Color material dispersion liquid, colored resin composition, cured product thereof, color filter, and display device

文档序号：555117 发布日期：2021-05-14 浏览：31次中文

阅读说明：本技术 色材分散液、着色树脂组合物及其固化物、彩色滤色器及显示装置 (Color material dispersion liquid, colored resin composition, cured product thereof, color filter, and display device ) 是由大友知亚纪冈田政人小仓教弘伊藤阳平和田榛奈于 2019-09-04 设计创作，主要内容包括：本发明提供一种色材分散液,其即便将规定的色淀色材与酞菁颜料在所期望的范围内混合,分散性与保存稳定性仍优异,且能够形成基板密合性与涂膜均匀性提高的着色层。本发明的色材分散液含有色材、酸性分散剂及溶剂,色材包含特定的色淀色材及经碱性处理的酞菁颜料,且上述酸性分散剂包含具有特定的酸性磷化合物基及其盐的聚合物。(The invention provides a color material dispersion liquid, which has excellent dispersibility and storage stability even if a prescribed color lake material and a phthalocyanine pigment are mixed in a desired range, and can form a colored layer with improved substrate adhesion and coating uniformity. The color material dispersion liquid of the present invention contains a color material, an acidic dispersant and a solvent, wherein the color material contains a specific lake color material and a phthalocyanine pigment subjected to alkali treatment, and the acidic dispersant contains a polymer having a specific acidic phosphorus compound group and a salt thereof.)

1. A color material dispersion liquid comprising a color material, an acidic dispersant and a solvent,

the color material comprises at least 1 kind of lake color material selected from the group consisting of color material represented by the following general formula (1) and color material represented by the following general formula (2), and phthalocyanine pigment treated by alkali,

the acidic dispersant comprises at least 1 polymer having a structural unit selected from the group consisting of those represented by the following general formula (I),

in the general formula (1), A is an a-valent organic group which does not have pi bonds with carbon atoms directly bonded with N, the organic group represents an aliphatic hydrocarbon group which has a saturated aliphatic hydrocarbon group at least at the end directly bonded with N, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain optionally contains heteroatoms; b is^c-Represents a polyacid anion having a valence of c; rⁱ～R^vEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vOptionally bonded to form a ring structure; r^viAnd R^viiEach independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group; ar (Ar)¹Represents a 2-valent aromatic group optionally having a substituent; there are a plurality of Rⁱ～R^viiAnd Ar¹Are respectively the same or different;

a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, and no bond is present when e is 0; f and g represent integers of 0 to 4 inclusive, and f + e and g + e are 0 to 4 inclusive; a plurality of e, f and g are the same or different;

in the general formula (2), R^I～R^VIEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R^IAnd R^II、R^IIIAnd R^IV、R^VAnd R^VIOptionally bonded to form a ring structure; r^VIIAnd R^VIIIEach independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group; ar (Ar)²Represents an optionally substituted 2-valent aromatic heterocyclic group, wherein R is present in plural^I～R^VIIIAnd Ar²Are respectively the same or different; e^m-Represents a polyacid anion having a valence of m;

m represents an integer of 2 or more; j is 0 or 1, and no bond is present when j is 0; k and l represent integers of 0 to 4 inclusive, and k + j and l + j are 0 to 4 inclusive; a plurality of j, k and 1 are the same or different;

in the general formula (I), L¹Is a direct bond or a 2-valent linking group, R¹Is a hydrogen atom or a methyl group, R²Is hydroxy, hydrocarbyl, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵or-O-R⁶A 1-valent group represented by, R⁶Is a hydrocarbyl radical, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵、-C(R⁷)(R⁸)-C(R⁹)(R¹⁰) -OH, or-CH₂-C(R¹¹)(R¹²)-CH₂-1-valent group represented by-OH;

R³and R⁴Each independently is a hydrogen atom or a methyl group, R⁵Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO、-CO-CH＝CH₂、-CO-C(CH₃)＝CH₂or-CH₂COOR¹³A 1-valent group represented by, R¹³Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; r⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having 1 or more kinds selected from an ether bond and an ester bond, R⁷And R⁹Optionally bonded to each other to form a ring structure; in the case of forming the cyclic structure, the cyclic structure optionally further has a substituent R¹⁴，R¹⁴Is a hydrocarbon group or a hydrocarbon group having 1 or more kinds selected from an ether bond and an ester bond; the hydrocarbon group optionally has a substituent; x represents a hydrogen atom or an organic cation; x1 represents an integer of 1 to 18 inclusive, y1 represents an integer of 1 to 5 inclusive, and z1 represents an integer of 1 to 18 inclusive.

2. The colorant dispersion liquid according to claim 1, wherein the content of the lake material is 20 mass% or more and 85 mass% or less with respect to the total content of the lake material and the phthalocyanine pigment.

3. The color material dispersion liquid according to claim 1 or 2, wherein the acidic dispersant further comprises a block copolymer containing: an A block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block comprising structural units derived from an alkyl (meth) acrylate.

4. A colored resin composition comprising a coloring material, an acidic dispersant, a binder component and a solvent,

the acidic dispersant comprises at least 1 polymer having a structural unit selected from the group consisting of those represented by the following general formula (I),

5. The colored resin composition according to claim 4, wherein the content of the lake material is 20 mass% or more and 85 mass% or less with respect to the total content of the lake material and the phthalocyanine pigment.

6. The colored resin composition according to claim 4 or 5, wherein the binder component comprises an alkali-soluble resin, a photopolymerizable compound and a photoinitiator, and the binder component is photosensitive.

7. The colored resin composition according to any one of claims 4 to 6, wherein the acidic dispersant further comprises a block copolymer containing: an A block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block comprising structural units derived from an alkyl (meth) acrylate.

8. A cured product of the colored resin composition according to any one of claims 4 to 7.

9. A color filter at least comprises a transparent substrate and a coloring layer provided on the transparent substrate,

at least one of the colored layers contains a color material containing at least 1 kind of lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2), and a phthalocyanine pigment subjected to alkaline treatment, and an acidic dispersant containing at least 1 kind of polymer having a structural unit selected from the group represented by the following general formula (I),

in the general formula (1), A is an a-valent organic group having no pi bond with a carbon atom directly bonded to N, and theThe organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain optionally contains a hetero atom; b is^c-Represents a polyacid anion having a valence of c; rⁱ～R^vEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vOptionally bonded to form a ring structure; r^viAnd R^viiEach independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group; ar (Ar)¹Represents a 2-valent aromatic group optionally having a substituent; there are a plurality of Rⁱ～R^viiAnd Ar¹Are respectively the same or different;

10. The color filter according to claim 9, wherein the content of the lake material is 20 mass% or more and 85 mass% or less with respect to the total content of the lake material and the phthalocyanine pigment.

11. The color filter according to claim 9 or 10, wherein the acidic dispersant further comprises a block copolymer containing: an A block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block comprising structural units derived from an alkyl (meth) acrylate.

12. A display device comprising the color filter according to any one of claims 9 to 11.

Technical Field

The present invention relates to a coloring material dispersion liquid, a coloring resin composition and a cured product thereof, a color filter and a display device.

Background

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (cell phones, smart phones, tablet PCs) has also increased, and the market for liquid crystal displays is expanding. In recent years, an organic light emitting display device such as an organic EL (Electroluminescence) display, which has high visibility by self-light emission, has been attracting attention as a next-generation image display device. Among the performances of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility is desired.

Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, in the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the colors of the respective pixels constituting the color filter, and the light of these colors is synthesized to form a color image. In this case, the light source may be an organic light emitting element emitting white light or an inorganic light emitting element emitting white light, in addition to the conventional cold cathode tube. In addition, in the organic light emitting display device, a color filter is used for color adjustment and the like.

In recent years, there has been a demand for power saving of image display devices, and in particular, for high luminance of color filters in order to improve the utilization efficiency of backlights. In particular, it is a major problem in mobile displays (mobile phones, smart phones, and tablet PCs).

Here, the color filter generally has: a substrate; a colored layer formed on the substrate and including a colored pattern of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate so as to partition each of the colored patterns.

As a method for forming such a colored layer, there are known: a method of applying a colored resin composition obtained by adding a curable binder component or the like to a colored material dispersion liquid in which a colored material is dispersed, to a substrate and curing the composition.

The color material dispersion liquid is required to have dispersibility and storage stability of the color material in order to stably obtain a colored layer having a high contrast. In addition, in response to the demand for higher contrast and higher brightness of color filters, studies have been made to use finely divided pigments as color materials, or to use dyes or lake materials having higher transmittance as color materials. A colored layer obtained from such a color material dispersion may have inferior various resistances in the production process, compared to a case where only a pigment is used.

Patent document 1 discloses a color filter using a specific color material containing a plurality of cations having a valence of 2 or more, which are crosslinked by a crosslinking group, and anions having a valence of 2 or more, and the like. It is described that: the color material has excellent heat resistance, and a color filter using the color material has high contrast, solvent resistance and excellent electrical reliability.

Patent document 2 discloses a color material dispersion liquid obtained by combining a color material, a polymer containing a structural unit having a specific acidic phosphorus compound group, and at least 2 solvents of a relatively high-polarity solvent and a relatively low-polarity solvent as solvents. It is described that: the color material dispersion liquid is excellent in dispersibility and storage stability, and can form a coating film having high contrast and excellent heat resistance and solvent resistance even after long-term storage. In addition, patent document 2 describes a color material dispersion liquid obtained by mixing a lake color material corresponding to a specific color material of patent document 1 with commercially available pigment blue15:6 at a mass ratio of 90: 10, and dispersing the color material with either a polymer containing a structural unit having a specific acid phosphorus structure or an alkaline dispersant, in example 17 and comparative examples 25 and 26.

Prior art documents

Patent document

Patent document 1: international publication No. 2012/144521

Patent document 2: japanese patent laid-open No. 2017-

Disclosure of Invention

Problems to be solved by the invention

However, even when the specific color material of patent document 1 is used, since the heat resistance is inferior to that of the pigment, the chromaticity is likely to change even after high-temperature heating (post-baking) in the color filter manufacturing process, and the luminance of the finally obtained colored layer is still insufficient, and further improvement is required.

The present inventors considered that a lake material such as the specific color material of patent document 1 is mixed with a pigment and used for suppressing the change in chromaticity after heating at a high temperature and improving the luminance of a colored layer to be finally obtained. However, as shown in patent document 2, when a lake material such as the specific lake material of patent document 1 is mixed with a phthalocyanine pigment such as pigment blue15:6 which is commercially available in large quantities, if the content of the phthalocyanine pigment is more than 10 parts by mass relative to 100 parts by mass of the total of the lake material and the phthalocyanine pigment, the dispersibility and the storage stability are remarkably deteriorated, and therefore, the content of the phthalocyanine pigment cannot be increased, and it is difficult to produce a colored resin composition by mixing the specific lake material and the phthalocyanine pigment within a desired range.

In addition, in the colored layer of the prior art described in patent document 2, the substrate adhesion and the coating film uniformity are not sufficient, and further improvement of the substrate adhesion and the coating film uniformity is required.

The present invention has been made based on the above-mentioned findings, and an object thereof is to provide a color material dispersion liquid and a colored resin composition which are excellent in dispersibility and storage stability and can form a colored layer having improved substrate adhesion and coating film uniformity even when a predetermined lake material and a phthalocyanine pigment are mixed within a desired range, a color filter having the colored layer, and a display device having excellent display characteristics using the color filter.

Means for solving the problems

The color material dispersion liquid of the present invention contains a color material, an acidic dispersant and a solvent,

the acidic dispersant contains at least 1 polymer selected from structural units represented by the following general formula (I).

[ solution 1]

General formula (1)

(in the general formula (1), each symbol is as follows)

[ solution 2]

General formula (2)

(in the general formula (2), each symbol is as follows)

[ solution 3]

(in the general formula (I), each symbol is as follows)

The colored resin composition of the present invention comprises a coloring material, an acidic dispersant, a binder component and a solvent,

the color material comprises at least 1 kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), and phthalocyanine pigment treated by alkali,

the acidic dispersant contains at least 1 polymer selected from the structural units represented by the general formula (I).

The present invention provides a cured product of the colored resin composition of the present invention.

The present invention provides a color filter, at least comprising a substrate and colored layers arranged on the substrate, wherein at least one of the colored layers comprises a color material and an acidic dispersant, the color material comprises at least 1 lake color material selected from the group consisting of a color material represented by the general formula (1) and a color material represented by the general formula (2), and a phthalocyanine pigment subjected to alkaline treatment, and the acidic dispersant comprises at least 1 polymer having a structural unit selected from the group represented by the general formula (I).

The present invention provides a display device having the color filter of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a color material dispersion liquid and a colored resin composition which are excellent in dispersibility and storage stability even when a predetermined lake material and a phthalocyanine pigment are mixed within a desired range and which are capable of forming a colored layer having improved substrate adhesion and coating film uniformity, a color filter provided with the colored layer, and a display device having excellent display characteristics using the color filter.

Brief description of the drawings

Fig. 1 is a schematic view showing an example of a color filter of the present invention.

Fig. 2 is a schematic view showing an example of the display device of the present invention.

Fig. 3 is a schematic view showing another example of the display device of the present invention.

Detailed Description

The color material dispersion liquid, the colored resin composition, the color filter, and the display device of the present invention will be described in detail in this order.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions and radiation, and radiation includes microwaves and electron beams, for example. Specifically, it refers to electromagnetic waves having a wavelength of 5 μm or less, and electron beams.

In the present invention, the (meth) acrylic acid means each of acrylic acid and methacrylic acid, and the (meth) acrylate means each of acrylate and methacrylate.

In the present specification, "to" indicating a numerical range is used in a meaning including numerical values described before and after the range as a lower limit value and an upper limit value.

I. Color material dispersion liquid

The color material dispersion liquid of the present invention contains a color material, an acidic dispersant and a solvent,

the acidic dispersant contains at least 1 polymer selected from structural units represented by the following general formula (I).

[ solution 4]

General formula (1)

(in the general formula (1), A is an a-valent organic group having no pi bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain optionally contains a hetero atom; B^c-Represents a polyacid anion having a valence of c. R¹～R^vEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vOptionally bonded to form a ring structure. R^viAnd R^viiEach independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. Ar (Ar)¹Represents a 2-valent aromatic group optionally having a substituent; there are a plurality of Rⁱ～R^viiAnd Ar¹Respectively, the same or different.

a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, no bond is present. f and g each represents an integer of 0 to 4 inclusive, and f + e and g + e are 0 to 4 inclusive. There are a plurality of e, f and g, each of which may be the same or different. )

[ solution 5]

General formula (2)

(in the general formula (2), R^I～R^VIEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R^IAnd R^II、R^IIIAnd R^IV、R^VAnd R^VIOptionally bonded to form a ring structure. R^VIIAnd R^VIIIEach independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. Ar (Ar)²Represents an optionally substituted 2-valent aromatic heterocyclic group, wherein R is present in plural^I～R^VIIIAnd Ar²Respectively, the same or different. E^m-Represents a polyacid anion having a valence of m.

m represents an integer of 2 or more. j is 0 or 1, and when j is 0, no bond is present. k and l each represents an integer of 0 to 4, and k + j and l + j are 0 to 4. There are a plurality of j, k and 1, which are the same or different, respectively. )

[ solution 6]

(in the general formula (I), L¹Is a direct bond or a 2-valent linking group, R¹Is a hydrogen atom or a methyl group, R²Is hydroxy, hydrocarbyl, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵or-O-R⁶A 1-valent group represented by, R⁶Is a hydrocarbyl radical, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵、-C(R⁷)(R⁸)-C(R⁹)(R¹⁰) -OH, or-CH₂-C(R¹¹)(R¹²)-CH₂A 1-valent group represented by-OH.

R³And R⁴Each independently is a hydrogen atom or a methyl group, R⁵Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO、-CO-CH＝CH₂、-CO-C(CH₃)＝CH₂or-CH₂COOR¹³A 1-valent group represented by, R¹³Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having 1 or more kinds selected from an ether bond and an ester bond, R⁷And R⁹Optionally bonded to each other to form a ring structure. In the case of forming the cyclic structure, the cyclic structure optionally further has a substituent R¹⁴，R¹⁴Is a hydrocarbon group or a hydrocarbon group having 1 or more kinds selected from ether bonds and ester bonds. The hydrocarbon group optionally has a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 to 18 inclusive, y1 represents an integer of 1 to 5 inclusive, and z1 represents an integer of 1 to 18 inclusive. )

The color material dispersion liquid according to the embodiment of the present invention is excellent in dispersibility and storage stability even when a predetermined lake material and a phthalocyanine pigment are mixed in a desired range, and can form a colored layer having improved substrate adhesion and coating film uniformity. Further, according to the color material dispersion liquid of the embodiment of the present invention, even when a predetermined lake material and a phthalocyanine pigment are mixed in a desired range, a colored resin composition which is excellent in dispersibility and storage stability and can form a colored layer having improved substrate adhesion and coating film uniformity can be obtained.

As shown in comparative example 4 below, a phthalocyanine pigment such as pigment blue15:6, which is commercially available in large quantities, is inferior in dispersibility and storage stability when at least 1 polymer having a structural unit selected from those represented by the above general formula (I) is used as a dispersant. When at least 1 polymer selected from the structural units represented by the above general formula (I) is used as a dispersant, even in the case of mixing a lake material with a commercially available phthalocyanine pigment distributed in a large amount, as shown in comparative example 5 below, the dispersibility or storage stability is significantly deteriorated by only slightly increasing the content of the phthalocyanine pigment, and therefore, it is not possible to increase the content of the phthalocyanine pigment to a large extent, and it is difficult to produce a colored resin composition by mixing a lake material such as the specific color material of patent document 1 with a phthalocyanine pigment in a desired range.

In contrast, in the present invention, by combining a phthalocyanine pigment subjected to alkali treatment with at least 1 lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2) and using an acidic dispersant containing at least 1 polymer having a structural unit selected from the group represented by the above general formula (I) as a dispersant, a color material dispersion liquid excellent in dispersibility and storage stability can be obtained even when a predetermined lake color material and the phthalocyanine pigment are mixed within a desired range. And (3) presuming: the reason why the alkali-treated phthalocyanine pigment is excellent in dispersibility and storage stability when used in combination is that the cationic moiety derived from the basic compound present on the surface of the phthalocyanine pigment particularly strongly adsorbs the acidic group of the acidic dispersant. In addition, it is estimated that: since the lake material is also a salt-forming compound, the adsorption with the acidic group of the acidic dispersant is strong. And (3) presuming: since both the lake material and the alkali-treated phthalocyanine pigment are favorably coated with the dispersant, the dispersibility and the storage stability are excellent even when the pigment is mixed in a desired range.

Further, a colored layer having improved substrate adhesion and coating film uniformity can be formed by combining a phthalocyanine pigment subjected to alkali treatment with at least 1 type of lake color material selected from the group consisting of color materials represented by the following general formula (1) and color materials represented by the following general formula (2), and using an acidic dispersant containing at least 1 type of polymer selected from structural units represented by the above general formula (I) as a dispersant. As this action, it is assumed that: among them, the alkali-treated phthalocyanine pigment and the acidic dispersant have a strong adsorption effect on the acidic group, so that the pigment surface is uniformly coated with the acidic dispersant, whereby the dispersibility of the coloring material is improved, the viscosity of the coloring material dispersion liquid or the resin composition is lowered, and the fluidity of the resin composition is improved, whereby a uniform coating film can be easily formed, and the uniformity of the coating film is also improved. In addition, it is estimated that: when the dispersant has an acidic group such as a phosphoric group or a carboxylic group, the dispersant is easily bonded not only to the surface of the coloring material but also to a polar group on the surface of the substrate (for example, an Si — OH group on the surface of the glass substrate), whereby the substrate adhesion is improved.

The color material dispersion liquid of the present invention contains at least a color material, an acidic dispersant and a solvent, and may optionally contain other components within a range not impairing the effect.

The respective components of the color material dispersion liquid are described in detail below.

[ color material ]

In the present invention, the following features are provided: the color material includes at least 1 kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), and the phthalocyanine pigment subjected to alkali treatment.

< the above lake Material >

The lake materials used in the present invention are at least 1 kind of lake material selected from the group consisting of the lake materials represented by the above general formula (1) and the lake materials represented by the above general formula (2).

Since the color material represented by the above general formula (1) contains anions having a valence of 2 or more and cations having a valence of 2 or more, in the aggregate of the color material, the anions and the cations are not ionically bonded to 1 molecule only by 1 molecule, but a molecular association body in which a plurality of molecules are associated via ionic bonds is formed, and therefore the apparent molecular weight is significantly increased as compared with the molecular weight of the conventional lake pigment. And (3) presuming: by forming such a molecular association, the cohesive force in a solid state is further increased, thermal motion is reduced, dissociation of an ion pair or decomposition of a cation portion can be suppressed, and discoloration is less likely to occur than in the case of a conventional lake pigment.

In the general formula (1), a is an a-valent organic group having no pi bond to a carbon atom directly bonded to N (nitrogen atom), and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom such as O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain. That is, the organic group means an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N and may contain a heteroatom such as O, S, N in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group at the end directly bonded to N and may contain a heteroatom such as O, S, N in the carbon chain. Since the carbon atom directly bonded to N does not have a pi bond, the color characteristics such as hue and transmittance of the cationic color-developing site are not affected by the linking group a or other color-developing sites, and the same color as that of the monomer can be maintained.

In a, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be any of a linear, branched or cyclic group as long as the terminal carbon atom directly bonded to N does not have a pi bond, the carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and may contain O, S, N in the carbon chain. For example, the compound may contain a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc., and the hydrogen atom may be further substituted with a halogen atom, etc.

In addition, in a, the aromatic group having the aliphatic hydrocarbon group may be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, may have a substituent, or may be a heterocyclic ring containing O, S, N.

Among them, a preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group in terms of the fastness of the skeleton.

Examples of the cyclic aliphatic hydrocarbon group include: comprising cyclohexane, cyclopentane, norbornane, bicyclo [2.2.2]Octane, tricyclo [5.2.1.0^2，6]Decane, adamantane, etc. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring. For example, when A is a 2-valent organic group, there may be mentioned an aromatic group obtained by substituting 2 carbon-1 to 20 alkylene groups such as a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms and xylylene group.

In the present invention, in terms of satisfying both the fastness and the degree of freedom of molecular motion and improving the heat resistance, a is preferably an aliphatic hydrocarbon group having 2 or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at the end directly bonded to N, and optionally containing O, S, N in the carbon chain. A is more preferably an aliphatic hydrocarbon group having 2 or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the end directly bonded to N, and containing O, S, N in the carbon chain, and is still more preferably a structure in which 2 or more cyclic aliphatic hydrocarbon groups are linked by a straight-chain or branched aliphatic hydrocarbon group.

The cyclic aliphatic hydrocarbon group having 2 or more atoms may be the same or different, and examples thereof include the same cyclic aliphatic hydrocarbon groups as those described above, and cyclohexane and cyclopentane are preferable.

In the present invention, among them, a is preferably a substituent represented by the following general formula (1a) in terms of heat resistance.

[ solution 7]

General formula (1a)

(in the general formula (1a), R^xiRepresents a C1-3 arylene group which may have an alkyl group having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms as a substituentAlkyl radical, R^xiiAnd R^xiiiEach independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p represents an integer of 1 to 3, and q and r each independently represents an integer of 0 to 4; at R^xi、R^xii、R^xiiiAnd when R is plural, R is plural^xi、R^xii、R^xiiiAnd r are the same or different respectively)

In terms of excellent compatibility between the fastness and the thermal motion of the color-developed part and improved heat resistance, R is preferably R^xiAn alkylene group having 1 to 3 carbon atoms in the molecule. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, and among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and the alkyl group may be straight or branched.

The alkoxy group having 1 to 4 carbon atoms includes methoxy, ethoxy, propoxy and butoxy, and may be straight or branched.

As R^xiiAnd R^xiiiIn the above-mentioned groups, the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are the same as those mentioned for R^xiThe same substituents may be present.

In the general formula (1a), in terms of heat resistance, the cyclohexane (cyclohexylene) is preferably 2 or more and 4 or less, that is, p is 1 or more and 3 or less, and more preferably p is 1 or more and 2 or less.

In addition, a substituent R of cyclohexylene group^xiiAnd R^xiiiThe number of substitution (b) is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, in terms of heat resistance. That is, q and r are preferably integers of 1 to 3, and more preferably integers of 1 to 2.

Preferred examples of the linking group a include the following, but are not limited thereto.

[ solution 8]

Rⁱ～R^vThe alkyl group in (1) is not particularly limited. Examples thereof include C1-20 linear, branched or cyclic alkyl groups, among which C1-8 linear or branched alkyl groups, and in terms of brightness and heat resistance, C1-5 linear or branched alkyl groups, and Rⁱ～R^vThe alkyl group in (1) is ethyl or methyl. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like, and examples thereof include an aralkyl group such as a benzyl group, and the like.

Rⁱ～R^vThe aryl group in (1) is not particularly limited. Examples thereof include phenyl and naphthyl. Examples of the substituent which the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group.

Wherein, in terms of chemical stability, as Rⁱ～R^vPreferably, each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vBonding to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

In terms of heat resistance, R is preferredⁱⁱ～R^vAt least one of them is a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. Consider that: by reacting Rⁱⁱ～R^vAt least one of them has a cycloalkyl group or an aryl group, and the intermolecular interaction due to steric hindrance is reduced, so that the influence of the color-developed site on heat can be suppressed, and thus the heat resistance is excellent.

In terms of heat resistance, R is preferredⁱⁱ～R^vAt least one of the substituents is a substituent represented by the following general formula (1b) or the following general formula (1 c).

[ solution 9]

General formula (1b)

(in the general formula (1b), R^xiv、R^xvAnd R^xviEach independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent. )

[ solution 10]

General formula (1c)

(in the general formula (1c), R^xvii、R^xviiiAnd R^xixEach independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent. )

As R^xiv、R^xv、R^xvi、R^xvii、R^xviiiAnd R^xixThe alkyl group having 1 to 4 carbon atoms in (b) includes methyl, ethyl, propyl and butyl groups, and may be linear or branched. The alkoxy group having 1 to 4 carbon atoms includes methoxy, ethoxy, propoxy and butoxy, and may be straight or branched.

Examples of the substituent that the alkyl group and the alkoxy group may have include a halogen atom and a hydroxyl group.

When the substituent represented by the above general formula (1b) is present, R is preferably R in terms of heat resistance^xiv、R^xvAnd R^xviAt least one of (A) and (B) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, more preferably R^xivAnd R^xvAt least one of the above groups is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

In the case where the substituent represented by the above general formula (1c) is present, R is preferably R in terms of heat resistance^xvii、R^xviiiAnd R^xixAt least one of (A) and (B) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, more preferably R^xviiAnd R^xviiiAt least one of the above groups is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

Preferred specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include the following, but are not limited thereto.

[ solution 11]

R^viAnd R^viiEach independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. As R^viAnd R^viiThe alkyl group in (b) is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and the alkyl group may be straight or branched. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.

In addition, as R^viAnd R^viiThe alkoxy group in (b) is not particularly limited, and preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. The alkoxy group having 1 to 4 carbon atoms includes methoxy, ethoxy, propoxy and butoxy groups, and may be straight or branched. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.

As R^viAnd R^viiExamples of the halogen atom in (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R^viAnd R^viiThe number of substitution(s) of (a), i.e., f and g, each independently represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1. The plurality of f and g may be the same or different.

In addition, R^viAnd R^viiAny part of the aromatic ring having a resonance structure which may be substituted in the triarylmethane skeleton or the xanthene skeleton is preferably-NRⁱⁱRⁱⁱⁱor-NR^ivR^vThe substitution position of the amino group shown is in the meta position.

Ar¹The 2-valent aromatic group in (1) is not particularly limited. Ar (Ar)¹The aromatic group in (1) may be a heterocyclic group, in addition to a carbocyclic aromatic hydrocarbon group. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, there can be mentioned: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and the like. The chain polycyclic hydrocarbon may have O, S, N in the chain skeleton, as in diphenyl ether and the like. On the other hand, as the heterocyclic ring in the heterocyclic group, there can be mentioned: 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocyclic rings such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine; condensed polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline, and the like. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted with these, or the like as a substituent.

In 1 molecule, there are a plurality of Rⁱ～R^viiAnd Ar¹The same or different. By Rⁱ～R^viiAnd Ar¹Can be adjusted to a desired color.

The valence a in A is the number of cation sites constituting the color former of the cation, and a is an integer of 2 or more. In this lake material, the cation has a valence a of 2 or more, and therefore, the heat resistance is excellent, and among these, the cation has a valence a of 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of production.

The molecular weight of the cation represented by the general formula (a) is preferably 1200 or more, and more preferably 1300 or more, from the viewpoint of excellent heat resistance and easy suppression of color change during heating.

In the color material represented by the general formula (1), the anion part (B)^c-) The anion is a polyacid anion having a valence of c and is an anion having a valence of 2 or more, in terms of high brightness and excellent heat resistance.

The polyacid anion obtained by condensing a plurality of oxo acids may be an isopoly acid anion (M)_mO_n)^c-Can also be heteropolyacid anions (X)_lM_mO_n)^c-. In the above ionic formula, M represents a polyatomic atom, X represents a heteroatom, M represents a composition ratio of polyatomic atoms, and n represents a composition ratio of oxygen atoms. Examples of the polyatomic atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co. In addition, Na may be partially contained⁺Or H⁺And the like counter cations.

Among them, a polyacid having 1 or more elements selected from tungsten (W) and molybdenum (Mo) is preferable in terms of excellent heat resistance.

Examples of such a polyacid include: tungstate radical ion [ W ] as isopoly acid₁₀O₃₂]^4-Molybdate ion [ Mo ]₆O₁₉]^2-Phosphotungstic acid radical ion [ PW ] as heteropoly acid₁₂O₄₀]^3-、[P₂W₁₈O₆₂]^6-Silicotungstic acid radical ion [ SiW₁₂O₄₀]^4-Phosphomolybdate ion [ PMo ]₁₂O₄₀]^3-Silicomolybdate radical ion [ SiMo ]₁₂O₄₀]^4-Phosphotungstomolybdate ion [ PW_12-sMo_sO₄₀]^3-(s is an integer of 1 to 11) and [ P ]₂W_18-tMo_tO₆₂]^6-(t is an integer of 1 to 17) and silicotungstomolybdate ion[SiW_12-uMo_uO₄₀]^4-(u is an integer of 1 to 11) and the like. Among the polyacids containing at least 1 of tungsten (W) and molybdenum (Mo), heteropoly acids are preferable, and heteropoly acids containing phosphorus (P) are more preferable, from the viewpoint of heat resistance and easiness of raw material acquisition.

In addition, in terms of heat resistance, phosphotungstic molybdate ion [ PW ] is more preferable₁₀Mo₂O₄₀]^3-、[PW₁₁Mo₁O₄₀]^3-Phosphotungstic acid radical ion [ PW₁₂O₄₀]^3-Any of the above.

In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular association, and b and d represent integers of 1 or more. When b is 2 or more, the number of cations present in the molecular association may be 1 or 2 or more. When d is 2 or more, the number of anions present in the molecular association may be 1 kind alone or 2 or more kinds in combination.

In the general formula (1), e is an integer of 0 or 1, and when e is 0, no bond is present. e-0 represents a triarylmethane skeleton, and e-1 represents a xanthene skeleton. There are a plurality of e which are the same or different. In the lake material represented by the general formula (1) used in the present invention, one containing at least a triarylmethane skeleton is suitably used.

The lake material represented by the general formula (1) can be produced, for example, by referring to the pamphlet of international publication No. 2012/144520 and the pamphlet of international publication No. 2018/003706.

On the other hand, in the general formula (2), R^I～R^VIEach independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R^IAnd R^II、R^IIIAnd R^IV、R^VAnd R^VIMay be bonded to form a ring structure. R^I～R^VIEach of which is as defined above for R of formula (1)ⁱ～R^vThe same is true.

In the general formula (2), R^VIIAnd R^VIIIEach is independentAnd (b) represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group, which may be substituted with R of the above general formula (1)^viAnd R^viiThe same is true.

In the general formula (2), Ar²Represents an optionally substituted 2-valent aromatic heterocyclic group, Ar²May be reacted with Ar of the above general formula (1)¹The aromatic heterocyclic groups in (A) are the same.

In the general formula (2), E^m-Represents a polyacid anion having a valence of m, which may be the same as the polyacid anion having a valence of c of the above general formula (1).

In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. The number of cations in the general formula (2) may be 1 alone or 2 or more in combination. Further, the anion may be 1 kind alone, or 2 or more kinds may be combined.

In the general formula (2), j is 0 or 1, and no bond is present when j is 0. J in the general formula (2) may be the same as e in the general formula (1) described above. In addition, k and l in the general formula (2) may be the same as f and g in the general formula (1).

The lake material represented by the general formula (2) can be prepared, for example, by referring to jp 2017-16099 a.

< phthalocyanine pigment treated with alkali >

The alkali-treated phthalocyanine pigment used in the present invention refers to a phthalocyanine pigment having a structure derived from a basic compound.

Examples of the phthalocyanine pigment having a structure derived from a basic compound include phthalocyanine pigments containing a basic compound such as a colorant derivative having a basic moiety.

The phthalocyanine pigment used for the alkali treatment is preferably a blue phthalocyanine pigment in combination with at least 1 lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2), and is preferably a copper phthalocyanine pigment in terms of relatively excellent brightness. The copper phthalocyanine pigment used for the alkali treatment may be a crude copper phthalocyanine pigment, or may be a copper phthalocyanine pigment having a crystal structure of α type, β type, γ type, or ε type. Among them, the copper phthalocyanine pigment used for the alkali treatment is preferably 1 or more selected from the group consisting of a copper phthalocyanine pigment having an epsilon-type crystal structure and a copper phthalocyanine pigment having a beta-type crystal structure in terms of excellent dispersion stability.

In the present invention, a derivative of a coloring material having a basic site or a derivative of a colorless compound having a basic site can be suitably used for the alkali treatment.

In the present invention, the basic site includes: examples of the substituent include a basic group, a salt of an acidic group with a basic compound in a substituent, and the like.

In the present invention, examples of the basic site of the derivative of the coloring material or the derivative of the colorless compound include: an amino group, a sulfonic acid ammonium salt, a sulfonamide group having an amino group, an amide group having an amino group, a basic heterocyclic group, and the like.

In the present invention, the basic moiety of the color material derivative may be contained in a state in which a hydrogen atom of the color material is substituted with the basic moiety, or may be contained in a state in which the basic moiety is substituted with the color material through a linking group. Examples of the basic moiety substituted for the color material via a linking group include: the color material is substituted with a C1-20 hydrocarbon group or a substituent having a hydrocarbon group, and the hydrogen atom of the hydrocarbon group is substituted with the basic moiety. The basic site of the derivative of the colorless compound may be the same as that of the derivative of the coloring material.

As the above-mentioned amino group, there may be mentioned-NR^aR^bIs represented by, herein R^aAnd R^bEach independently may be enumerated by a hydrogen atom, or may be substituted by-NR^a′R^b′A substituted hydrocarbon group having 1 to 30 carbon atoms, R^a′And R^b′Each independently includes a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

The ammonium sulfonate salt is represented by-SO₃ ^-·NHR^cR^dR^e+Is represented by, herein R^c、R^dAnd R^eEach independently includes a hydrogen atom and a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with the amino group.

As the amino sulfonamide group, among them, in terms of dispersibility of the coloring material, -SO is preferable₂NH-(CH₂)_m-NR^fR^gGroup (here, R)^fAnd R^gEach independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with the amino group, or a group bonded to each other and forming a basic heterocycle together with the adjacent nitrogen atom, and m represents an integer of 1 to 15).

Among them, the amide group having the amino group is preferably-CONH- (CH) in view of dispersibility of the coloring material₂)_m′-NR^jR^kGroup (here, R)^jAnd R^kEach independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with the amino group, or a group bonded to each other and forming a basic heterocycle together with the adjacent nitrogen atom, and m' represents an integer of 1 to 15).

In the above-mentioned R^a、R^b、R^a′、R^b′、R^c、R^d、R^e、R^f、R^g、R^jAnd R^kIn (1) the hydrocarbon group having 1 to 30 carbon atoms includes: aliphatic hydrocarbon groups having 1 to 30 carbon atoms, aromatic hydrocarbon groups, and combinations thereof, for example, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, benzyl, and the like.

R is as defined above^a、R^b、R^a′、R^b′、R^c、R^d、R^e、R^f、R^g、R^jAnd R^kEach independently preferably a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, still more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and yet more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

M and m' represent an integer of 1 to 15, preferably 2 to 8, and particularly preferably 3 to 6.

In addition, in R^f、R^g、R^jAnd R^kIn the structure in which the basic heterocyclic ring is formed by bonding to each other and the adjacent nitrogen atom, the heterocyclic ring may further contain a nitrogen, oxygen or sulfur atom, and examples thereof include morpholine, piperidine, pyridine, triazine and thiazole.

In addition, as the basic site of the basic heterocyclic group, there may be mentioned: morpholinyl, piperidinyl, pyridyl, triazinyl, and the like.

Among these, the basic site of the derivative is preferably a sulfonic acid ammonium salt or a sulfonamide group having an amino group, and among these, -SO is preferable, from the viewpoint of easy interaction with the acidic dispersant₂NH-(CH₂)_m-NR^fR^gThe group shown.

The basic site of the derivative is not particularly limited as long as it is at least 1 per molecule of the color material or the colorless compound 1, and is preferably 1 or 2 in terms of dispersibility of the color material. The position of the basic moiety of the derivative substituted for the color material or the colorless compound is not particularly limited.

The colorant used for the colorant derivative having a basic site can be used by appropriately selecting a known colorant, and preferably has a structure that is easily adsorbed to the phthalocyanine pigment used for the basic treatment, and preferably has the same or similar pigment skeleton and is easily interacted with each other. Further, a color material which does not impair the color and taste of the phthalocyanine pigment used for the alkali treatment is preferable.

Among the color material derivatives having a basic site, a blue color material derivative is preferable.

The blue color material used for the color material derivative having a basic site is the following color material: when a 2.5 μm coating film was formed at a P/V ratio ((total mass of color materials in the composition)/(total mass of solid components other than color materials in the composition)) of 0.2 and the spectral transmittance spectrum was measured, the color material had a 420nm transmittance of 20% or more and a 520nm transmittance of 10% or more and a 580nm transmittance of less than 10%.

In order to form a single-component coating film of the color material and measure the color, a coating liquid may be prepared by mixing an appropriate binder component and a solvent with the color material, and the coating liquid may be applied to a transparent substrate, dried, and cured as necessary. As the binder component, a non-curable thermoplastic resin composition, or a photocurable (photosensitive) or thermosetting resin composition may be used as long as a transparent coating film capable of color measurement can be formed. In the colored resin composition of the present invention described below, color measurement can also be performed by using a composition containing only a blue color material as a color material to form a coating film containing only a blue color material as a color material. Specifically, for example, solid components other than the color material used in the resin composition of example 1 described below can be used as the binder component. A color material dispersion liquid may be prepared as necessary, and a color material dispersion liquid and a colored resin composition may be prepared separately in the same manner as in example 1 below, and a cured film may be prepared in the same manner as in the case of evaluating the optical performance of the following example.

The transparent color-measurable coating film containing a binder component can be standardized, for example, to a film thickness of 2.0 μm and a transmittance of 95% or more in a spectral transmittance spectrum of 380nm to 780 nm.

The spectral transmittance spectrum can be measured using a spectroscopic measuring apparatus (e.g., a microspectrophotometer OSP-SP200 manufactured by Olympus).

As the blue color material used for the color material derivative having a basic site, a phthalocyanine-based color material, a triarylmethane-based color material, an anthraquinone-based color material, a naphthol-based color material, a benzimidazolone-based color material, or the like can be used, and the phthalocyanine-based color material is preferably used in terms of color tone or heat resistance. Examples of the phthalocyanine-based coloring material include: pigment Blue (PB)15, PB15:1, PB15:2, PB15:3, PB15:4, PB15:5, PB15:6 and other copper phthalocyanines, PB16, PB75, PB79 and other pigments expressed as color indices.

Among them, in terms of improvement in dispersibility and luminance, it is preferable to use a phthalocyanine-based colorant having the same skeleton as that of the phthalocyanine pigment used for the alkali treatment as the colorant used for the colorant derivative having a basic site.

Among them, copper phthalocyanine is preferably used as the blue coloring material used as the coloring material derivative having a basic site in terms of improvement in dispersibility and luminance.

The colorless compound used as the derivative of the colorless compound having a basic site can be a compound whose color of the phthalocyanine pigment does not change before and after the alkali treatment even when the phthalocyanine pigment is subjected to the alkali treatment using the derivative of the colorless compound. The color measurement of the phthalocyanine pigment before and after the alkali treatment can be performed in the same manner as in the case of the blue color material. Specifically, a colorant dispersion and a colored resin composition were prepared in the same manner as in example 1 below using the phthalocyanine pigment before and after the alkali treatment, and cured films were prepared in the same manner as the cured films obtained in the evaluation of the optical properties of the following examples. The chromaticity of each cured film was measured by the method described in the following examples, and the chromaticity (L) of the cured film containing the phthalocyanine pigment before the alkali treatment was measured₀、a₀、b₀) Color (L) of cured film containing alkali-treated phthalocyanine pigment₁、a₁、b₁) Is (d) { (L)₁-L₀)²+(a₁-a₀)²+(b₁-b₀)²}^1/2If the color is less than 10, the color is assumed to be unchanged.

As the colorless compound used as the derivative of the colorless compound having a basic site, for example, an organic compound having an extremely large absorption in a wavelength region of 400nm or less can be used by appropriately selecting it. The colorless compound preferably has a structure that is easily adsorbed to the phthalocyanine pigment used for the alkali treatment, and preferably has a structure that is easily interacted with. As the colorless compound, for example, a fused ring compound such as a naphthalene-based or triazine-based compound or an aromatic polycyclic compound in which a plurality of aromatic rings are bonded can be used. Examples of the triazine-based aromatic polycyclic compound include a triazine ring substituted with 3 substituents having an aromatic hydrocarbon group such as a phenylamino group. Among them, triazine-based aromatic polycyclic compounds are preferably used in terms of improvement in dispersibility and luminance.

The color material derivative having a basic site can be produced by a conventionally known method. For example, the coloring material can be produced by a method of sulfonating the coloring material and then forming a salt with ammonia or an organic amine, or a method of sulfonating a substituent of the coloring material.

Specifically, for example, the following methods can be mentioned: a coloring material is added to concentrated sulfuric acid or fuming sulfuric acid, and the mixture is heated to be sulfonated. Next, the reaction solution is poured into a large amount of ice water to precipitate a sulfonated derivative, and the sulfonated derivative is separated by filtration using a filter press or the like and washed with water. The obtained water slurry of the sulfonated derivative is redispersed in a large amount of water, neutralized with a basic compound, more specifically, a method of adding ammonia or an organic amine aqueous solution to a pH of 7 and salifying sulfonic acid with ammonia or an organic amine. Thereafter, the resultant is subjected to filtration separation, washing with water, drying, and pulverization to obtain a powdery color material derivative having an alkaline site.

Examples of the organic amine used for the sulfonylation or the organic amine salt of the color material derivative having a basic site include: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, ethylmethylamine, n-propylmethylamine, isopropylmethylamine, 1, 7, 7-tetramethyl-1, 4, 7-triazaheptane, 1, 7, 7-tetraethyl-1, 4, 7-triazaheptane, 1, 7, 7-tetrapropyl-1, 4, 7-triazaheptane, 1, 7, 7-tetraisopropyl-1, 4, 7-triazaheptane, 1, 7, 7-tetrabutyl-1, 4, 7-triazaheptane, 1-dimethyl-1, 5-diazapene, 1-diethyl-1, 5-diazapene, 1-diisopropyl-1, 5-diazapene, 1-dibutyl-1, 5-diazapene, etc., but is not limited thereto.

The derivative of the colorless compound having a basic site can be produced by a conventionally known method in the same manner as the derivative of the coloring material having a basic site.

As the phthalocyanine pigment having a structure derived from a basic compound, for example, as a method for producing a phthalocyanine pigment containing a colorant derivative having a basic site, for example, the following methods can be cited: after the color material derivative having a basic site and the phthalocyanine pigment are dry-pulverized, the color material derivative having a basic site is further mixed. In this case, as the dry type pulverizer, a ball mill, a vibration mill, an attritor, or the like can be used, and the pulverizing temperature can be freely set within a range of 20 to 130 ℃.

In addition, as a method for producing a phthalocyanine pigment containing a colorant derivative having a basic site, the following methods can be mentioned: a colorant derivative having a basic moiety, a phthalocyanine pigment, a water-soluble inorganic salt such as sodium chloride, calcium chloride or ammonium sulfate, and a water-soluble organic solvent such as an alcohol-based organic solvent are mixed, and kneaded by a solvent salt milling method using a kneader-type mill.

The alkali-treated phthalocyanine pigment is prepared or prepared in advance before the dispersion of the color material, and the color material is dispersed, whereby the dispersibility of the color material can be improved.

In the phthalocyanine pigment including the derivative of the coloring material or the derivative of the colorless compound having a basic site, the content of the derivative of the coloring material or the derivative of the colorless compound having a basic site is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and further more preferably 8 parts by mass or more, relative to 100 parts by mass of the phthalocyanine pigment, from the viewpoint of dispersibility and storage stability. On the other hand, the content of the derivative of the coloring material having a basic site or the derivative of the colorless compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the phthalocyanine pigment in terms of excellent brightness.

The phthalocyanine pigment treated with alkali can be appropriately analyzed by, for example, mass spectrometry, elemental analysis, surface analysis, potential difference titration, or a combination thereof. More specifically, for example, the confirmation can be made as follows: after washing the alkali-treated phthalocyanine pigment with an alcohol solvent such as methanol, ethanol, or isopropanol, or a solvent such as N-methylpyrrolidone, the washed phthalocyanine pigment is subjected to mass spectrometry, and a peak derived from the structure of a desired basic compound such as a colorant derivative having a basic site is detected.

< other color materials >

The color material used in the present invention contains at least 1 lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2), and the alkali-treated phthalocyanine pigment as essential components, and may be used in combination with another color material in order to adjust the color tone within a range not to impair the effects of the present invention.

As the other color materials, known pigments, dyes, lake materials, and the like can be used alone or in combination of 2 or more.

As the other color material, other blue color material, purple color material, and red color material can be preferably used, but the invention is not limited to these.

Examples of the other blue color materials include known organic blue pigments different from the phthalocyanine pigment, triarylmethane-based color lake materials different from the color material represented by the general formula (1) and the color material represented by the general formula (2), and the like.

Examples of the violet colorant include known organic violet pigments such as c.i. pigment violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.

Examples of the red or magenta coloring material include xanthene dyes and lake coloring materials of xanthene dyes different from the coloring materials represented by the general formula (1) and the coloring materials represented by the general formula (2).

< content ratio of color Material >

In the color material dispersion liquid of the present invention, the content ratio of each of at least 1 kind of lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2) and the alkali-treated phthalocyanine pigment, and the content ratio in the case where another color material is used, is preferably the content ratio used in the following colored resin composition. Specifically, the following content ratio is preferably used. However, since the coloring material dispersion can be used by mixing 2 or more kinds of coloring materials as appropriate to produce a colored resin composition, the following colored resin composition can be used without being used in a content ratio.

In the color material dispersion liquid of the present invention, it is preferable that the content of at least 1 lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is 20 mass% or more and 85 mass% or less with respect to the total content of the phthalocyanine pigment and at least 1 lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), in order to suppress a change in chromaticity of a colored layer after a high-temperature heating step (post-baking) in a color filter manufacturing step, to improve luminance, and to form a pattern with a desired line width.

The present inventors have obtained the following findings: when a blue colored layer is formed using only a phthalocyanine pigment, a colored layer having a design may not be formed. It is presumed that the reason for this is that the blue phthalocyanine pigment absorbs around 300nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, and therefore cannot sufficiently undergo photopolymerization reaction, and insufficient curing occurs inside the colored layer during exposure. In contrast, it is estimated that: by using the specific lake material in combination with the phthalocyanine pigment at the specific ratio, the specific lake material is less likely to absorb a wavelength around 300nm, and therefore, even when a photosensitive coloring resin composition for a blue coloring layer is formed by combining a negative photosensitive binder component, insufficient curing inside the coloring layer is less likely to occur during exposure, and a pattern can be easily formed with a desired line width.

Further, it is presumed that: by using a phthalocyanine pigment in combination with a color material represented by the above specific general formula (1) at a specific ratio, the chromaticity change due to the color material represented by the above specific general formula (1) is suppressed, the transmittance can be improved, and the luminance of a colored layer finally obtained after high-temperature heating (post-baking) in the color filter production process can be improved.

Among them, the content of at least 1 kind of lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2) is preferably 30% by mass or more, more preferably 40% by mass or more, with respect to the total content of the at least 1 kind of lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2) and the above phthalocyanine pigment, in terms of the lightness and the easiness of patterning at a desired line width, on the other hand, is preferably 80% by mass or less, more preferably 75% by mass or less, in terms of the heat resistance, and further improves the substrate adhesion, further, in terms of improvement in developability in the case of producing a photosensitive resin composition, it is more preferably 55% by mass or less.

In the color material dispersion liquid of the present invention, the color material may further contain a phthalocyanine pigment and another color material other than the color material represented by the above general formula (1) within a range not impairing the effects of the present invention, and the total content of the phthalocyanine pigment and the color material represented by the above general formula (1) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the color materials.

The average primary particle size of the color material used in the present invention is not particularly limited as long as a desired color development can be achieved in the case of a colored layer of a color filter, and may vary depending on the type of the color material used, but is preferably in the range of 10nm to 100nm, more preferably 15nm to 60 nm. By setting the average primary particle size of the color material to the above range, a display device including a color filter manufactured using the color material dispersion liquid of the present invention can have high contrast and high quality.

The average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material used, and is preferably in the range of 10nm to 150nm, more preferably in the range of 15nm to 60 nm.

The average dispersed particle diameter of the color material in the color material dispersion liquid is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser scattering particle size distribution meter. As the measurement of the particle diameter by the laser scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted (for example, 1000 times or the like) to a concentration that can be measured by the laser scattering particle size distribution meter by using a solvent used for the color material dispersion liquid, and the particle diameter can be measured by a dynamic light scattering method at 23 ℃ by using the laser scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by japanese mechanical instruments). The average distribution particle diameter herein is a volume average particle diameter.

In the color material dispersion liquid of the present invention, the content of the color material is not particularly limited. The content of the color material is preferably 5 to 80 mass%, more preferably 8 to 70 mass%, based on the total amount of solid components in the color material dispersion liquid, in terms of dispersibility and dispersion stability.

In particular, when a coating film or a colored layer having a high color material concentration is formed, it is preferably blended at a ratio of 30 to 80 mass%, more preferably 40 to 75 mass%, with respect to the total amount of solid components in the color material dispersion.

In the present invention, the solid component is not limited to the above solvent, and includes monomers dissolved in the solvent.

[ acidic dispersing agent ]

The acidic dispersant used in the present invention comprises at least 1 polymer having a structural unit selected from those represented by the above general formula (I).

When at least 1 polymer selected from the structural units represented by the general formula (I) is used as the acidic dispersant, the dispersibility and heat resistance of the lake material can be improved, the change in chromaticity of the lake material after heating can be suppressed, the dispersibility and storage stability of the phthalocyanine pigment can be improved, and a colored layer having improved substrate adhesion and coating film uniformity can be formed.

And (3) presuming: since at least 1 polymer having a structural unit selected from those represented by the above general formula (I) is an ethylenically unsaturated monomer polymer, the heat resistance of the skeleton is higher than that of a polyether polymer or a polyester polymer, and the polymerIn the presence of a plurality of acidic phosphorus compound groups (-P (═ O) (-R)²) (OH)) and salts thereof (-P (═ O) (-R)²)(O^-X⁺) Strong adsorption force to the surface of the micronized color material. In addition, it is estimated that: when the surface of the color material is coated with at least one of the acidic phosphorus compound group and the salt thereof, attack (hydrogen abstraction, substitution reaction, etc.) of the color material on the pigment skeleton by active oxygen such as peroxy radicals is suppressed, and deterioration (oxidative deterioration) of the color material is suppressed.

< polymers having at least 1 species selected from the structural units represented by the above general formula (I) >

In the general formula (I), L¹Is a direct bond or a 2-valent linking group. Here, L is¹The term "directly bonded" means that the phosphorus atom is directly bonded to a carbon atom of the main chain skeleton without via a linking group.

As L¹The 2-valent linking group in (2) is not particularly limited as long as it can link a carbon atom of the main chain skeleton and a phosphorus atom. As L¹Examples of the 2-valent linking group in (1) include: a linear, branched or cyclic alkylene group; a linear, branched or cyclic alkylene group having a hydroxyl group; arylene groups, -CONH-groups, -COO-groups, -NHCOO-groups, ether groups (-O-groups), thioether groups (-S-groups), combinations thereof, and the like. In the present invention, the bonding direction of the 2-valent linking group is arbitrary. That is, when the 2-valent linking group includes-CONH-, it may be such that-CO is on the carbon atom side of the main chain and-NH is on the phosphorus atom side of the side chain, or conversely-NH is on the carbon atom side of the main chain and-CO is on the phosphorus atom side of the side chain.

Wherein, in terms of dispersibility, L in the general formula (I)¹Preference is given to 2-valent linking groups which comprise-CONH-groups or-COO-groups.

For example, at L¹In the case of a 2-valent linking group containing a-COO-group, L¹Is preferably-COO-L^1′-radical (here, L)^1′Is an alkylene group having 1 to 8 carbon atoms which may have a hydroxyl group, - [ CH (R)^L11)-CH(R^L12)-O]_x-, or- [ (CH)₂)_y-O]_z-(CH₂)_y-O-、-[CH(R^L13)]_w-O-，R^L11、R^L12And R^L13Each independently is a hydrogen atom, a methyl group, or a hydroxyl group; x represents an integer of 1 to 18 inclusive, y represents an integer of 1 to 5 inclusive, z represents an integer of 1 to 18 inclusive, and w represents an integer of 1 to 18 inclusive).

L^1′The alkylene group having 1 to 8 carbon atoms in the group (b) may be any of linear, branched, or cyclic, and examples thereof include methylene, ethylene, trimethylene, propylene, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, and a part of hydrogen may be substituted with a hydroxyl group.

x is an integer of 1 to 18, preferably 1 to 4, more preferably 1 to 2, and y is an integer of 1 to 5, preferably 1 to 4, more preferably 2 or 3. z is an integer of 1 to 18 inclusive, preferably 1 to 4 inclusive, and more preferably 1 to 2 inclusive. w is an integer of 1 to 18 inclusive, preferably 1 to 4 inclusive.

As L in the general formula (I)¹Suitable specific examples of (b) include, for example: -COO-CH₂CH(OH)CH₂-O-、-COO-CH₂CH₂-O-CH₂CH(OH)CH₂-O-、-COO-CH₂C(CH₂CH₃)(CH₂OH)CH₂O-and the like, but is not limited thereto.

As R²Examples of the hydrocarbon group in (1) include: an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, and the like.

The alkyl group having 1 to 18 carbon atoms may be any of linear, branched, and cyclic, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentyl, adamantyl, lower alkyl-substituted adamantyl, and the like.

The alkenyl group having 2 to 18 carbon atoms may be any of straight-chain, branched, and cyclic. Examples of such alkenyl groups include: vinyl, allyl, propenyl, and the like. The position of the double bond of the alkenyl group is not limited, and it is preferable that the double bond is present at the terminal of the alkenyl group in terms of reactivity of the obtained polymer.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and the aryl group may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

The alkyl group or alkenyl group may have a substituent, and examples of the substituent include a halogen atom such as F, Cl, and Br, and a nitro group.

Examples of the substituent of the aromatic ring such as the aryl group or the aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom.

The preferred carbon number includes no carbon number of a substituent.

R is as defined above²Wherein x1 is the same as x, y1 is the same as y, and z1 is the same as z.

As R⁵～R¹²Examples of the hydrocarbon group in (1) include the above-mentioned groups R²The hydrocarbon group in (1) is the same.

R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²The hydrocarbon group having 1 or more kinds selected from an ether bond and an ester bond in (b) means: a group represented by-R '-O-R', -R '- (C ═ O) -O-R', or-R '-O- (C ═ O) -R' (wherein R 'and R' are each a hydrocarbon group or a group in which a hydrocarbon group is bonded through at least one of an ether bond and an ester bond). 1 group may have 2 or more ether bonds and ester bonds. Examples of the hydrocarbyl group having a valence of 1 include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group, and examples of the hydrocarbyl group having a valence of 2 include an alkylene group, an alkenylene group, an arylene group, and a combination thereof.

At R⁷And R⁹When the ring structure is formed by bonding, the number of carbon atoms forming the ring structure is preferably 5 to 8, more preferably 6, that is, a 6-membered ring, and a cyclohexane ring is preferably formed.

Substituent R¹⁴The hydrocarbon group (B) or the hydrocarbon group having 1 or more kinds selected from the ether bond and the ester bond may be the same as R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²The hydrocarbon group in (1) is the same.

The above R is a group having excellent dispersibility and dispersion stability of the particles to be dispersed²Preferably a hydroxyl group, a hydrocarbon group, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵or-O-R⁶The 1-valent group is more preferably a hydroxyl group, a methyl group, an ethyl group, a vinyl group, an optionally substituted aryl or aralkyl group, a vinyl group, an allyl group, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵、-[(CH₂)_y1-O]_z1-R⁵or-O-R⁶A 1-valent group represented by, and R³And R⁴Each independently is a hydrogen atom or a methyl group, R⁵is-CO-CH ═ CH₂or-CO-C (CH)₃)＝CH₂Wherein R is²More preferred are aryl, vinyl, methyl and hydroxyl groups which may have a substituent.

In addition, R is for improvement of alkali resistance²Preferably a hydrocarbon group, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵Or- [ (CH)₂)_y1-O]_z1-R⁵1-valent radical as shown. In the case of a structure in which carbon atoms are directly bonded to phosphorus atoms, it is assumed that hydrolysis is not likely to occur, and therefore a resin layer having excellent alkali resistance can be formed. Among them, R is preferable in terms of excellent alkali resistance and excellent dispersibility and dispersion stability of particles to be dispersed²Is methyl, ethyl, aryl or aralkyl which may have a substituent, vinyl, allyl, - [ CH (R)³)-CH(R⁴)-O]_x1-R⁵Or- [ (CH)₂)_y1-O]_z1-R⁵A 1-valent group represented by, R³And R⁴Each independently is a hydrogen atom or a methyl group, R⁵is-CO-CH ═ CH₂or-CO-C (CH)₃)＝CH₂. Among them, R is more preferable in terms of dispersibility²Is an aryl group which may have a substituent.

In the general formula (I), X represents a hydrogen atom or an organic cation. By organic cation is meant a cation comprising a carbon atom in its part. Examples of the organic cation include: and an ammonium cation such as an imidazolium cation, a pyridinium cation, an amidinium cation, a piperidinium cation, a pyrrolidinium cation, a tetraalkylammonium cation, or a trialkylammonium cation, a sulfonium cation such as a trialkylsulfonium cation, or a phosphonium cation such as a tetraalkylphosphonium cation. Among them, a protonated nitrogen-containing organic cation is preferable in terms of dispersibility and alkali developability.

Among them, in the case where the organic cation has an ethylenically unsaturated double bond, it is preferable in terms of imparting curability.

The structural unit represented by the general formula (I) may be contained in the polymer in 1 kind alone, or may be contained in 2 or more kinds.

The polymer may contain two kinds of structural units, i.e., a structural unit in which X is a hydrogen atom and a structural unit in which X is an organic cation, among the structural units represented by the general formula (I). When the two kinds of structural units are contained, the ratio of the number of structural units in which X is an organic cation to the total number of structural units represented by the general formula (I) is preferably 0 to 50 mol% as long as good dispersibility and dispersion stability can be exhibited, and is not particularly limited.

The method for synthesizing the polymer having at least 1 kind selected from the structural units represented by the general formula (I) is not particularly limited. The polymer having at least 1 type selected from the structural units represented by the general formula (I) can be synthesized, for example, with reference to Japanese patent laid-open publication No. 2017-2191. The polymer having at least 1 kind selected from the structural units represented by the general formula (I) is preferably a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in a side chain thereof and an acidic phosphorus compound, and is a polymer in which at least a part of the acidic phosphorus compound group can form a salt.

In the embodiment of the present invention, the polymer having at least 1 kind selected from the structural units represented by the general formula (I) preferably further has a solvent affinity site in terms of dispersibility. Among these polymers, in terms of excellent dispersibility and storage stability and the ability to form a coating film having a high contrast even after long-term storage, preferred are: a graft copolymer having at least 1 kind selected from the structural units represented by the above general formula (I) and a structural unit represented by the following general formula (II); or a block copolymer having at least 1 kind selected from the structural units represented by the above general formula (I) and a structural unit represented by the following general formula (III).

[ solution 12]

(in the general formula (II), L²Represents a direct bond or a 2-valent linking group, R²¹Represents a hydrogen atom or a methyl group, and Polymer represents a Polymer chain having a structural unit represented by the following general formula (IV);

in the general formula (III), R²²Is a hydrogen atom or a methyl group, R²³Is a hydrocarbyl radical, - [ CH (R)²⁴)-CH(R²⁵)-O]_x2-R²⁶、-[(CH₂)_y2-O]_z2-R²⁶、-[CO-(CH₂)_y2-O]_z2-R²⁶、-CO-O-R^26′or-O-CO-R^26″A 1-valent group represented by, R²⁴And R²⁵Each independently is a hydrogen atom or a methyl group, R²⁶Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO or-CH₂COOR²⁷A 1-valent group represented by, R^26′Is a hydrocarbyl radical, - [ CH (R)²⁴)-CH(R²⁵)-O]_x2′-R²⁶、-[(CH₂)_y2′-O]_z2′-R²⁶、-[CO-(CH₂)_y2′-O]_z2′-R²⁶1-valent radical of formula，R^26″Is an alkyl group having 1 to 18 carbon atoms, R²⁷Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The above hydrocarbon group may have a substituent.

x2 and x2 ' represent integers of 1 to 18 inclusive, y2 and y2 ' represent integers of 1 to 5 inclusive, and z2 and z2 ' represent integers of 1 to 18 inclusive. )

[ solution 13]

(in the general formula (IV), R³¹Is a hydrogen atom or a methyl group, R³²Is a hydrocarbyl radical, - [ CH (R)³³)-CH(R³⁴)-O]_x3-R³⁵、-[(CH₂)_y3-O]_z3-R³⁵、-[CO-(CH₂)_y3-O]_z3-R³⁵、-CO-O-R³⁶or-O-CO-R³⁷A 1-valent group represented by, R³³And R³⁴Each independently is a hydrogen atom or a methyl group, R³⁵Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO or-CH₂COOR³⁸A 1-valent group represented by, R³⁶Is a hydrocarbyl radical, - [ CH (R)³³)-CH(R³⁴)-O]_x4-R³⁵、-[(CH₂)_y4-O]_z4-R³⁵、-[CO-(CH₂)_y4-O]_z4-R³⁵A 1-valent group represented by, R³⁷Is an alkyl group having 1 to 18 carbon atoms, R³⁸The hydrocarbon group may have a substituent, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

n represents an integer of 5 to 200 inclusive. x3 and x4 each represents an integer of 1 to 18. y3 and y4 each represents an integer of 1 to 5. z3 and z4 each represents an integer of 1 to 18. )

(graft copolymer)

In the above general formula (II), L²Is a direct bond or a 2-valent linking group. As L²The 2-valent linking group in (2) is not particularly limited as long as it can link a carbon atom derived from an ethylenically unsaturated double bond to a polymer chain. As L²Examples of the 2-valent linking group in (1) include those mentioned above for L¹The 2-valent linking group in (1) is the same.

In the general formula (II), Polymer represents a Polymer chain having a structural unit represented by the general formula (IV).

In the formula (IV), as R³²The hydrocarbon group in (2) is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. Examples of these include the above-mentioned compounds R²The same is true.

R³⁵Preferably a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH₂CHO or-CH₂COOR³⁸A 1-valent group represented by, R³⁶Preferably an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, - [ CH (R) is³³)-CH(R³⁴)-O]_x4-R³⁵、-[(CH₂)_y4-O]_z4-R³⁵、-[CO-(CH₂)_y4-O]_z4-R³⁵1-valent radical as shown. R³⁷Is an alkyl group having 1 to 18 carbon atoms, R³⁸Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R is as defined above³⁵And R³⁶The alkyl, aralkyl and aryl groups having 1 to 18 carbon atoms in the group (A) include those mentioned above for R²The same is true.

R is as defined above³⁷And R³⁸The alkyl group in (1) is exemplified by the above-mentioned R²The same is true.

In the above-mentioned R³⁵、R³⁶、R³⁷And R³⁸In the case of a group having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include linear, branched, and cyclic alkyl groups having 1 to 5 carbon atoms, and halogen atoms such as alkenyl, nitro, F, Cl, and Br.

The preferred carbon number does not include the carbon number of the substituent.

R is as defined above³²And R³⁶Wherein x3 and x4 are the same as the above-mentioned xSimilarly, y3 and y4 are the same as y described above, and z3 and z4 are the same as z described above.

Further, the above R³²、R³⁵、R³⁶、R³⁷And R³⁸The graft copolymer may be further substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group, within a range not to impair the dispersibility of the graft copolymer. Further, after the graft copolymer having these substituents is synthesized, a compound having a functional group reactive with the substituents and a polymerizable group may be reacted to add the polymerizable group. For example, the polymerizable group can be added by reacting glycidyl (meth) acrylate with a graft copolymer having a carboxyl group, or by reacting hydroxyethyl (meth) acrylate with a graft copolymer having an isocyanate group.

The polymer chain included in the structural unit represented by the general formula (IV) preferably further includes a structural unit derived from methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α -methylstyrene, vinylcyclohexane, or the like, among the above structural units. However, it is not limited to these.

In an embodiment of the present invention, R is the above-mentioned³²And R³⁶Among them, those having excellent solubility in the following organic solvents are preferably used, and may be appropriately selected depending on the organic solvent used for the color material dispersion liquid. Specifically, for example, when an ether alcohol acetate-based, ether-based, ester-based or other organic solvent that is generally used as an organic solvent for the color material dispersion is used as the organic solvent, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl or the like is preferable.

Here, the above-mentioned R is set so that³²And R³⁶The reason for (A) is that R is contained³²And R³⁶The structural unit (b) has solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and the part of the salt thereof have high adsorbability to particles such as a color material, and thus the dispersibility and stability of the particles such as a color material can be particularly excellent.

The mass average molecular weight Mw of the Polymer chain in the Polymer is preferably in the range of 500 to 15000, and more preferably in the range of 1000 to 8000. By setting the range above, it is possible to maintain a sufficient steric repulsion effect as a dispersant, and also to suppress an increase in time required for dispersing particles of a color material or the like due to a steric hindrance effect.

In addition, the Polymer chain in the Polymer preferably has a solubility at 23 ℃ of 50(g/100g of solvent) or more with respect to the organic solvent used in combination as a standard.

The polymer chain may be a homopolymer or a copolymer. The number of the polymer chains contained in the structural unit represented by the general formula (II) may be 1 by itself or 2 or more by mixing in the graft copolymer.

The total of the structural units represented by the general formula (I) is contained in a proportion of preferably 3 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total structural units of the graft copolymer. When the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the structural units to the affinity sites of the particles in the graft copolymer becomes appropriate, and the decrease in solubility in an organic solvent can be suppressed. Further, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the color material, a color filter having excellent heat resistance and contrast can be obtained.

On the other hand, the structural unit represented by the general formula (II) is preferably contained at a ratio of 20 mass% to 97 mass%, more preferably 25 mass% to 95 mass%, and still more preferably 40 mass% to 90 mass% with respect to the total structural units of the graft copolymer.

The content ratio of the structural units is calculated from the amount of addition in the synthesis of a graft copolymer having at least 1 type selected from the structural units represented by the general formula (I) and the structural units represented by the general formula (II).

The mass average molecular weight Mw of the graft copolymer is preferably in the range of 1000 to 500000, more preferably 3000 to 400000, and still more preferably 5000 to 300000. When the amount is within the above range, particles such as a color material can be uniformly dispersed.

In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). In the measurement, HLC-8220GPC manufactured by Tosoh was used, and the elution solvent was N-methylpyrrolidone to which 0.01 mol/l of lithium bromide was added, and the calibration curve was Mw: 8X 10⁵(F-80)、Mw：4×10⁵(F-40)、Mw：2×10⁵(F-20)、Mw：1×10⁵(F-10)、Mw：4×10⁴(F-4)、Mw：2×10⁴(F-2)、Mw：5×10³(A-5000)、Mw：2.5×10³(A-2500)、Mw：1×10³(A-1000)、Mw：5×10²(A-500) (manufactured by Tosoh above), the measurement was performed using TSK-GEL ALPHA-Mx 2 roots (manufactured by Tosoh).

The graft copolymer used in the embodiment of the present invention may have other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). An ethylene unsaturated monomer copolymerizable with at least one ethylene unsaturated monomer derived from the structural unit represented by the above general formula (I) may be appropriately selected and copolymerized to introduce another structural unit.

(Block copolymer)

In the block portion containing at least one kind selected from the structural units represented by the general formula (I), the structural unit represented by the general formula (I) preferably contains 3 or more in total. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferably contained in an amount of 3 or more and 200 or less, more preferably 3 or more and 50 or less, and still more preferably 3 or more and 30 or less.

At least one kind selected from the structural units represented by the general formula (I) may include only 1 kind of structural unit or 2 or more kinds of structural units as long as the structural unit functions as a color material affinity site. When 2 or more kinds of structural units are contained, 2 or more kinds of structural units may be randomly arranged in a block portion containing at least one kind selected from the structural units represented by the general formula (I).

In the block copolymer, the total content ratio of the structural units represented by the general formula (I) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total structural units of the block copolymer.

When the content is within the above range, the ratio of the affinity site with the particle in the block copolymer becomes appropriate, and the decrease in solubility in an organic solvent can be suppressed, so that the adsorption property to the particle such as a color material becomes good, and excellent dispersibility and dispersion stability can be obtained. Further, since the acidic phosphorus compound group of the block copolymer can be stably localized in the vicinity of the color material, a color filter having excellent heat resistance and contrast can be obtained.

The content ratio of the structural unit can be calculated from the amount added in the synthesis of the block copolymer.

The block copolymer has a block portion containing a structural unit represented by the general formula (III), and thus has good solvent affinity, good dispersibility and dispersion stability of a color material, good heat resistance, and further excellent NMP (N-methylpyrrolidinone) resistance.

In the general formula (III), R²³Is a hydrocarbyl radical, - [ CH (R)²⁴)-CH(R²⁵)-O]_x2-R²⁶、-[(CH₂)_y2-O]_z2-R²⁶、-[CO-(CH₂)_y2-O]_z2-R²⁶、-CO-O-R^26′or-O-CO-R^26″1-valent radical as shown.

As R²³The hydrocarbon group in (1) may be the same as R²The same hydrocarbon groups as shown in (1).

In addition, the above R²⁶Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO or-CH₂COOR²⁷A 1-valent group represented by, R^12′Is a hydrocarbyl radical, - [ CH (R)²⁴)-CH(R²⁵)-O]_x2′-R²⁶、-[(CH₂)_y2′-O]_z2′-R²⁶、-[CO-(CH₂)_y2′-O]_z2′-R²⁶A 1-valent group represented by, R^26″Is an alkyl group having 1 to 18 carbon atoms, R²⁷The hydrocarbon group may have no substituent, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R is as defined above²⁶The hydrocarbon group in (1) may be the same as R²The same hydrocarbon groups as shown in (1).

R is as defined above²³And R^26′Wherein x2 and x2 ' are the same as x, y2 and y2 ' are the same as y, and z2 and z2 ' are the same as z.

R in the structural unit represented by the above general formula (III)²³May be the same or different.

As the above-mentioned R²³And R^26′Among them, those having excellent solubility in the following solvents are preferably used, and examples thereof include those having excellent solubility in the above-mentioned solvent R³²And R³⁶The same is true.

In addition, the above R²³、R²⁶、R^26′、R^26″And R²⁷The block copolymer may be substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group within a range not to impair dispersibility or the like of the block copolymer, or the block copolymer may be synthesized and then reacted with a compound having the substituent to add the substituent. Alternatively, after the block copolymer having these substituents is synthesized, a compound having a functional group reactive with the substituents and a polymerizable group may be addedThe reaction proceeds to add a polymerizable group. For example, the polymerizable group can be added by reacting (meth) acrylic acid with a block copolymer having a glycidyl group, or by reacting hydroxyethyl (meth) acrylate with a block copolymer having an isocyanate group.

The number of the structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, but is preferably 10 to 200, more preferably 20 to 100, and further more preferably 30 to 80, in terms of effectively functioning the solvent affinity site and the color material affinity site to improve the dispersibility of the color material dispersion.

In the block copolymer, the content ratio of the structural unit represented by the general formula (III) is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, based on the total structural units of the block copolymer.

The content ratio of the structural unit is calculated from the amount added in synthesizing the block copolymer.

The block portion containing the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity site, and the structural unit represented by the general formula (III) may contain 1 type, or may contain 2 or more types. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes 2 or more kinds of structural units, 2 or more kinds of structural units may be randomly arranged in the block portion including the structural unit represented by the general formula (III).

In the block copolymer used as a dispersant, the ratio m/n of the number m of the structural units including the block portion of at least one kind selected from the structural units represented by the general formula (I) and the structural units represented by the general formula (I') to the number n of the structural units including the block portion of the structural units represented by the general formula (III) is preferably in the range of 0.01 to 1, and more preferably in the range of 0.1 to 0.7 in terms of dispersibility and dispersion stability of the colorant.

The bonding order of the block copolymer is not particularly limited as long as it has a block portion containing at least one kind selected from the structural units represented by the general formula (I) and a block portion containing the structural unit represented by the general formula (III) and can stably disperse the color material, and it is preferable that the block portion containing at least one kind selected from the structural units represented by the general formula (I) be bonded only to one end of the block copolymer in terms of excellent interaction with the color material and effective suppression of aggregation of the dispersing agents.

The mass average molecular weight of the block copolymer is not particularly limited, and is preferably 2500 to 500000, more preferably 3000 to 400000, and even more preferably 6000 to 300000 in terms of satisfactory dispersibility and excellent heat resistance.

In terms of dispersibility and storage stability of the coloring material, the acid value of the polymer having at least 1 kind selected from the structural units represented by the general formula (I) is preferably 20mgKOH/g or more, more preferably 30mgKOH/g or more, and still more preferably 40mgKOH/g or more. On the other hand, in terms of excellent developability, the acid value of the polymer having at least 1 kind selected from the structural units represented by the above general formula (I) is preferably 150mgKOH/g or less, more preferably 120mgKOH/g or less, and still more preferably 100mgKOH/g or less.

In the present invention, the acid value is the number of mg of potassium hydroxide required for neutralizing the acid component contained in sample 1g, and can be determined in accordance with JIS K0070: 1992.

< other acidic dispersant >

The color material dispersion liquid of the present invention may further contain another acidic dispersant different from the polymer having at least 1 kind of structural unit selected from the group represented by the general formula (I).

Examples of the other acidic dispersants include dispersants having an acidic group. Examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and among these, a carboxyl group is preferable in terms of excellent dispersibility as an acidic group contained in a dispersant of another acidic dispersant.

The acid value of the other acidic dispersant is preferably 40mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of excellent dispersibility. On the other hand, the acid value of the other acidic dispersant is preferably 200mgKOH/g or less, more preferably 190mgKOH/g or less, and still more preferably 180mgKOH/g or less, from the viewpoint of suppressing the development residue.

In the present invention, as the other acidic dispersant, a polymeric dispersant having a carboxyl group is preferable in that the inhibition of development residue is improved by using it in combination with at least 1 polymer having a structural unit selected from the group consisting of the structural units represented by the above general formula (I), and in that the inhibition of development residue is improved and the uniformity of a coating film is improved by using it in combination with at least 1 polymer having a structural unit selected from the group consisting of the structural units represented by the above general formula (I), it is preferable to further include a block copolymer containing: an A block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block comprising structural units derived from an alkyl (meth) acrylate.

(Block copolymer comprising A block comprising structural units derived from carboxyl group-containing ethylenically unsaturated monomer and B block comprising structural units derived from alkyl (meth) acrylate)

Hereinafter, the block copolymer containing an a block comprising a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and a B block comprising a structural unit derived from an alkyl (meth) acrylate may be simply referred to as "carboxyl group-containing block copolymer".

{ A Block }

The a block is a polymer block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer.

Examples of the carboxyl group-containing ethylenically unsaturated monomer used for the A block include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride with a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; vinyl monomers having a carboxyl group such as vinyl benzoic acid, and the like.

The structural units derived from ethylenically unsaturated monomers mean: the carbon-carbon double bond of the ethylenically unsaturated monomer capable of radical polymerization is a structural unit of a carbon-carbon single bond.

When the a block contains 2 or more kinds of structural units, each structural unit may be contained in the a block in an arbitrary form such as random copolymerization, block copolymerization, or the like, and is preferably contained in a random copolymerization form from the viewpoint of uniformity.

The structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer in the a block is preferably 40% by mass or more, more preferably 70% by mass or more, and still more preferably a polymer block composed only of the structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer, relative to the entire structural units of the a block.

The a block may be composed of only a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer, or may include a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer in a range where the a block is more acidic than the B block. When the a block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer, the content is preferably 60% by mass or less, more preferably 30% by mass or less, based on the total structural units of the a block. Examples of the ethylenically unsaturated monomer other than the carboxyl group-containing ethylenically unsaturated monomer include the structural units used in the following B block.

The content of the a block is preferably 5 mass% or more, preferably 10 mass% or more, on the other hand, preferably 95 mass% or less, more preferably 40 mass% or less, with respect to the total structural units of the block copolymer, from the viewpoint of dispersibility and dispersion stability.

{ B Block }

The B block is a polymer block comprising structural units derived from an alkyl (meth) acrylate.

The alkyl (meth) acrylate monomer used for the B block may be used in the same manner as the alkyl (meth) acrylate monomer used for the polymer chain contained in the structural unit represented by the general formula (IV), and 1 or 2 or more kinds may be mixed.

In the B block, structural units derived from other ethylenically unsaturated monomers may be contained in addition to structural units derived from alkyl (meth) acrylates. Examples of the structural unit derived from another ethylenically unsaturated monomer include: among the structural units represented by the above general formula (III), a structural unit different from a structural unit derived from an alkyl (meth) acrylate.

When the B block contains 2 or more kinds of structural units, each structural unit may be contained in the B block in any form such as random copolymerization, block copolymerization, or the like, and is preferably contained in the form of random copolymerization from the viewpoint of uniformity. For example, the B block can also be formed from a copolymer of structural units comprising the B1 block and structural units comprising the B2 block.

In the B block, the structural unit derived from the ethylenically unsaturated monomer having an acidic group is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less, based on the total structural units of the B block. In the present invention, the B block is more preferably a polymer block containing no structural unit derived from an ethylenically unsaturated monomer having an acidic group.

The block copolymer containing a carboxyl group may be an AB block copolymer or a BAB block copolymer. When the block copolymer is a BAB block copolymer, the content ratio of 2B blocks is preferably adjusted within a range of (50: 50) to (70: 30) in terms of the dispersibility.

The acid value of the above-mentioned carboxyl group-containing block copolymer is preferably in the range of 30mgKOH/g to 250mgKOH/g in view of dispersibility, and it is preferable that the a block contains a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer so that the acid value of the block copolymer falls within this range. The acid value is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The acid value is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

In terms of dispersibility, the mass average molecular weight (Mw) of the carboxyl group-containing block copolymer is preferably 5000 to 100000. Mw is more preferably 8000 or more, and further preferably 10000 or more. Mw is more preferably 80000 or less, and still more preferably 70000 or less.

The molecular weight distribution of the block copolymer having a carboxyl group is preferably less than 2, more preferably less than 1.5, and still more preferably less than 1.3. In the present invention, the molecular weight distribution is determined by (mass average molecular weight (Mw))/(number average molecular weight (Mn)). The larger the molecular weight distribution, the more the polymer contains a smaller molecular weight or a larger molecular weight than the molecular weight of the designed polymer, and the dispersibility of the colored material tends to deteriorate.

As the method for producing the above-mentioned carboxyl group-containing block copolymer, a conventionally known method for producing a block copolymer can be appropriately selected and used. In terms of ease of production of a polymer having a uniform composition, a living polymerization method is preferably used, and examples of the living polymerization method include: a method using an organic acid catalyst and a silane initiator (GTP method), a method using a transition metal catalyst (ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), a method using an organic tellurium compound (TERP method), and the like.

< content ratio of acidic dispersant >

When a polymer having at least 1 kind of structural unit selected from the structural units represented by the general formula (I) is used in combination with an acidic dispersant other than the polymer, the content ratio of the polymer having at least 1 kind of structural unit selected from the structural units represented by the general formula (I) to the acidic dispersant other than the polymer can be appropriately selected and used. Among them, in terms of dispersibility and suppression of development residue, it is preferable that the mass ratio of the at least 1 polymer having a structural unit selected from the group represented by the above general formula (I) to the other acidic dispersant different from the polymer is used in the same manner as the mass ratio of the at least 1 lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the following general formula (2) contained in the color material to the alkali-treated phthalocyanine pigment.

That is, in the case where the content of at least 1 kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is 20 mass% or more and 85 mass% or less with respect to the total content of the at least 1 kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) and the phthalocyanine pigment, it is preferable that the content of at least 1 kind of polymer having a structural unit selected from the group represented by the general formula (I) in the acid dispersant is 20 mass% or more and 85 mass% or less with respect to the total content of the polymer having at least 1 kind of structural unit selected from the group represented by the general formula (I) and the other acid dispersant different from the polymer, in terms of dispersibility and development residue suppression.

The content ratio of the acidic dispersant in the color material dispersion liquid may be appropriately adjusted, and is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the color material, in terms of dispersibility and storage stability.

In addition, the content of the acidic dispersant in the color material dispersion is more preferably in a ratio of 3 mass% to 45 mass%, more preferably 5 mass% to 35 mass% with respect to the total amount of solid components in the color material dispersion, from the viewpoint of dispersibility and dispersion stability.

[ solvent ]

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse them. The solvents may be used alone or in combination of 2 or more.

Specific examples of the solvent include: alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methyl alcohol, and ethyl alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, Butyl Carbitol Acetate (BCA), and carbitol acetate; diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ -butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of the solubility of other components. Among them, as the solvent used in the present invention, in terms of solubility and coatability of other components, 1 or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Butyl Carbitol Acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate is preferable.

In the color material dispersion liquid of the present invention, the solvent as described above is preferably in the range of usually 55 mass% to 95 mass%, more preferably 65 mass% to 90 mass%, and still more preferably 70 mass% to 88 mass%, based on the total amount of the color material dispersion liquid containing the solvent. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. In addition, if the solvent is too much, the color material concentration decreases, and it is difficult to achieve the target chromaticity coordinates.

[ other ingredients ]

In the color material dispersion liquid of the present invention, a dispersion auxiliary resin and other components may be further blended as necessary as long as the effects of the present invention are not impaired.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified for the colored resin compositions described below. The dispersion stabilization may be achieved by making the color material particles less likely to contact each other due to the steric hindrance of the alkali-soluble resin, or the dispersion stabilization effect may provide an effect of reducing the dispersant.

Examples of the other components include: a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, a shrinkage preventing agent, an antioxidant, an anti-coagulation agent, an ultraviolet absorber, and the like.

The color material dispersion liquid of the present invention is used as a preparation for preparing the following colored resin composition. Namely, the color material dispersion liquid is: a color material dispersion liquid prepared in advance in the previous stage of the preparation of the following colored resin composition and having a relatively high P/V (mass of color material component in composition)/(mass of solid component other than color material component in composition). Specifically, the ratio (mass of color material component in the composition)/(mass of solid component other than color material component in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the following components, a colored resin composition having excellent dispersibility can be produced.

[ Process for producing a colorant Dispersion ]

In the present invention, the method for producing the color material dispersion liquid is not particularly limited as long as the method can obtain a color material dispersion liquid in which the color material is dispersed in a solvent by the dispersant.

For example, the method for producing the color material dispersion liquid of the present invention includes the following steps: preparing the color material; preparing the dispersant; and a step of dispersing the color material in a solvent in the presence of the dispersant. In the solvent, 2 or more kinds of color materials may be co-dispersed in the presence of the above-mentioned dispersant, or 2 or more kinds of color material dispersions may be mixed after 1 or more kinds of color materials are dispersed or co-dispersed, thereby obtaining the color material dispersion liquid of the present invention.

Among them, in terms of the dispersibility of the color material, the storage stability, the substrate adhesion and the uniformity of the coating film being easily improved, it is preferable to prepare a color material dispersion a in which at least 1 kind of lake color material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2) is dispersed in a solvent in the presence of at least 1 kind of polymer having a structural unit selected from the group represented by the above general formula (I), and to prepare a color material dispersion B in which the alkali-treated phthalocyanine pigment is dispersed in a solvent in the presence of a block copolymer containing an a block derived from a carboxyl group-containing ethylenically unsaturated monomer and a B block derived from a structural unit derived from an alkyl (meth) acrylate, and to mix the color material dispersion a and the color material dispersion B, the color material dispersion liquid of the present invention is thus produced.

In the above-described manufacturing method, the color material may be dispersed using a conventionally known dispersing machine.

Specific examples of the dispersing machine include: a roll mill such as a double roll mill or a three roll mill, a ball mill such as a ball mill or a vibration ball mill, a bead mill such as a paint conditioner, a continuous disk bead mill, or a continuous ring bead mill. As the preferable dispersing condition of the bead mill, the bead diameter to be used is preferably 0.03mm to 3.0mm, more preferably 0.05 to 2.0 mm.

Colored resin composition

The colored resin composition of the present invention is characterized by containing a coloring material, an acidic dispersant, a binder component and a solvent,

the acidic dispersant contains at least 1 polymer selected from the structural units represented by the general formula (I).

The colored resin composition of the present invention has the following effects by the same action as described above for the color material dispersion liquid: even if a predetermined lake material and a phthalocyanine pigment are mixed in a desired range, a colored layer having excellent dispersibility and storage stability and improved substrate adhesion and coating film uniformity can be formed.

The colored resin composition of the present invention contains at least a coloring material, a dispersant, a binder component and a solvent, and may further contain other components within a range not to impair the effects of the present invention. The respective components contained in the colored resin composition of the present invention will be described below, but the color material, the dispersant, and the solvent are the same as those described in the color material dispersion liquid of the present invention, and therefore, the description thereof will be omitted.

Hereinafter, each component of the colored resin composition of the present invention will be described in detail in order.

[ Binder component ]

The colored resin composition of the present invention contains a binder component in order to impart film formability or adhesion to a surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. The curable binder component is not particularly limited, and a curable binder component used for forming a colored layer of a conventionally known color filter can be suitably used.

As the curable binder component, for example, there can be used: the curable adhesive composition contains a photocurable adhesive component containing a photocurable resin which can be polymerized and cured by visible light, ultraviolet light, electron beams, or the like, and a curable adhesive component containing a thermosetting resin which can be polymerized and cured by heating.

When a photolithography step is used for forming a colored layer, a photosensitive binder component having alkali developability is preferably used. In addition, a thermosetting adhesive component may be further used as the photosensitive adhesive component.

Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a type containing an alkali-soluble resin and an o-quinonediazido group-containing compound as a photosensitivity-imparting component.

On the other hand, as the negative photosensitive binder component, a type containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is suitably used.

In the colored resin composition of the present invention, a negative photosensitive binder component is preferable in that a pattern can be easily formed by photolithography using a conventional process.

The alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described below.

< alkali-soluble resin >

The alkali-soluble resin of the present invention has an acidic group, and can be suitably selected from alkali-soluble resins which function as binder resins and are soluble in an alkali developing solution used for pattern formation.

In the present invention, the alkali-soluble resin may be used as a standard having an acid value of 40mgKOH/g or more.

The alkali-soluble resin preferred in the present invention is a resin having an acidic group and usually a carboxyl group, and specific examples thereof include: acrylic resins such as acrylic copolymers having a carboxyl group and styrene-acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like.

Among these, particularly preferred is an alkali-soluble resin having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain. When the photopolymerizable functional group is contained, the alkali-soluble resins may form a crosslinking bond with each other or with a photopolymerizable compound such as a polyfunctional monomer in a curing step of the resin composition in the production of the color filter. The cured film further has improved film strength and improved development resistance, and further has suppressed thermal shrinkage of the cured film and excellent adhesion to the substrate.

The method for introducing an ethylenic double bond into an alkali-soluble resin may be appropriately selected from conventionally known methods. Examples thereof include: a method of introducing an ethylenic double bond into a side chain of a compound having an epoxy group and an ethylenic double bond in a molecule, for example, glycidyl (meth) acrylate, by adding a carboxyl group of an alkali-soluble resin to the compound; a method in which a compound having an isocyanate group and an ethylenic double bond in the molecule is added to introduce a structural unit having a hydroxyl group into the copolymer, and an ethylenic double bond is introduced into a side chain.

In addition, the alkali-soluble resin preferably further has a hydrocarbon ring in terms of excellent adhesion of the colored layer. By having a hydrocarbon ring as a bulky group in the alkali-soluble resin, shrinkage during curing can be suppressed, peeling from the substrate can be alleviated, and substrate adhesion can be improved.

Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a combination thereof, and the hydrocarbon ring may have a substituent such as an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.

The hydrocarbon ring may be contained as a 1-valent group or may be contained as a group having a valence of 2 or more.

Specific examples of the hydrocarbon ring include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo [5.2.1.0(2, 6) ] decane (dicyclopentane), adamantane and the like; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic and Cardo structure (9, 9-diaryl fluorene) such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene and the like; a group in which a part of these groups is substituted with a substituent, and the like.

Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

When an aliphatic hydrocarbon ring is contained as the hydrocarbon ring, it is preferable in terms of improvement in heat resistance and adhesion of the colored layer and improvement in luminance of the obtained colored layer.

In addition, when the Cardo structure is included, the improvement of the curability of the colored layer, the suppression of the color fading of the color material, and the improvement of the solvent resistance (NMP swelling suppression) are particularly preferable.

Acrylic resins such as acrylic copolymers containing a structural unit having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are (co) polymers obtained by (co) polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, another copolymerizable monomer by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω -carboxy-polycaprolactone mono (meth) acrylate can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride or the like, which is a precursor of the carboxyl group, may also be used. Among them, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin in the present invention is preferably an acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, or a carboxyl group-containing copolymer such as a styrene-acrylic copolymer, and more preferably an acrylic copolymer containing a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond, or a carboxyl group-containing copolymer such as a styrene-acrylic copolymer.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like, and at least 1 selected from cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene is preferably used in terms of having a large effect of maintaining the cross-sectional shape of the colored layer after development even in heat treatment.

The carboxyl group-containing copolymer may further contain other structural units such as structural units having an ester group, such as methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group functions not only as a component for suppressing alkali solubility of the colored resin composition but also as a component for improving solubility in a solvent and resolubility in a solvent.

The carboxyl group-containing copolymer can be an alkali-soluble resin having desired properties by appropriately adjusting the amount of each structural unit added.

The amount of the carboxyl group-containing ethylenically unsaturated monomer added is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxyl group-containing ethylenically unsaturated monomer added is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the monomers, in terms of suppressing film roughness and the like on the pattern surface after development.

In addition, in a carboxyl group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer containing a structural unit having an ethylenic double bond, which is more preferably used as an alkali-soluble resin, the amount of the compound having both an epoxy group and an ethylenic double bond added to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less.

The preferable mass average molecular weight (Mw) of the carboxyl group-containing copolymer is in the range of 1000 to 50000, and more preferably 3000 to 20000. When the amount is 1000 or more, the binder function after curing is improved, and when the amount is 50000 or less, pattern formation is favorable upon development with an alkali developer.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and is preferably an epoxy (meth) acrylate compound obtained by reacting an acid anhydride with a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid.

The epoxy compound, the unsaturated group-containing monocarboxylic acid and the acid anhydride can be appropriately selected from known ones and used.

The epoxy (meth) acrylate resin having a carboxyl group preferably has the above-mentioned hydrocarbon ring in the molecule, and particularly preferably contains a Cardo structure in terms of improving the curability of the colored layer, suppressing the discoloration of the color material, and increasing the residual film ratio of the colored layer.

The epoxy (meth) acrylate resin having a carboxyl group may be used alone in 1 kind or in combination of two or more kinds.

In terms of the developability (solubility) of the alkaline aqueous solution used in the developer, the alkali-soluble resin is preferably selected from those having an acid value of 30mgKOH/g or more. The acid value of the alkali-soluble resin is preferably 40mgKOH/g to 300mgKOH/g, and particularly preferably 50mgKOH/g to 280mgKOH/g, in terms of the developability (solubility) of an alkaline aqueous solution used in a developer and the adhesion to a substrate.

In order to obtain the effects of improving the film strength of the cured film, improving the development resistance, and having excellent adhesion to the substrate, the equivalent weight of the ethylenically unsaturated bond in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the equivalent weight of the ethylenically unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. Further, when the content is 100 or more, the ratio of other structural units such as the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring can be relatively increased, and thus, the developing property and the heat resistance are excellent.

Here, the equivalent weight of the ethylenically unsaturated bond means a mass average molecular weight per 1 mole of the ethylenically unsaturated bond of the alkali-soluble resin, and is represented by the following numerical formula (1).

Digital type (1)

Equivalent of ethylenically unsaturated bond (g/mol) ═ W (g)/M (mol)

(in the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenic double bonds contained in the alkali-soluble resin W (g))

The above ethylenically unsaturated bond equivalent can be determined, for example, by the following method in accordance with JIS K0070: 1992 the iodine value was determined by measuring the number of ethylenic double bonds contained in 1g of the alkali-soluble resin.

The alkali-soluble resin used in the colored resin composition may be used alone in 1 kind, or may be used in combination with 2 or more kinds, and the content thereof is not particularly limited, but the alkali-soluble resin is preferably within a range of 5 mass% or more and 60 mass% or less, and more preferably 8 mass% or more and 40 mass% or less, with respect to the total solid content of the colored resin composition. When the content of the alkali-soluble resin is not less than the lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the upper limit, film roughness or pattern defects can be suppressed during development.

< photopolymerizable Compound >

The photopolymerizable compound used in the colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and a compound having 2 or more ethylenically unsaturated double bonds is usually suitably used, and a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups is particularly preferable.

Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in Japanese patent laid-open publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone in 1 kind, or may be used in combination with 2 or more kinds. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition of the present invention, the photopolymerizable compound is preferably a poly (meth) acrylate having 3 or more (trifunctional) polymerizable double bonds, preferably a 3-membered or more polyhydric alcohol, or a dicarboxylic acid modified product thereof, and specifically preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, or the like. The use of a polyfunctional (meth) acrylate containing a phosphorus atom such as tris (2- (meth) acryloyloxyethyl) phosphate is preferable in that discoloration of the lake material is easily suppressed and the brightness after post-baking is easily improved.

The content of the photopolymerizable compound used in the colored resin composition is not particularly limited, and is preferably within a range of 5 mass% to 60 mass%, and more preferably 10 mass% to 50 mass%, relative to the total solid content of the colored resin composition. When the content of the photopolymerizable compound is not less than the lower limit, photocuring is sufficiently performed, and elution during development of an exposed portion can be suppressed, and when the content of the photopolymerizable compound is not more than the upper limit, alkali developability is sufficient.

< photoinitiator >

The photoinitiator used in the colored resin composition of the present invention is not particularly limited, and 1 or 2 or more types of initiators can be used in combination from among various initiators known in the art.

As the photoinitiator, there may be mentioned: aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α -aminoketones, bisimidazoles, N-dimethylaminobenzophenones, halomethyl-s-triazine compounds, thioxanthones, and the like. Specific examples of the photoinitiator include: aromatic ketones such as benzophenone, 4 '-bisdiethylaminobenzophenone, and 4-methoxy-4' -dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, benzoins such as ethylbenzoin, bisimidazoles such as 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer, halomethyl oxadiazole compounds such as 2-trichloromethyl-5- (p-methoxystyryl) -1, 3, 4-oxadiazole, and halomethyl-s such as 2- (4-butoxy-naphthalen-1-yl) -4, 6-bis-trichloromethyl-s-triazine; 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone, 1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1-hydroxy-cyclohexyl-phenylketone, benzil, benzoylbenzoic acid methyl ester, 4-benzoyl-4' -methyldiphenylsulfide, benzil methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, methyl-p-toluenesulfonate, methyl acetate, methyl, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, α -dimethoxy- α -phenylacetophenone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, and the like.

Among them, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (e.g., Irgacure 907, manufactured by BASF corporation), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (e.g., Irgacure 369, manufactured by BASF corporation), 4' -bis (diethylamino) benzophenone (e.g., HIQURE ABP, manufactured by Kaikou pharmaceuticals), and diethylthioxanthone are preferably used. In addition, it is preferable to combine an α -aminophenylketone photoinitiator such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one and a thioxanthone photoinitiator such as diethylthioxanthone in terms of adjustment of sensitivity, suppression of water damage, and improvement of development resistance.

In the present invention, the photoinitiator particularly preferably contains an oxime ester photoinitiator from the viewpoint of improving sensitivity. By using the oxime ester photoinitiator, it is easy to suppress the in-plane line width unevenness when forming a fine line pattern. Further, the use of an oxime ester photoinitiator tends to improve the development resistance and increase the effect of inhibiting the generation of water stain. The water stain means: if the component for improving the alkali developability is used, traces such as water penetration occur after the alkali development and the rinsing with pure water. Such water stains disappear after post-baking, and thus there is no problem as a product, but they are detected as irregularity abnormality in appearance inspection of the patterned surface after development, and there is a problem that a normal product and an abnormal product cannot be distinguished from each other. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered, which is problematic.

Among these, those having an aromatic ring, more preferably those having a fused ring containing an aromatic ring, and still more preferably those having a fused ring containing a benzene ring and a heterocycle are preferable from the viewpoint of reducing contamination of the colored resin composition and contamination of the device due to the decomposition product.

The oxime ester photoinitiator may be suitably selected from the oxime ester photoinitiators described in 1, 2-octanedione-1- [4- (phenylthio) -, 2- (o-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime), Japanese patent application laid-open No. 2000-80068, Japanese patent application laid-open No. 2001-233842, Japanese patent application laid-open No. 2010-527339, Japanese patent application laid-open No. 2010-527338, Japanese patent application laid-open No. 2013-041153, and the like. As commercially available products, Irgacure OXE-01 (manufactured by BASF) having a carbazole skeleton, Adeka arkls NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Strong Electron New Material Co., Ltd.), Adeka arkls NCI-930 (manufactured by ADEKA Co., Ltd.), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Strong Electron New Material Co., Ltd.), TR-PBG-365 (manufactured by Changzhou Strong Electron New Material Co., Ltd.) having a fluorene skeleton, SPI-04 (manufactured by Sanzhi) and the like can be used. In particular, an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton is preferably used in terms of improvement of brightness. In addition, in terms of high sensitivity, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton.

Further, the use of 2 or more oxime ester photoinitiators in combination is preferable in that the line width at the time of pattern formation can be adjusted while maintaining good sensitivity by appropriately selecting 2 or more oxime ester compounds having different sensitivities and combining them, and that development resistance and brightness are easily improved and the effect of suppressing the generation of water stains is high. In particular, when 2 kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton are used in combination, or an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton are used in combination, it is preferable in terms of high heat resistance and easiness in improvement of luminance.

When a highly sensitive photoinitiator is used for patterning with a small exposure amount, radicals move to unexposed portions after the radicals are generated. Therefore, when patterning the colored layer and forming desired fine holes in the colored layer at the same time, it is difficult to form the unexposed portion peripheral portion without unevenness (japanese: ビリツキ) while maintaining the shape of the unexposed portion located inside the exposed portion. On the other hand, when an oxime ester photoinitiator having a fluorene skeleton is used in the combination of color materials of the present invention, the following advantages are obtained: when the colored layer is patterned, desired fine holes are easily formed in the colored layer at the same time. Among them, an oxime ester photoinitiator having a fluorene skeleton and an oxime ester photoinitiator having a phenylsulfide skeleton are preferably used in combination in terms of easily improving the shape of micropores without significantly lowering the brightness and sensitivity. In the case where desired fine pores are easily formed in the colored layer, the colored resin composition of the present invention is also suitable for, for example, the following uses: in order to form a reflective color filter, a colored layer is formed on a TFT substrate, and a through hole for conduction is formed in the colored layer. The term "unevenness" means a problem that the dimensional accuracy is deteriorated due to uneven distribution of straight lines or curved lines at the pattern edge.

In addition, it is preferable to use an oxime ester photoinitiator in combination with the α -aminophenylacetate photoinitiator in order to suppress water staining and improve sensitivity. This is because a photoinitiator having a tertiary amine structure such as an α -aminoacetophenone has a tertiary amine structure as an oxygen quencher in the molecule, and therefore radicals generated from the initiator are less likely to be inactivated by oxygen, and sensitivity can be improved.

In addition, it is preferable to combine the oxime ester photoinitiator with the thioxanthone photoinitiator in terms of sensitivity adjustment, inhibition of water stain, and improvement of development resistance, and it is preferable to combine 2 or more oxime ester photoinitiators with the thioxanthone photoinitiator in terms of improvement of brightness and development resistance, easy adjustment of sensitivity, high effect of inhibiting water stain generation, and improvement of development resistance.

The total content of the photoinitiators used in the colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and is preferably in the range of 0.1 mass% to 12.0 mass%, and more preferably 1.0 mass% to 8.0 mass%, based on the total solid content of the colored resin composition. If the content is not less than the lower limit, the photocuring is sufficiently performed to suppress elution of the exposed portion during development, while if the content is not more than the upper limit, the yellowing of the obtained colored layer is suppressed from becoming strong and the luminance is reduced.

< antioxidant >

The colored resin composition of the present invention further contains an antioxidant, and is preferably improved in heat resistance, suppressed in color fading of a coloring material, and improved in brightness. The colored resin composition of the present invention contains an antioxidant in combination with an oxime ester photoinitiator, and thus can control excessive radical chain reaction in micropores without impairing curability when the micropores are formed by a cured film, and thus can more easily form micropores of a desired shape.

The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include: hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants and the like are preferably used in terms of heat resistance and in terms of improving the shape of micropores. It may be a latent antioxidant as described in International publication No. 2014/021023.

Examples of the hindered phenol antioxidant include: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010 manufactured by BASF Co.), 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114 manufactured by BASF), 2, 4, 6-tris (4-hydroxy-3, 5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330 manufactured by BASF), 2 '-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S manufactured by Sumitomo chemical Co., Ltd.), 6' -thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox1081 manufactured by BASF), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGAMOD195, BASF), and the like. Among them, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF) is preferable in terms of heat resistance and light resistance.

The content of the antioxidant is preferably 0.1 to 10.0 mass%, more preferably 0.5 to 5.0 mass%, based on the total solid content of the colored resin composition. When the average molecular weight is not less than the above lower limit, the heat resistance and light resistance are excellent. On the other hand, if the upper limit value is less than the above, the colored resin composition of the present invention can be a photosensitive resin composition with high sensitivity.

When an antioxidant is used in combination with the oxime ester photoinitiator, the content of the antioxidant is preferably 1 part by mass or more and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of the total amount of the oxime ester photoinitiators. When the content is within the above range, the effect of the combination is excellent.

< optional additional Components >

The colored resin composition of the present invention may contain various additives as required. Examples of additives include: mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

Specific examples of the surfactant and the plasticizer include those described in Japanese patent laid-open publication No. 2013-029832.

< blending ratio of respective ingredients in colored resin composition >

The total content of the coloring materials is preferably 3 to 65 mass%, more preferably 4 to 60 mass%, based on the total solid content of the colored resin composition. When the lower limit value is not less than the above lower limit value, the color layer has a sufficient color density when the colored resin composition is applied to a predetermined film thickness (usually, 1.0 μm or more and 5.0 μm or less). When the amount is equal to or less than the above upper limit, a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate can be obtained. In particular, when a colored layer having a high color material concentration is formed, the content of the color material is preferably 15 to 65 mass%, more preferably 25 to 60 mass%, based on the total solid content of the colored resin composition.

The total content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed, and may be, for example, 1 mass% or more and 40 mass% or less with respect to the total solid content of the colored resin composition. The amount of the coloring resin composition is preferably 2 to 30 mass%, particularly preferably 3 to 25 mass%, based on the total solid content of the coloring resin composition. When the content is not less than the lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the colored resin composition is further excellent. If the upper limit value is less than the upper limit value, the developability is good. In particular, when a colored layer having a high color material concentration is formed, the content of the dispersant is preferably 2 to 25 mass%, more preferably 3 to 20 mass%, based on the total solid content of the colored resin composition.

The total content of the binder component is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, based on the total solid content of the colored resin composition.

The content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. The content is preferably in the range of usually 55 to 95% by mass, more preferably 65 to 88% by mass, based on the total amount of the colored resin composition containing the solvent. When the content of the solvent is within the above range, the coating property is excellent.

In the colored resin composition of the present invention, the P/V ratio ((mass of the color material component in the composition)/(mass of the solid component other than the color material component in the composition)) is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of desired color development, in the case of producing a blue colored resin composition. On the other hand, in terms of excellent patterning characteristics and the like, 0.65 or less is preferable, 0.50 or less is more preferable, and 0.45 or less is even more preferable.

< method for producing colored resin composition >

The method for producing the colored resin composition of the present invention is not particularly limited, and for example, it can be obtained by adding a binder component and other components as required to the color material dispersion liquid of the present invention and mixing them by a known mixing means. Alternatively, the dispersion medium may be obtained by preparing a dispersion liquid of each color material using the dispersant, and mixing the dispersion liquid of each color material, a binder component, and other components as necessary using a known mixing means.

The colored resin composition of the present invention is suitably used for color filter applications because it has excellent dispersibility and storage stability and can form a colored layer having improved substrate adhesion and coating film uniformity even when a predetermined lake material and a phthalocyanine pigment are mixed within a desired range.

III cured product

The cured product of the present invention is a cured product of the colored resin composition of the present invention.

The cured product of the present invention can be produced by appropriately selecting the curing properties of the binder component. For example, in the case of using a photosensitive binder component, the resin composition can be obtained by forming a coating film of the colored resin composition of the present invention, drying the coating film, exposing the coating film to light, and optionally developing the coating film. The method of forming, exposing, and developing a coating film may be, for example, the same method as that used for forming a colored layer included in a color filter of the present invention described below. In addition, for example, in the case of using a thermosetting binder component, the coating film of the colored resin composition of the present invention can be applied by patterning as necessary, and the coating film is dried and then heated.

The cured product of the present invention has excellent dispersibility and storage stability, and improves substrate adhesion and coating film uniformity, even when a predetermined lake material and a phthalocyanine pigment are mixed in a desired range, and is suitably used as a colored layer of a color filter.

IV. color filters

The color filter of the present invention comprises at least a transparent substrate and colored layers provided on the transparent substrate, wherein at least one of the colored layers comprises a coloring material and an acidic dispersant, the coloring material comprises at least 1 lake material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2), and a phthalocyanine pigment subjected to alkali treatment, and the acidic dispersant comprises at least 1 polymer having a structural unit selected from the group represented by the general formula (I).

The color filter of the present invention has high brightness and improved heat resistance, at least one of the colored layers comprises a color material and an acidic dispersant, the color material comprises at least 1 kind of lake material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), and a phthalocyanine pigment subjected to alkaline treatment, and the acidic dispersant comprises at least 1 kind of polymer selected from the structural units represented by the general formula (I), so that the color filter has excellent dispersibility and storage stability, and improves substrate adhesion and coating uniformity. The specific color material is dispersed in the specific dispersant, whereby the dispersibility and the storage stability are improved, and the luminance and the heat resistance of the colored layer are improved. In addition, even if a fine pattern is formed in the patterning process, the coating film is not easily peeled off, and the burden of management and cost in manufacturing can be reduced. Further, when the coating film uniformity is improved, a color filter with reduced color unevenness even in a large substrate can be obtained.

Such a color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. Referring to fig. 1, a color filter 10 according to the present invention includes a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

[ coloring layer ]

At least one of the colored layers used in the color filter of the present invention contains a color material containing at least 1 kind of lake material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), and a phthalocyanine pigment subjected to alkali treatment, and an acidic dispersant containing at least 1 kind of polymer selected from the structural units represented by the general formula (I).

The colored layer is usually formed in an opening of a light shielding portion on a transparent substrate described below, and usually includes a colored pattern of 3 colors or more.

The arrangement of the colored layers is not particularly limited, and may be, for example, a typical arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement type. The width, area, and the like of the colored layer can be set arbitrarily.

The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition, and is preferably in the range of 1 μm to 5 μm.

For example, when the colored resin composition is a photosensitive resin composition, the colored layer can be formed by the following method. The colored layer used for the color filter is preferably formed using a colored resin composition, preferably a cured product of the colored resin composition, the colored resin composition containing the color material, an acidic dispersant, a solvent and a binder component, the color material containing at least 1 lake material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), and a phthalocyanine pigment subjected to alkali treatment, and the acidic dispersant containing at least 1 polymer having a structural unit selected from the group represented by the general formula (I).

First, a wet coating film is formed by applying a colored resin composition onto a transparent substrate described below by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, or a spin coating method.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, whereby an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized to form a photosensitive coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and electron beams. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.

In addition, heat treatment may be performed to promote the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, by performing a developing treatment using a developing solution, unexposed portions are dissolved and removed, and a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. In addition, a general method can be employed for the development method.

After the development treatment, the cured coating film of the colored resin composition is usually washed with a developer and dried to form a colored layer. After the development treatment, a heating treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

[ light-shielding portion ]

The light-shielding portion of the color filter of the present invention is formed in a pattern on the following substrate, and can be made the same as that used as a light-shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a thin metal film of chromium or the like formed by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

The thickness of the light-shielding portion is set to be about 0.2 μm to about 0.4 μm in the case of a thin metal film, and is set to be about 0.5 μm to about 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[ transparent substrate ]

The transparent substrate is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, there may be mentioned: a non-flexible transparent rigid material such as quartz glass, alkali-free glass, or synthetic quartz plate, or a transparent flexible material having flexibility or bendability such as a transparent resin film, an optical resin plate, or flexible glass. The transparent substrate used for such a color filter usually has a polar group on the surface.

In order to improve the substrate adhesion of the colored resin composition of the present invention, a substrate containing silica such as quartz glass, alkali-free glass, or a synthetic quartz plate is preferable as the transparent substrate.

The thickness of the transparent substrate is not particularly limited, and for example, a transparent substrate having a thickness of 50 μm or more and 1mm or less can be used depending on the application of the color filter.

In addition to the transparent substrate, the light-shielding portion, and the colored layer, the color filter of the present invention may further include, for example, an overcoat layer or a transparent electrode layer, an alignment film for aligning a liquid crystal material, or a columnar spacer. The color filter of the present invention is not limited to the above-described exemplary configuration, and any known configuration generally used for color filters can be appropriately selected and used.

V display device

The display device of the present invention is characterized by having the color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device, an organic light emitting display device, and the like.

[ liquid Crystal display device ]

The liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a display device of the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As illustrated in fig. 2, a liquid crystal display device 40 according to the present invention includes a color filter 10, a counter substrate 20 including a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used for a liquid crystal display device can be generally employed. Examples of such a driving method include a TN (Twisted Nematic) method, an IPS (In-Plane Switching) method, an OCB (optically compensated bend) method, and an MVA (Multi-Domain Vertical Alignment) method. In the present invention, any of these methods can be suitably used.

The counter substrate may be used by appropriately selecting a driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method, a liquid crystal dropping method, and the like.

[ organic light emitting display device ]

The organic light emitting display device of the present invention is characterized by having the color filter and the organic light emitting body of the present invention.

Such an organic light emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing another example of the display device of the present invention, and is a schematic view showing an example of an organic light emitting display device. As illustrated in fig. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

Examples of the method for stacking the organic light-emitting bodies 80 include: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; or a method of bonding the organic light-emitting body 80 formed on a separate substrate to the inorganic oxide film 60. In the organic light-emitting device 80, known structures such as the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 can be used as appropriate. The organic light emitting display device 100 thus manufactured can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.

The organic light emitting display device of the present invention is not limited to the configuration shown in fig. 3, and may be a configuration generally known as an organic light emitting display device using a color filter.

[ examples ]

The present invention will be specifically described below with reference to examples. The invention is not limited by these statements.

The acid value is determined by the following method in accordance with JIS K0070: 1992, etc.

The mass average molecular weight (Mw) is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.

(Synthesis example 1: Synthesis of lake Material 1)

(1) Synthesis of intermediate 1

Intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%) by referring to the processes for producing intermediate A-2, intermediate B-1 and compound 1-3 described in Japanese patent application laid-open No. 2018-3013.

The obtained compound was confirmed as the target compound according to the following analysis results.

MS (ESI) (m/z): 677(+), valence 2

Elemental analysis value: CHN found (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

[ solution 14]

Chemical formula (a)

(2) Synthesis of lake Material 1

2.59g (0.76mmol) of 12-tungstophosphoric acid n-hydrate (Kanto chemical Co., Ltd.) was dissolved in a mixture of 40mL of methanol and 40mL of water under heating, and 11.6g (1.19mmol) of the intermediate was added thereto, followed by stirring for 1 hour. The precipitate was filtered and washed with water. The obtained precipitate was dried under reduced pressure to obtain a laked material 1 represented by the following chemical formula (b) (yield 95%).

The obtained compound was confirmed as the target compound according to the following analysis results.

·31P NMR(d-dmso、ppm)δ-15.15

·MS(MALDI)(m/z)：1355(M⁺)、2879(MH₂ ^-)

Elemental analysis value: CHN found (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)

Fluorescent X-ray analysis: measured MoW ratio (0%, 100%); theoretical value (0%, 100%)

[ solution 15]

Chemical formula (b)

(Synthesis example 2 Synthesis of lake Material 2)

(1) Synthesis of intermediate 2

Referring to the production methods of intermediate 3 and intermediate 4 described in international publication No. 2012/144521, 215.9 g (yield 70%) of intermediate represented by the following chemical formula (c) was obtained.

The obtained compound was confirmed as the target compound according to the following analysis results.

MS (ESI) (m/z): 511(+), 2-valent

Elemental analysis value: CHN found (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

[ solution 16]

Chemical formula (c)

(2) Synthesis of lake Material 2

Intermediate 25.00g (4.58mmol) was added to 300ml of water and dissolved at 90 ℃ to prepare intermediate 2 solution. Next, the phosphotungstic acid n hydrate H prepared by the inorganic chemical industry of Japan₃[PW₁₂O₄₀]·nH₂O (n ═ 30)10.44g (3.05mmol) was added to 100mL of water, and stirred at 90 ℃ to prepare an aqueous phosphotungstic acid solution. An aqueous solution of phosphotungstic acid was mixed with the previous intermediate 2 solution at 90 ℃ and the resulting precipitate was filtered off and washed with water. The obtained cake was dried to obtain 213.25g (yield 98%) of a lake material represented by the following chemical formula (d).

The obtained compound was confirmed as the target compound according to the following analysis results. (molar ratio W/Mo 100/0)

MS (ESI) (m/z): 510(+), 2 price

Elemental analysis value: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%, 5.17%, 4.11%)

In addition, according to³¹P-NMR confirmed that: the polyacid structure of phosphotungstic acid is also maintained after forming into the lake material 2.

[ solution 17]

Chemical formula (d)

(Synthesis example 3 Synthesis of alkali-treated phthalocyanine pigment 1)

300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were charged into a reaction vessel, and after completely dissolving, 24 parts by mass of thionyl chloride was added, and the mixture was gradually heated to react at 101 ℃ for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, stirred, and then filtered and washed with water. After the obtained press cake was made into a slurry with 300 parts by mass of water, 13 parts by mass of 1, 1-diethyl-1, 5-diazapene was added, and after stirring at 65 ℃ for 4 hours, filtration, washing with water, and drying were performed to obtain blue color material derivative 1 having a basic site for surface treatment. The obtained blue color material derivative 1 having a basic site was confirmed to have a structure represented by the following chemical formula (e).

·TOF-MS：768.35

[ solution 18]

Chemical formula (e)

Commercially available c.i.pigment Blue15:6 (Epsilon-type copper phthalocyanine pigment, produced by DIC, FASTOGEN BLUE A510) and 5 parts by mass of the BLUE colorant derivative 1 having a basic moiety were dry-pulverized at 60 ℃ for 1.5 hours by means of an attritor. This pulverized product was further mixed with 5 parts by mass of the blue colorant derivative 1 having a basic site, thereby obtaining a target alkali-treated phthalocyanine pigment 1, i.e., an alkali-treated phthalocyanine pigment.

(Synthesis example 4 Synthesis of alkali-treated phthalocyanine pigment 2)

In the synthesis of the alkali-treated phthalocyanine pigment 1 of synthesis example 3, as a pigment surface-treated with the Blue colorant derivative 1 having a basic moiety, a commercially available c.i. pigment Blue15: basic-treated phthalocyanine pigment 2 was obtained in the same manner as in synthesis example 3 except that 3 (. beta. -type copper phthalocyanine pigment, manufactured by DIC, FASTOGEN BLUE SFJ-SD) was used in place of commercially available C.I. pigment BLUE15: 6.

(Synthesis example 5 Synthesis of alkali-treated phthalocyanine pigment 3)

In synthesis example 3, a blue color material derivative 2 was synthesized in the same manner as in the synthesis method of the blue color material derivative 1, except that 16 parts by mass of 1, 1-diisopropyl-1, 5-diazapene was used in place of 13 parts by mass of 1, 1-diethyl-1, 5-diazapene in the synthesis method of the blue color material derivative 1.

The obtained blue color material derivative 2 having a basic site was confirmed to have a structure represented by the following chemical formula (f).

·TOF-MS：796.4

[ solution 19]

Chemical formula (f)

A base-treated phthalocyanine pigment 3 was obtained in the same manner as in synthesis example 3, except that a blue colorant derivative 2 was used in place of the blue colorant derivative 1 in the synthesis of the base-treated phthalocyanine pigment 1 in synthesis example 3.

(Synthesis example 6 Synthesis of alkali-treated phthalocyanine pigment 4)

In synthesis example 3, a blue color material derivative 3 was synthesized in the same manner as in the synthesis method of the blue color material derivative 1, except that 19 parts by mass of 1, 1-dibutyl-1, 5-diazapene was used instead of 13 parts by mass of 1, 1-diethyl-1, 5-diazapene in the synthesis method of the blue color material derivative 1.

The obtained blue color material derivative 3 having a basic site was confirmed to have a structure represented by the following chemical formula (g).

·TOF-MS：824.15

[ solution 20]

Chemical formula (g)

A base-treated phthalocyanine pigment 4 was obtained in the same manner as in synthesis example 3, except that a blue colorant derivative 3 was used in place of the blue colorant derivative 1 in the synthesis of the base-treated phthalocyanine pigment 1 in synthesis example 3.

Synthesis example 7 Synthesis of acidic dispersant A1 (Polymer having at least 1 selected from the structural units represented by the above general formula (I))

(1) Synthesis of macromonomer MM-1

Into a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen gas, a mechanical stirrer, and a digital thermometer, 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA for short) was charged, and the temperature was raised to 90 ℃ while stirring in a nitrogen gas stream. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α, α' -azobisisobutyronitrile (AIBN for short) was added dropwise over 1.5 hours, and the reaction was further carried out for 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80 ℃ and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko K.K.), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added and stirred for 3 hours, thereby obtaining a 49.5 mass% solution of macromonomer MM-1. GPC measurement showed that the macromonomer MM-1 obtained had a mass average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw/Mn) of 2.10.

(2) Synthesis of graft copolymer A1

85.0 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen gas, a mechanical stirrer, and a digital thermometer, and the temperature was raised to 90 ℃ while stirring in a nitrogen gas stream. A mixed solution of 67.34 parts by mass (solid content: 33.33 parts by mass) of the macromonomer MM-1 solution, 16.67 parts by mass of glycidyl methacrylate (GMA for short), 1.24 parts by mass of n-dodecylmercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, and after stirring under heating for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, followed by aging at the same temperature for 1 hour, whereby a 25.0% by mass solution of graft copolymer A1 was obtained. GPC measurement showed that the graft copolymer A1 obtained had a mass average molecular weight (Mw) of 10570, a number average molecular weight (Mn) of 4370 and a molecular weight distribution (Mw/Mn) of 2.42.

(3) Production of at least 1 polymer (acidic dispersant A1) having structural units selected from those represented by the general formula (I)

27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA" manufactured by Nissan chemical Co., Ltd.) were charged into a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen gas, a mechanical stirrer and a digital thermometer, and the mixture was heated to 90 ℃ while stirring the mixture under a stream of nitrogen gas.

1100.0 parts by mass of the above graft copolymer A was added dropwise over 30 minutes, and stirred with heating for 2 hours, thereby obtaining a solution (solid content: 25.0% by mass) of at least 1 kind of polymer (acidic dispersant A1) having a structural unit selected from those represented by the above general formula (I). The esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was carried out by measuring the acid value and¹H-NMR measurement was carried out to confirm (disappearance of peak derived from epoxy group was confirmed). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.

(Synthesis example 8 Synthesis of acidic dispersant A2 (Polymer having at least 1 selected from the structural units represented by the above general formula (I))

(1) Synthesis of Block copolymer A2

Referring to synthetic example 6 described in japanese patent No. 5895925, a40 mass% PGMEA solution of a diblock copolymer having a block of 50 parts by mass of Methyl Methacrylate (MMA), 30 parts by mass of n-Butyl Methacrylate (BMA), 20 parts by mass of benzyl methacrylate (BzMA), and 25 parts by mass of Glycidyl Methacrylate (GMA) was obtained. The obtained block copolymer A2 had a mass average molecular weight (Mw) of 9470, a number average molecular weight (Mn) of 7880, and a molecular weight distribution (Mw/Mn) of 1.20.

(2) Production of at least 1 polymer (acidic dispersant A2) having structural units selected from those represented by the general formula (I)

To a reactor, 2100.0 parts by mass of block copolymer a, 86.70 parts by mass of PGMEA, and 8.90 parts by mass of phenylphosphonic acid (PPA) were charged, and the mixture was stirred at 90 ℃ for 2 hours, thereby obtaining a solution (solid content: 25 mass%) of at least 1 polymer (acidic dispersant a2) having a structural unit selected from the group represented by the above general formula (I). The esterification reaction of GMA and PPA of Block copolymer A2 was carried out by measuring the acid value and¹H-NMR measurement was carried out. The acid value of the obtained acidic dispersant A2 was 65 mgKOH/g.

Synthesis example 9 Synthesis of acidic dispersant B1 (Block copolymer containing A Block comprising structural units derived from a carboxyl-containing ethylenically unsaturated monomer and B Block comprising structural units derived from an alkyl (meth) acrylate)

Referring to example 1 described in international publication No. 2016/132863, a triblock copolymer having blocks of 20 parts by mass of MMA, 40 parts by mass of BMA, 20 parts by Mass of Acrylic Acid (MAA), 20 parts by mass of BMA, and blocks of 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized. The obtained block copolymer had a mass average molecular weight (Mw) of 11000, a molecular weight distribution (Mw/Mn) of 1.50 and an acid value of 130 mgKOH/g.

Synthesis example 10 Synthesis of acidic dispersant B2 (Block copolymer containing A Block comprising structural units derived from a carboxyl-containing ethylenically unsaturated monomer and B Block comprising structural units derived from an alkyl (meth) acrylate)

A triblock copolymer having 30 parts by mass of MMA, 40 parts by mass of BMA, 10 parts by Mass of Acrylic Acid (MAA), 20 parts by mass of BMA, and 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized in the same manner as in synthesis example 9, except that the monomer addition ratio was changed to the following composition. The obtained block copolymer had a mass average molecular weight (Mw) of 15500, a molecular weight distribution (Mw/Mn) of 1.35 and an acid value of 80 mgKOH/g.

(Synthesis example 11 Synthesis of basic dispersant 1)

A salt-type amine block copolymer (basic dispersant 1) solution (solid content: 25 mass%) was prepared by charging 51.13 mass parts of PGMEA and 30.00 mass parts of a block copolymer (trade name: BYK-LPN6919, manufactured by BYK-Chemie) (amine number 120mgKOH/g, solid content 60 mass%) (solid content: 18.00 mass parts) into a reactor, adding 3.04 mass parts of PPA (0.5 molar equivalent to the tertiary amino group of the block copolymer), and stirring at 40 ℃ for 30 minutes.

(Synthesis example 12 Synthesis of alkali-soluble resin A)

150 parts by mass of PGMEA was charged into a polymerization vessel, and after raising the temperature to 100 ℃ under a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 6 parts by mass of PERBUTYL O (manufactured by Nichikoku Co., Ltd.), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100 ℃ and, after the completion of the dropwise addition of the main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.

Then, 14 parts by mass of Glycidyl Methacrylate (GMA) as an epoxy group-containing compound was added while blowing air, the temperature was raised to 110 ℃, 0.8 part by mass of triethylamine was added, and an addition reaction was carried out at 110 ℃ for 15 hours to obtain an alkali-soluble resin a solution (mass average molecular weight (Mw)9000, acid value 90mgKOH/g, solid content 40 mass%).

Preparation example 1 preparation of photosensitive Binder component CR-1)

To 36.5 parts by mass of the alkali-soluble resin a solution (solid content 40 mass%) obtained in synthesis example 12 were added 21.9 parts by mass of dipentaerythritol hexaacrylate (DPHA) (aronex M402 (manufactured by east asia) as a photopolymerizable compound), 1.1 parts by mass of Irgacure 907 (manufactured by BASF, an α -aminobenzone photoinitiator) as an initiator, 1.3 parts by mass of SPI-04 (manufactured by sanxiao, an oxime ester photoinitiator having a fluorene skeleton), 0.3 parts by mass of kayacure DETX-S (manufactured by japan chemicals, a thioxanthone photoinitiator), 0.8 parts by mass of an antioxidant IRGANOX1010 (manufactured by BASF), and 38.1 parts by mass of PGMEA, to obtain a photosensitive binder component CR-1.

(example 1)

(1) Color material dispersion liquid B1

(1-1) preparation of color Material Dispersion B1a1 of lake Material 1

110 parts by mass of the lake material of Synthesis example 1, 20 parts by mass of the acidic dispersant A1 solution of Synthesis example 7 (5.0 parts by mass of the effective solid content), 7.5 parts by mass of the alkali-soluble resin A of Synthesis example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA were mixed, and dispersed for 1 hour as pre-dispersion and further dispersed for 4 hours as main dispersion with 2mm zirconia beads by a paint shaker (manufactured by Haitian iron works), to obtain a color material dispersion liquid B1a 1.

(1-2) preparation of color Material Dispersion B1B1 of alkali-treated phthalocyanine pigment 1

110 parts by mass of the alkali-treated phthalocyanine pigment of synthesis example 3, 16.7 parts by mass of the acidic dispersant B1 solution of synthesis example 9 (5.0 parts by mass of the effective solid content), 7.5 parts by mass of the alkali-soluble resin A of synthesis example 12 (3.0 parts by mass of the effective solid content), and 65.8 parts by mass of PGMEA were mixed, and dispersed with 2mm zirconia beads by a paint shaker (manufactured by Haitian Seisaku-Sho Ltd.) for 1 hour as preliminary dispersion, and further dispersed with 0.1mm zirconia beads for 6 hours as main dispersion, to obtain a color material dispersion B1B 1.

(1-3) preparation of color Material Dispersion B1

The color material dispersion liquid B1 was prepared by mixing 198 parts by mass of the color material dispersion liquid B1B obtained in (1-2) with 12 parts by mass of the color material dispersion liquid B1a obtained in (1-1).

(2) Colored resin composition B1

116.7 parts by mass of a coloring material dispersion liquid B, 124.0 parts by mass of the photosensitive binder component CR-124.0 parts by mass of preparation example 1, 0.3 part by mass of a surfactant MEGAFAC R08MH (manufactured by DIC), and 59.0 parts by mass of PGMEA were mixed to obtain a colored resin composition B1 of example 1.

(examples 2 to 13)

(1) Color material dispersion liquid B2-B13

Color material dispersions B2 to B13 were prepared in the same manner as in example 1, except that the mixing ratio of the color material dispersion B1a1 and the color material dispersion B1B1 was changed to obtain the color material ratio (mass ratio) shown in table 1.

(2) Colored resin compositions B2-B13

Colored resin compositions B2 to B13 were obtained in the same manner as in example 1, except that in example 1, the color material dispersions B2 to B13 were used in place of the color material dispersion B1, respectively.

(examples 14 to 21)

(1) Color material dispersion liquid B14-B21

In the same manner as in (1-1) of example 1, a color material dispersion liquid B1a1 was obtained.

A color material dispersion liquid B2a1 was obtained in the same manner as in (1-1) of example 1, except that the lake material 2 of synthesis example 2 was used in place of the lake material 1 of synthesis example 1.

In addition, a color material dispersion liquid B1a2 was obtained in the same manner as in (1-1) of example 1 except that the acidic dispersant a2 solution of synthesis example 8 was used instead of the acidic dispersant a1 solution of synthesis example 7.

Further, in the same manner as in (1-2) of example 1, a color material dispersion liquid B1B1 was obtained.

A color material dispersion liquid B2B1 was obtained in the same manner as in (1-2) of example 1, except that the alkali-treated phthalocyanine pigment 2 of synthesis example 4 was used in place of the alkali-treated phthalocyanine pigment 1 of synthesis example 3.

A color material dispersion liquid B3B1 was obtained in the same manner as in (1-2) of example 1, except that the alkali-treated phthalocyanine pigment 3 of synthesis example 5 was used in place of the alkali-treated phthalocyanine pigment 1 of synthesis example 3.

A color material dispersion liquid B4B1 was obtained in the same manner as in (1-2) of example 1, except that the alkali-treated phthalocyanine pigment 4 of synthesis example 6 was used in place of the alkali-treated phthalocyanine pigment 1 of synthesis example 3.

In addition, a color material dispersion liquid B1B2 was obtained in the same manner as in (1-2) of example 1 except that the acidic dispersant B2 solution of synthesis example 10 was used instead of the acidic dispersant B1 solution of synthesis example 9.

Color material dispersions B14 to B21 were prepared in the same manner as in example 1 except that the mixing ratio of the color material dispersion B1a1, B2a1, or B1a2 to the color material dispersion B1B1, B2B1, B3B1, B4B1, or B1B2 was changed so as to obtain the color material ratio (mass ratio) shown in table 2.

(2) Colored resin compositions B14-B21

Colored resin compositions B14 to B21 were obtained in the same manner as in example 1, except that in example 1, the color material dispersions B14 to B21 were used in place of the color material dispersion B1, respectively.

(example 22)

(1) Color material dispersion liquid B22

15.0 parts by mass of the lake pigment of Synthesis example 1, 15.0 parts by mass of the alkali-treated phthalocyanine pigment of Synthesis example 3, 20 parts by mass of the acidic dispersant A1 solution of Synthesis example 7 (5.0 parts by mass of the effective solid content), 7.5 parts by mass of the alkali-soluble resin A of Synthesis example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA were mixed, and dispersed for 1 hour as a predispersion with 2mm zirconia beads by a paint shaker (manufactured by Haitian iron works), and further dispersed for 6 hours with 0.1mm zirconia beads to obtain a pigment dispersion B main 22.

(2) Colored resin composition B22

A colored resin composition B22 was obtained in the same manner as in example 1, except that in example 1, the color material dispersion liquid B22 was used in place of the color material dispersion liquid B1, respectively.

(examples 23 to 24)

(1) Color material dispersion liquid B23-B24

Color material dispersions B23 to B24 were prepared in the same manner as in example 22, except that the content ratio of the color material and the type of the lake material in example 22 were changed as shown in table 2.

(2) Colored resin compositions B23-B24

Colored resin compositions B23 to B24 were obtained in the same manner as in example 1, except that in example 1, the color material dispersions B23 to B24 were used in place of the color material dispersion B1, respectively.

Comparative examples 1 and 5

(1) Colorant dispersions CB1 and CB5

In example 22, color material dispersions CB1 and CB5 were prepared in the same manner as in example 22, except that commercially available pigment BLUE15:6 (FASTOGEN BLUE a510, manufactured by DIC) was used in place of the alkali-treated phthalocyanine pigment 1 and the content ratio of the color material was changed as shown in table 2.

(2) Colored resin compositions CB1 and CB5

Colored resin compositions CB1 and CB5 were obtained in the same manner as in example 1, except that in example 1, the color material dispersion liquids CB1 and CB5 were used in place of the color material dispersion liquid B1, respectively.

Comparative example 2

(1) Colorant dispersion CB2

A color material dispersion CB2 was prepared in the same manner as in comparative example 1, except that in comparative example 1, the solution of the basic dispersant 1 in synthesis example 11 was changed to the solution of the acidic dispersant a1 in synthesis example 7.

(2) Colored resin composition CB2

A colored resin composition CB2 was obtained in the same manner as in example 1, except that in example 1, the color material dispersion liquid CB2 was used in place of the color material dispersion liquid B1.

Comparative example 3

(1) Colorant dispersion CB3

A color material dispersion CB3 was prepared in the same manner as in example 22, except that 110 parts by mass of the lake material of synthesis example 1 was used instead of the alkali-treated phthalocyanine pigment 1 in example 22.

(2) Colored resin composition CB3

A colored resin composition CB3 was obtained in the same manner as in example 1, except that in example 1, the color material dispersion liquid CB3 was used in place of the color material dispersion liquid B1, respectively.

Comparative example 4

(1) Colorant dispersion CB4

A colorant dispersion CB4 was prepared in the same manner as in example 22, except that 10 parts by mass of commercially available pigment BLUE15:6 (FASTOGEN BLUE a510, manufactured by DIC) was used in example 22 instead of using the lake colorant 1 and the alkali-treated phthalocyanine pigment 1 in synthesis example 1.

(2) Colored resin composition CB4

A colored resin composition CB4 was obtained in the same manner as in example 1, except that in example 1, the color material dispersion liquid CB4 was used in place of the color material dispersion liquid B1, respectively.

[ evaluation method ]

< dispersibility >

The initial viscosities of the color material dispersions obtained in examples and comparative examples were measured. The viscosity was measured at 25.0. + -. 0.5 ℃ using a vibration viscometer.

(Standard for evaluation of dispersibility)

AA: viscosity of less than 5cP

A: viscosity of 5cP or more and less than 10cP

B: viscosity of 10cP or more and less than 15cP

C: viscosity of 15cP or more and less than 20cP

D: viscosity of 20cP or more

Here, this is a value when the color material is 10 mass% with respect to the total mass of the color material dispersion liquid including the solvent.

< storage stability >

The initial viscosity immediately after the preparation and the viscosity after 7 days of storage at 25 ℃ were measured for each of the color material dispersions obtained in examples and comparative examples, and the change in viscosity was confirmed.

(evaluation criteria for storage stability)

A: the absolute value of the difference between the viscosities before and after storage was within the measurement error range (less than 0.5cP)

B: the absolute value of the difference between the viscosities before and after storage is 0.5cP or more and less than 1.0cP

C: the absolute value of the difference between the viscosities before and after storage is 1.0cP or more

Here, this is a value when the color material is 10 mass% with respect to the total mass of the color material dispersion liquid including the solvent.

< optical Properties >

The colored resin compositions of examples and comparative examples were coated on GLASS substrates (NH techon GLASS co., ltd. "NA 35") having a thickness of 0.7mm so that the color values after baking became y 0.100 using a spin coater. Thereafter, the mixture was dried by heating on a heating plate at 80 ℃ for 3 minutes. Irradiating with an ultra-high pressure mercury lamp to 60mJ/cm without using a light-shielding cover²Followed by post-baking in a dust-free oven at 230 ℃ for 30 minutes, thereby obtaining a cured film (blue-colored film). The chromaticity (x, Y) and the luminance (Y) of the obtained colored substrate were measured using a "microspectrophotometer OSP-SP 200" manufactured by Olympus corporation.

< substrate adhesion >

The cured films (blue-colored films) obtained in the examples and comparative examples were subjected to a cross cut test in accordance with JIS K5600-5-6, and after repeating 5 times of peeling operations with a tape, the cured films were observed for the presence or absence of peeling, and evaluated according to the following evaluation criteria.

(evaluation criteria for substrate adhesion)

AA: no peeling of the seam of any lattice

A: there are portions where the cured film peeled off along the cut lines, but there are no portions where the entire lattice was peeled off

B: the whole part of the grid is stripped, and the special area for stripping is less than 25 percent

C: the whole part of the grid is stripped, and the exclusive area for stripping is more than 25 percent

< coating film uniformity >

The colored resin compositions of examples and comparative examples were applied to 100mm square glass substrates deposited with chromium, respectively, using a spin coater. The coated substrate was placed in a vacuum dryer and dried under reduced pressure at 30 Pa. The cured film thus produced was observed with an interference fringe inspection lamp (sodium lamp), and the presence or absence of drying unevenness generated in the coating film was visually evaluated.

(evaluation criteria for film uniformity)

A: no unevenness of cured film

B: slight unevenness was observed in the range of not reaching 50% of the whole cured film

C: the cured film has a variation in the range of 50% or more of the entire cured film

< developability >

The colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (NH TECHNO GLASS Co., Ltd. "NA 35") having a thickness of 0.7mm using a spin coater. Thereafter, the mixture was dried by heating on a heating plate at 80 ℃ for 3 minutes. An ultrahigh pressure mercury lamp is used at 60mJ/cm to separate the color layer with an independent fine line pattern mask having a line width of 1-100 μm²The glass substrate was exposed to ultraviolet light to form a colored layer having a thickness of 2.0 μm on the glass substrate.

Next, a 0.05 mass% aqueous solution of potassium hydroxide (KOH) was used as a developer to perform rotary development, and after contacting the developer, the developer was washed with pure water to perform development treatment, thereby performing pattern formation and evaluating developability. In the above-described development treatment, the time until the unexposed portion is dissolved and removed was measured. The completion of development was visually observed, and the development time was determined according to the following criteria.

(evaluation criteria for developability)

AA: less than 40 seconds

A: 40 seconds or more and less than 60 seconds

B: 60 seconds or more and less than 80 seconds

C: more than 80 seconds

< line width offset >

The colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (manufactured by NH techon GLASS co., ltd., "NA 35") having a thickness of 0.7mm so that the film thickness became 3 μm using a spin coater. Then, the mixture was dried by heating on a hot plate at 80 ℃ for 3 minutesAfter drying, a mask pattern having a fine line pattern (line width deviation evaluation pattern) with an opening width of 90 μm and a pattern (fine hole evaluation pattern) in which a chrome mask of 20 μm × 20 μm is disposed at the center in an independent fine line having an opening size of 90 μm × 300 μm was irradiated with 60mJ/cm using an ultra-high pressure mercury lamp²Ultraviolet rays of (1). Thereafter, the glass plate on which the colored layer was formed was subjected to spray development using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution, and post-baked in a dust-free oven at 230 ℃ for 30 minutes. The width (line width) of the individual fine line actually measured when the opening width of the mask in the individual fine line of the colored layer fine line pattern formed on the glass substrate was 90 μm and the design line width was 95 μm was measured and evaluated according to the following criteria.

(line Width offset evaluation Standard)

The line width offset value (μm) which is the deviation from the designed line width was calculated from the following formula.

Linewidth offset value (μm) — measured linewidth (μm) -95(μm)

A: the line width deviation value is more than-2 μm and less than 2 μm

B: the line width deviation value is more than-4 μm and less than-2 μm

C: the line width deviation value is less than-4 μm or more than 2 μm

The evaluation was: as the deviation of the self-designed line width is smaller, a pattern can be formed with a desired line width.

< color change after heating step (. DELTA.Eab) >

The colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (NH techon GLASS co., ltd., "NA 35") having a thickness of 0.7mm using a spin coater so that the chromaticity after the baking was 0.100. Thereafter, the mixture was dried by heating on a heating plate at 80 ℃ for 3 minutes. Irradiating with an ultra-high pressure mercury lamp to 60mJ/cm without using a light-shielding cover²Thereby obtaining a cured film (blue-colored film). The obtained film was post-baked in a dust-free oven at 230 ℃ for 30 minutes, and the color (L) of the colored film was measured using a micro-spectroscopic measuring apparatus OSP-SP200 manufactured by Olympus corporation₀、a₀、b₀)。Thereafter, the colored film was further baked in a dust-free oven at 230 ℃ for 150 minutes, and the chromaticity (L) of the obtained colored film was measured again₁、a₁、b₁)。

The change in the color of the colored film after 30 minutes to 150 minutes at 230 ℃ was evaluated according to the following formula.

ΔEab＝{(L₁-L₀)²+(a₁-a₀)²+(b₁-b₀)²}^1/2

(Delta Eab evaluation criteria)

AA: delta Eab is 3 or less

A: Δ Eab is more than 3 and 5 or less

B: Δ Eab is more than 5 and 7 or less

C: Δ Eab is more than 7 and 10 or less

D: Δ Eab exceeds 10

< evaluation of development residue >

The colored resin compositions of examples and comparative examples were applied to GLASS substrates (NH techon GLASS ltd. "NA 35") having a thickness of 0.7mm using a spin coater, and then dried at 60 ℃ for 3 minutes using a hot plate, thereby forming colored layers having a thickness of 2.5 μm. The glass plate on which the above colored layer was formed was subjected to 60-second shower development using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. The unexposed portion (50mm × 50mm) of the glass substrate on which the colored layer was formed was observed by visual observation, and then sufficiently wiped with a lens cleaner (manufactured by Toray, trade name Toraysee MK Clean Cloth) containing ethanol, and the degree of coloring of the lens cleaner was observed by visual observation.

(evaluation criteria of development residue)

A: by visual non-confirmation of development residue, the lens cleaner was not colored at all

B: coloring of the lens cleaner was slightly confirmed by visual observation without confirming the development residue

C: the development residue was slightly confirmed by visual observation, and the coloring of the lens cleaner was confirmed

D: the development residue was visually confirmed, and the coloring of the lens cleaner was confirmed

In tables 1 and 2, the color material ratio is a ratio when the total color material amount is 100, and the dispersant ratio is a ratio when the total dispersant amount is 100.

[ Collection of results ]

The results in the table show that examples 1 to 24, in which a phthalocyanine pigment subjected to alkali treatment was combined with at least 1 kind of lake material selected from the group consisting of the color material represented by the above general formula (1) and the color material represented by the above general formula (2), and an acidic dispersant containing at least 1 kind of polymer selected from the structural unit represented by the above general formula (I) was combined as a dispersant, were able to form a colored layer having excellent dispersibility and storage stability and improved substrate adhesion and coating film uniformity even when a predetermined lake material and the phthalocyanine pigment were mixed within a desired range.

On the other hand, in comparative examples 1 and 5 in which a commercially available phthalocyanine pigment without alkali treatment was used as the phthalocyanine pigment, it was revealed that the dispersibility and the storage stability were deteriorated only by slightly increasing the content of the phthalocyanine pigment. In comparative examples 1 and 5 in which a commercially available phthalocyanine pigment without alkali treatment was used as the phthalocyanine pigment, substrate adhesion and coating film uniformity were inferior to those of the examples.

In comparative example 2 in which a commercially available phthalocyanine pigment without alkali treatment was used as the phthalocyanine pigment and a basic dispersant was used as the dispersant, the dispersibility and storage stability of the coloring material were poor, the substrate adhesion and coating film uniformity were poor, and further, the developability, the change in chromaticity after heating, and the development residue were poor.

In comparative example 3 in which only a lake material was used without using a phthalocyanine pigment, the dispersibility was inferior to that of examples, and the substrate adhesion and the coating film uniformity were inferior.

In comparative example 4 in which only a commercially available phthalocyanine pigment without alkali treatment was dispersed using a polymer having at least 1 kind selected from the structural units represented by the above general formula (I), the initial viscosity was too high to form a coating film that could be evaluated.

In the examples, a comparison of examples 1 to 13 shows that: when the content of the lake material is 20 mass% or more and 85 mass% or less with respect to the total content of the lake material and the phthalocyanine pigment, it is preferable to form a pattern with a desired line width by suppressing a change in chromaticity after the high-temperature heating step and suppressing a shift in line width.

Further, comparing examples 1 to 13 with examples 22 to 24, it is shown that: the acidic dispersant further contains a block copolymer containing: an A block comprising structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block comprising structural units derived from an alkyl (meth) acrylate.

Description of the reference numerals

1 substrate

2 light-shielding part

3 coloured layer

10 color filter

20 opposite substrate

30 liquid crystal layer

40 liquid crystal display device

50 organic protective layer

60 inorganic oxide film

71 transparent anode

72 hole injection layer

73 hole transport layer

74 luminescent layer

75 electron injection layer

76 cathode

80 organic light-emitting body

100 organic light emitting display device

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Color material dispersion liquid, colored resin composition, cured product thereof, color filter, and display device

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