above-mentioned structure)

2.50 parts by mass of the No. 1 dispersant (resin K of the above-mentioned structure)

2.50 parts by mass of the No. 2 dispersant (resin L having the following structure)

80.00 parts by mass of PGMEA

Resin L: a compound having the structure. The number attached to the brackets of the main chain represents the molar ratio of each repeating unit, and the number attached to the brackets of the side chain represents the number of repeating units. The weight average molecular weight is 20000.

[ chemical formula 30]

(pigment Dispersion liquid P-Z)

After uniformly stirring and mixing a mixture of the following composition, using zirconia beads having a diameter of 1mm, dispersion was carried out for 5 hours using an Eiger Motor Mill ("EIGER CO., manufactured by Ltd." Mini Model M-250MKII "). Then, the mixture was filtered through a filter having a pore size of 5 μm to prepare a pigment dispersion liquid P-Z.

C.i. pigment yellow 13913.33 parts by mass

1.67 parts by mass of a pigment derivative (pigment derivative 2A having the above-mentioned structure)

2.50 parts by mass of the No. 1 dispersant (resin K of the above-mentioned structure)

2.50 parts by mass of the No. 2 dispersant (resin L having the above structure)

80.00 parts by mass of PGMEA

< preparation of coloring composition >

(coloring composition of example 1)

After mixing and stirring the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nihon Pall ltd.) having a pore size of 0.45 μm, thereby preparing a coloring composition having a solid content of 19.05 mass%. The solid content concentration of the coloring composition was adjusted according to the amount of PGMEA added.

65 parts by mass of pigment Dispersion liquid P-R

2 parts by mass of a photo radical polymerization initiator (initiator 1)

5.5 parts by mass of resin (resin A)

5.5 parts by mass of a furyl group-containing compound (F1)

2.6 parts by mass of a radically polymerizable monomer (M1)

Residual part of PGMEA

(coloring compositions of examples 2 to 23 and comparative examples 1 to 2)

The pigment dispersion, photo radical polymerization initiator, resin, compound containing a furan group, radical polymerizable monomer and the type and content (parts by mass) of the solvent were changed as described in table 1 below, and a colored composition was prepared in the same manner as in example 1. The solid content concentration (mass%. described in the column of "solid content") of each coloring composition was adjusted according to the amount of the solvent to be added. In Table 2, the M/I ratio (mass ratio) and M/I are shown for each of the coloring compositions_A1A ratio (mass ratio), and a pigment concentration (mass%: a ratio of the content of the pigment to the amount of the solid component).

< preparation of cured film >

Each of the colored compositions of examples 1 to 23 was coated on a glass substrate using a spin coater so that the thickness of the final film after drying became 2.0. mu.m, and dried on a hot plate at 100 ℃ for 2 minutes. Then, using an ultra-high pressure mercury lamp, at an exposure illuminance of 20mW/cm²And an exposure amount of 1J/cm²I-ray exposure was performed under the conditions of (1). Then, the substrate was heated on a heating plate at 100 ℃ for 20 minutes and left to cool, thereby obtaining a cured film-attached substrate for evaluation.

The colored compositions of comparative examples 1 and 2 were applied onto a glass substrate by using a spin coater so that the thickness of the final film after drying became 2.0. mu.m,and dried on a hot plate at 100 c for 2 minutes. Then, using an ultra-high pressure mercury lamp, at an exposure illuminance of 20mW/cm²And an exposure amount of 50mJ/cm²I-ray exposure was performed under the conditions of (1). Then, the substrate was heated on a heating plate at 100 ℃ for 20 minutes and left to cool, thereby obtaining a cured film-attached substrate for evaluation.

In the production of the cured films of the examples and comparative examples, the temperature of the substrate was in the range of 20 to 100 ℃ throughout the entire process.

[ Table 2]

The raw materials listed in the above table are as follows.

(photo radical polymerization initiator)

Initiator 1: IRGACURE-OXE02 (a compound having the following structure manufactured by BASF corporation, having an absorption coefficient at 365nm in methanol of 7749 mL/gcm. corresponds to photopolymerization initiator A1.)

Initiator 2: IRGACURE-OXE01 (a compound having the following structure manufactured by BASF corporation, having an absorption coefficient at 365nm in methanol of 69669 mL/gcm. corresponds to photopolymerization initiator A1.)

Initiator 3: a compound having the following structure (having an absorption coefficient of light having a wavelength of 365nm in methanol of 18900 mL/gcm. corresponding to a photopolymerization initiator A1.)

Initiator 4: IRGACURE-2959 (a compound having the following structure manufactured by BASF corporation, having an absorption coefficient of 48.93mL/gcm at 365nm in methanol and an absorption coefficient of 3.0X 10 at 254nm⁴mL/gcm. Corresponds to the photopolymerization initiator A2. )

Initiator 5: IRGACURE-184 (a compound having the following structure manufactured by BASF corporation, having an absorption coefficient of 88.64mL/gcm at 365nm in methanol and an absorption coefficient of 3.3X 10 at 254nm⁴mL/gcm. Corresponds to the photopolymerization initiator A2. )

Initiator 6: a compound having the following structure (absorption coefficient of light having a wavelength of 365nm in methanol: 13200 mL/gcm. corresponding to photopolymerization initiator A1.)

Initiator 7: a compound of the structure

[ chemical formula 31]

(resin)

Resin A: is a resin synthesized by the following method.

A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device was charged with 70.0 parts by mass of cyclohexanone, the flask was heated to 80 ℃ and the inside of the flask was replaced with nitrogen, and then a mixture of 13.3 parts by mass of n-butyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, 4.3 parts by mass of methacrylic acid, 7.4 parts by mass of p-cumylphenol ethylene oxide-modified acrylate (TOAGOSEI co., ltd., aronii M110) and 0.4 part by mass of 2,2' -azobisisobutyronitrile was dropped through the dropping tube over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a 30 mass% solution of resin a (Mw 26000).

Resin B: is a resin synthesized by the following method.

A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas inlet tube was charged with 90.0 parts by mass of PGMEA, heated to 60 ℃ while injecting nitrogen gas into the vessel, and a mixture of 10.0 parts by mass of methacrylic acid, 45.0 parts by mass of methyl methacrylate, 45.0 parts by mass of n-butyl methacrylate, and 2.5 parts by mass of 2,2' -azobisisobutyronitrile was dropped at the same temperature over 2 hours to perform polymerization. After completion of the dropwise addition, the mixture was further reacted at 60 ℃ for 1 hour, and then 0.5 part by mass of 2,2' -azobisisobutyronitrile was dissolved in 10.0 parts by mass of PGMEA, followed by further stirring at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, it was diluted with PGMEA, thereby obtaining a solution of resin B containing an alkali-soluble functional group with a nonvolatile content of 20 mass%. The weight-average molecular weight of resin B was 27000.

(Compound having furyl group)

F1: is a compound containing a furyl group synthesized by the following method.

In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser and a gas inlet tube, 90.0 parts by mass of PGMEA was placed, and while nitrogen gas was injected into the vessel, the vessel was heated to 60 ℃, and a mixture of 50.0 parts by mass of furfuryl methacrylate, 26.7 parts by mass of 2-methacryloyloxyethylsuccinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate and 2.5 parts by mass of 2,2' -azobis (2, 4-dimethylpentanenitrile) was dropped at the same temperature over 2 hours to carry out polymerization. After completion of the dropwise addition, the reaction mixture was further reacted at 60 ℃ for 1 hour, and then 0.5 part by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of PGMEA, followed by further stirring at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the solution was diluted with PGMEA, whereby a 20 mass% solution of compound F1 containing a furyl group (Mw 52000) was obtained.

F2: is a compound containing a furyl group synthesized by the following method.

A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas inlet tube was charged with 90.0 parts by mass of PGMEA, heated to 60 ℃ while injecting nitrogen gas into the vessel, and a mixture of 50.0 parts by mass of furfuryl methacrylate, 10 parts by mass of methacrylic acid, 40.0 parts by mass of methyl methacrylate, and 5.0 parts by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added dropwise at the same temperature over 2 hours to perform polymerization. After completion of the dropwise addition, the reaction mixture was further reacted at 60 ℃ for 1 hour, and then 1.0 part by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of PGMEA, followed by further stirring at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the solution was diluted with PGMEA, whereby a 20 mass% solution of compound F2 containing a furyl group (Mw 26000) was obtained.

(radically polymerizable monomer)

M1: ARONIX M-402(TOAGOSEI co., ltd. manufactured, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

M2: a compound of the structure (a + b + c ═ 3)

[ chemical formula 32]

(solvent)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol methyl ether

(examples 24 to 36 and comparative example 3)

Using a coloring composition having the same composition as that of the coloring composition prepared in example 1, i-ray exposure was performed under various exposure illuminance, exposure amount, and environmental environment shown in table 3, respectively. The "nitrogen atmosphere" in the table is an atmosphere in which the atmosphere is replaced with nitrogen until the oxygen concentration becomes 50ppm or less. Then, the substrate was heated on a hot plate at 100 ℃ for 20 minutes, and left to cool, to obtain a cured film-attached substrate for evaluation (examples 24 to 36 and comparative example 3). In the production of the cured film of the above examples, the temperature of the substrate was 100 ℃ or lower throughout the entire process.

[ Table 3]

< examples 37 to 41 >

A cured film was produced using the coloring composition prepared by the following method in the same manner as in example 1 to obtain a substrate for evaluation (example 37). Further, by changing the content of the pigment derivative in example 37 as described in the following table 4, a coloring composition was prepared and a cured film was produced in the same manner as in example 37, thereby obtaining evaluation substrates (examples 38 to 41). In the production of the cured film of the above examples, the temperature of the substrate was 100 ℃ or lower throughout the entire process.

(coloring composition of example 37)

A mixed solution obtained by mixing the following raw materials was mixed and dispersed for 3 hours by using a bead mill (zirconia beads having a diameter of 0.1 mm), thereby preparing a pigment dispersion. Then, a high-pressure disperser NANO-3000-10(Nippon BEE Co., Ltd.) with a pressure reducing mechanism was used at a pressure of 2000kg/cm³And a flow rate of 500 g/min. This dispersion treatment was all repeated up to 10 times, thereby obtaining a pigment dispersion liquid P-B2.

Raw materials of pigment dispersion liquid P-B2:

c.i. pigment blue 15: 9.6 parts by mass of 6(PB 15: 6)

2.4 parts by mass of C.I. pigment Violet 23(PV23)

1.0 parts by mass of pigment derivative 2B

24.7 parts by mass of dispersant

82.3 parts by mass of PGMEA

Pigment derivative 2B: a compound having the structure

[ chemical formula 33]

Dispersant 2: a compound having the structure. The number attached to the main chain is the molar ratio of each repeating unit, and the number attached to the side chain is the number of repetitions of each repeating unit.

[ chemical formula 34]

Then, the mixed liquid of the following raw materials was stirred and mixed, and then filtered by using a nylon filter (manufactured by Nihon Pall ltd.) having a pore size of 0.45 μm, to obtain a colored composition of example 37.

Raw materials for the coloring composition of example 37:

254.1 parts by mass of pigment Dispersion liquid P-B

Resin 2(40 mass% PGMEA solution) 1.0 part by mass

20.9 parts by mass of a polymerizable monomer

100.6 parts by mass of photopolymerization initiator

4.2 parts by mass of surfactant 2 (1% by mass of PGMEA solution)

20.1 parts by mass of an ultraviolet absorber

20.1 parts by mass of an epoxy resin

39.0 parts by mass of PGMEA

Resin 2: a compound having the structure. The numerical value attached to the main chain represents the molar ratio of each repeating unit.

[ chemical formula 35]

Polymerizable monomer 2: a compound having the structure

[ chemical formula 36]

Photopolymerization initiator 10: a compound having the structure

[ chemical formula 37]

Surfactant 2: a mixture of two compounds each having the following structure (Mw 14000, described in mass%)

[ chemical formula 38]

Uv absorber 2: a compound having the structure

[ chemical formula 39]

Epoxy resin 2: EHPE3150 (1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2' -bis (hydroxymethyl) -1-butanol, manufactured by Daicel Corporation)

[ Table 4]

< examples 42 to 55 >

The kinds and contents of the pigment dispersion, photo radical polymerization initiator, resin, compound containing a furan group, radical polymerizable monomer and solvent were changed as described in table 5 below, and the colored compositions of examples 42 to 55 were prepared in the same manner as in example 1. The solid content concentration (mass%. described in the column of "solid content") of each coloring composition was adjusted according to the amount of the solvent to be added. In Table 6, the M/I ratio (mass ratio) and M/I are shown for each of the coloring compositions_A1Ratio (mass ratio) and pigment concentration. Then, using the colored composition prepared as described above, a cured film was produced in the same manner as in example 1 to obtain evaluation substrates (examples 42 to 55). In the production of the cured film of the above examples, the temperature of the substrate was 100 ℃ or lower throughout the entire process.

[ Table 6]

In table 5, the specifications of the raw materials newly shown are as follows.

(resin)

Resin C: a solution obtained by dissolving a compound having the following structure (Mw 11000) in PGMEA. The amount of the solid component was 30% by mass. The number of the label on the main chain represents the molar ratio of each repeating unit.

[ chemical formula 40]

Resin PA-1: this is the same solution as that of the resin PA-1 described above for the pigment dispersion.

(radically polymerizable monomer)

M3: a compound having the structure

[ chemical formula 41]

M4: a compound having the structure

[ chemical formula 42]

M5: a compound having the structure

[ chemical formula 43]

(additives)

E1: EPICLON N-695(DIC Corporation)

E2: EHPE3150 (manufactured by Daicel Corporation)

(surfactant)

G1: MEGAFACE F-781F (DIC Corporation)

G2: KF-6001(Shin-Etsu Chemical Co., Ltd.) < examples 56 to 86 >

Preparation of pigment dispersion

As shown in table 7, after uniformly stirring and mixing the mixture of each composition, various pigment dispersions were produced in the same manner as in the case of the pigment dispersions P to R.

[ Table 7]

In table 7 above, the specifications of the raw materials are as follows.

(coloring agent)

PR 177: c.i. pigment red 177

PR 254: c.i. pigment red 254

PY 139: c.i. pigment yellow 139

PY 150: c.i. pigment yellow 150

PY 185: c.i. pigment yellow 185

PG 7: c.i. pigment green 7

PG 36: c.i. pigment green 36

PB15: 6: C.I. pigment blue 15:6

PV 23: c.i. pigment violet 23

(pigment derivative)

Pigment derivative 3: a compound having the structure.

[ chemical formula 44]

Pigment derivative 4: a compound having the structure.

[ chemical formula 45]

(dispersing agent)

Resin M: a compound having the structure. The numerical values attached in parentheses indicate the number of repetitions of the repeating unit.

[ chemical formula 46]

Resin N: a compound having the structure. The number attached to the brackets of the main chain represents the molar ratio of each repeating unit, and the number attached to the brackets of the side chain represents the number of repeating units. Weight average molecular weight 24000.

[ chemical formula 47]

Resin O: a compound having the structure. The numerical values enclosed in parentheses indicate the molar ratio of the respective repeating units. The weight average molecular weight is 11000.

[ chemical formula 48]

Dispersant D: DISPERBYK-161, BYK-Chemie GmbH.

Preparation of colored composition and production of cured film

The raw materials shown in tables 8 to 10 below were mixed and stirred, and then filtered using a nylon filter (manufactured by Nihon Pall Ltd.) having a pore size of 0.45 μm, thereby preparing colored compositions of examples 56 to 86. The contents in the table are expressed in parts by mass. The solid content concentration (mass%. described in the column of "solid content") of each coloring composition was adjusted according to the amount of the solvent to be added. In Table 11, the M/I ratio (mass ratio) and M/I are shown for each of the coloring compositions_A1A ratio (mass ratio) and a pigment concentration (mass%: a ratio of the content of the pigment to the amount of the solid component). Then, a cured film was produced using the coloring composition prepared as described above by the same method as in example 1 to obtain a substrate for evaluation (Examples 56 to 86).

In the production of the cured film of the above examples, the temperature of the substrate was 100 ℃ or lower throughout the entire process.

[ Table 11]

The raw materials described in tables 8 to 10 are as follows.

(photopolymerization initiator)

1-4% of an initiator: the photo radical polymerization initiators were the same types as the initiators 1 to 4 described in Table 1.

(resin)

Resin A: the resin was the same type as the resin a described in table 1.

Resin C: the resin C was the same kind of resin as the resin C described in table 5.

Resin D: a solution obtained by dissolving a compound having the following structure (Mw 12000) in PGMEA. The amount of the solid component was 30% by mass. The numerical value attached to the main chain represents the molar ratio of each repeating unit.

[ chemical formula 49]

Resin E: a solution obtained by dissolving a compound having the following structure (Mw 14000) in PGMEA. The amount of the solid component was 30% by mass. The numerical value attached to the main chain represents the molar ratio of each repeating unit.

[ chemical formula 50]

(Compound having furyl group)

F1: is the same kind of compound as the furyl group-containing compound F1 described in connection with table 1.

(radically polymerizable monomer)

M4: the monomer is the same as the radical polymerizable monomer M4 described in table 5.

M6: a compound having the structure.

[ chemical formula 51]

M7: 3-Ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } oxetane (TOAGOSEI CO., LTD. manufactured by OXT-221).

M8: methyl (3-ethyloxetan-3-yl) methacrylate (Ube Industries, Ltd., ETERNACOLL OXMA).

(surfactant)

G1, G2: the surfactants were the same types as the surfactants G1 and G2 described in table 5.

(solvent)

PGMEA: propylene glycol monomethyl ether acetate

CyH: cyclohexanone

BA: acetic acid butyl ester

< evaluation of stability of spectroscopic characteristics >

The cured film was subjected to a high temperature and high humidity test of exposure to 85% at 85 ℃ for 1000 hours, and the spectral transmittances before and after the test were measured. Then, the transmittance change rate was calculated for each measurement wavelength in the wavelength range of 400 to 1100nm, and the maximum value of these change rates was used as an index to evaluate the transmittance as described below. The evaluation results are shown in tables 2 to 4 and 6. When the evaluation value is 2 or more, the stability as spectral characteristics is better than the conventional level.

5: the index change rate is 1% or less.

4: the index change rate is greater than 1% and not more than 2%.

3: the index change rate is greater than 2% and not more than 3%.

2: the index change rate is greater than 3% and not more than 4%.

1: the change rate of the index is more than 4%.

As shown in tables 2 to 4,6 and 11, the cured films formed using the colored compositions of the examples had excellent stability of spectral characteristics.

As a result, for example, by incorporating a color filter formed using the colored composition of the present invention into an organic electroluminescent display device, an organic electroluminescent display device having excellent stability of display performance can be obtained.

Further, as is clear from comparison between example 2 and example 4, the resin a having a structure derived from the compound represented by the following formula (III), more specifically, having a p-cumylphenol group contributes more to the stability of the spectral characteristics of the cured film.

Further, from the results of example 13 and example 14, it is understood that even when the specific photopolymerization initiator a1 and the specific photopolymerization initiator a2 are used in combination, a composition excellent in stability of the spectral characteristics of the cured film can be obtained.

Further, from the results of examples 37 to 40, it is understood that the composition having more excellent stability can be obtained by setting the content of the pigment derivative to 0.5 parts by mass or less relative to the pigment in the dispersion liquid.