Photosensitive coloring composition, color filter and image display device

文档序号：152568 发布日期：2021-10-26 浏览：18次中文

阅读说明：本技术 感光性着色组合物、彩色滤光片及图像显示装置 (Photosensitive coloring composition, color filter and image display device ) 是由常川美沙绪吉良沙也加小野寺由宇宫村护嗣吉田寛之于 2021-04-21 设计创作，主要内容包括：本发明的目的在于提供一种感光性着色组合物,其可抑制显影后的被膜的水印,残膜率良好且可形成良好形状的图案、使用所述感光性着色组合物而形成的彩色滤光片、以及包括所述彩色滤光片的图像显示装置。所述感光性着色组合物包括下述通式(1)所表示的光聚合引发剂(A)、粘合剂树脂(B)、光聚合性化合物(C)及着色剂(D)。通式(1)。(The invention aims to provide a photosensitive coloring composition which can inhibit watermark of a film after development, has good residual film rate and can form a pattern with good shape, a color filter formed by using the photosensitive coloring composition, and an image display device comprising the color filter. The photosensitive coloring composition comprises a photopolymerization initiator (A) represented by the following general formula (1), a binder resin (B), a photopolymerizable compound (C) and a colorant (D). Tong (Chinese character of 'tong')Formula (1) 。)

1. A photosensitive coloring composition comprising: a first photopolymerization initiator represented by the following general formula (1), a binder resin, a photopolymerizable compound and a colorant,

general formula (1)

In the general formula (1), R₁And R₂Each independently represents R₁₁Or COR₁₁，R₁₁R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₁₁The alkyl part of the alkyl, aryl, arylalkyl or heterocyclic radical can be branched side chain or can be cyclic alkyl, R₃Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R₄Represents a hydroxyl group, a cyano group, a nitro group or a halogen atom, and n represents 0 or 1.

2. The photosensitive coloring composition according to claim 1, wherein the binder resin comprises an alkali-soluble resin selected from the group consisting of the following (I), (II) and (III) and having a carboxyl group and a polymerizable unsaturated group in a side chain,

(I) an alkali-soluble resin which is obtained by reacting a polybasic acid or a polybasic acid anhydride with a reaction product of an epoxy group and a carboxyl group-containing monomer in an epoxy group-containing polymer and further contains a polycyclic alicyclic monomer unit;

(II) an alkali-soluble resin which is a reaction product of a carboxyl group and an epoxy-containing monomer in a polymer having a carboxyl group and further contains a polycyclic alicyclic monomer unit;

(III) an alkali-soluble resin which is a reaction product of hydroxyl groups and isocyanate group-containing monomers in a polymer having hydroxyl groups and carboxyl groups.

3. The photosensitive coloring composition according to claim 1 or 2, further comprising a polyfunctional thiol.

4. The photosensitive coloring composition according to claim 1 or 2, further comprising a second photopolymerization initiator different from the first photopolymerization initiator.

5. The photosensitive coloring composition according to claim 4, wherein the second photopolymerization initiator comprises one or more compounds selected from the group consisting of oxime ester compounds, acetophenone compounds, phosphine compounds and imidazole compounds.

6. The photosensitive coloring composition according to claim 4, wherein the second photopolymerization initiator comprises a third photopolymerization initiator represented by the following general formula (2),

the first photopolymerization initiator includes a fourth photopolymerization initiator represented by the following general formula (3),

general formula (2)

In the general formula (2), R₁Represents an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group, R₂R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₃Represents a hydrogen atom, a nitro group, a group having an ether bond, or a group showing aromatic character,

general formula (3)

In the general formula (3), R₄And R₅Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

7. The photosensitive coloring composition according to claim 6, wherein the content of the third photopolymerization initiator is 5 to 95 parts by mass based on 100 parts by mass of the total content of the third photopolymerization initiator and the fourth photopolymerization initiator.

8. The photosensitive coloring composition according to claim 4, further comprising a fifth photopolymerization initiator different from the first photopolymerization initiator and the second photopolymerization initiator.

9. The photosensitive coloring composition according to claim 8, wherein the second photopolymerization initiator comprises a third photopolymerization initiator represented by the following general formula (2),

the first photopolymerization initiator includes a fourth photopolymerization initiator represented by the following general formula (3),

general formula (2)

general formula (3)

10. The photosensitive coloring composition according to claim 6, wherein the total content of the third photopolymerization initiator and the fourth photopolymerization initiator is 30 parts by mass or more per 100 parts by mass of the total content of photopolymerization initiators contained in the photosensitive coloring composition.

11. The photosensitive coloring composition according to claim 1 or 2, wherein the polymerizable compound comprises a polymerizable compound having a structure derived from caprolactone.

12. The photosensitive coloring composition according to claim 1 or 2, wherein the polymerizable compound comprises a polymerizable compound having an acidic group.

13. The photosensitive coloring composition according to claim 1 or 2, further comprising a sensitizer.

14. A color filter, comprising: a substrate; and a filter segment formed using the photosensitive coloring composition according to any one of claims 1 to 13.

15. An image display device comprising the color filter according to claim 14.

Technical Field

The present invention relates to a photosensitive coloring composition for manufacturing a color filter used in a liquid crystal display device, a solid-state imaging element, an organic Electroluminescence (EL) display device, a quantum dot display device, an electronic paper, and the like, a color filter formed using the photosensitive coloring composition, and an image display device including the color filter.

Background

The color filter is formed by arranging two or more kinds of fine band-shaped filter segments (filter segments) having different hues in parallel (stripe) or cross with each other on a transparent substrate such as a glass substrate, or by arranging two or more kinds of fine filter segments having different hues in order in each of the longitudinal and transverse directions. The filter has a small size of several micrometers to several hundred micrometers, and is arranged in a predetermined arrangement for each color phase.

Currently, as a method for manufacturing a color filter, a filter pattern of a first color is obtained by the following steps: a step of applying a photosensitive coloring composition to a transparent substrate such as glass and removing a solvent from the coating film by drying; a step of irradiating the coating film with radiation through a photomask having a desired pattern shape and curing the coating film (hereinafter referred to as exposure); subsequently, a step of cleaning and removing (hereinafter referred to as development) an unexposed portion of the coating film; thereafter, a heat treatment (hereinafter, referred to as a post-baking) step is performed as necessary to sufficiently cure the cured film. Then, by performing the same operation as above, filter patterns of other colors are formed, and these are combined to complete the color filter.

In the developing step, an alkaline developer is used as the developer, and the unexposed portion is cleaned and removed. In this case, there is a problem that the exposed portion is lost or peeled off, and the pattern shape is defective. Further, there is a problem that when the coating film is exposed to an alkaline developer, a phenomenon (hereinafter referred to as "watermark") in which the coating film is discolored occurs. Therefore, there is a need for a photosensitive colored composition that does not cause defects in pattern shape and watermarks in the developing process. Further, there is a problem that the film thickness of the coating film changes due to elution and vaporization of unreacted materials or the like in the developing step and the post-baking step (hereinafter, the rate of change in film thickness is referred to as the residual film ratio).

Therefore, patent document 1 discloses a photosensitive coloring composition containing a resin-type surfactant having a fluorinated alkyl group. Further, patent document 2 discloses a photosensitive coloring composition containing a resin having a side chain having a polymerizable unsaturated group at the end of a polyalkylene oxide chain containing a poly (perfluoroalkylene ether) chain.

In addition, as a measure for improving the watermark, patent document 3 discloses a colored photosensitive resin composition containing an alkali-soluble resin having a specific structure and an oxime ester fluorene derivative compound as a photopolymerization initiator. Further, patent document 4 discloses a resist composition containing a fluorine-based surfactant having a specific structure.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2010-164965

[ patent document 2] Japanese patent laid-open No. 2014-65865

[ patent document 3] Japanese patent laid-open publication No. 2017-173787

[ patent document 4] Japanese patent laid-open No. 2016-102212

Disclosure of Invention

[ problems to be solved by the invention ]

However, the conventional photosensitive coloring composition has problems that the suppression of the watermark is insufficient and it is difficult to obtain a pattern having a good shape. In addition, there is a problem that the pattern shape and the film thickness of the pattern after post-baking are greatly reduced (the residual film ratio is low).

The invention aims to provide a photosensitive coloring composition which can inhibit watermark of a film after development, has good film residue rate and can form a pattern with good shape.

[ means for solving problems ]

One embodiment of the invention relates to a photosensitive coloring composition, which contains a first photopolymerization initiator represented by the following general formula (1), a binder resin, a photopolymerizable compound and a colorant.

General formula (1)

In the formula, R₁And R₂Each independently represents R₁₁Or COR₁₁，R₁₁R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₁₁The alkyl part of the alkyl, aryl, arylalkyl or heterocyclic radical may be a branched side chain or a cyclic alkyl radical, R₃Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R₄Represents a hydroxyl group, a cyano group (-CN), a nitro group or a halogen atom, and n represents 0 or 1.

Another embodiment of the present invention relates to the above-described photosensitive coloring composition, wherein the binder resin comprises an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in a side chain, the alkali-soluble resin being selected from the group consisting of the following (I), (II), and (III).

(I) An alkali-soluble resin which is obtained by reacting a polybasic acid or a polybasic acid anhydride with a reaction product of an epoxy group and a carboxyl group-containing monomer in an epoxy group-containing polymer and which further contains a polycyclic alicyclic monomer unit.

(II) an alkali-soluble resin which is a reaction product of a carboxyl group and an epoxy group-containing monomer in a polymer having a carboxyl group and further contains a polycyclic alicyclic monomer unit.

(III) an alkali-soluble resin which is a reaction product of hydroxyl groups and isocyanate group-containing monomers in a polymer having hydroxyl groups and carboxyl groups.

Still another embodiment of the present invention relates to the photosensitive coloring composition as described above, further comprising a polyfunctional thiol.

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, further comprising a second photopolymerization initiator different from the first photopolymerization initiator.

Still another embodiment of the present invention relates to the photosensitive coloring composition as described above, wherein the second photopolymerization initiator includes at least one compound selected from the group consisting of an oxime ester compound, an acetophenone compound, a phosphine compound, and an imidazole compound.

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, wherein the second photopolymerization initiator includes a third photopolymerization initiator represented by the following general formula (2), and the first photopolymerization initiator includes a fourth photopolymerization initiator represented by the following general formula (3).

General formula (2)

In the formula, R₁The alkyl group has 4-20 carbon atoms and contains an alicyclic hydrocarbon group. R₂Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R₃Represents a hydrogen atom, a nitro group, a group having an ether bond, or a group showing aromatic properties.

General formula (3)

In the formula, R₄And R₅Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, wherein the content of the third photopolymerization initiator is 5 to 95 parts by mass based on 100 parts by mass of the total content of the third photopolymerization initiator and the fourth photopolymerization initiator.

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, further comprising a fifth photopolymerization initiator different from the first photopolymerization initiator and the second photopolymerization initiator.

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, wherein the second photopolymerization initiator comprises a third photopolymerization initiator represented by the general formula (2), and the first photopolymerization initiator comprises a fourth photopolymerization initiator represented by the general formula (3).

Still another embodiment of the present invention relates to the photosensitive colored composition as described above, wherein the total content of the third photopolymerization initiator and the fourth photopolymerization initiator is 30 parts by mass or more based on 100 parts by mass of the total content of the photopolymerization initiators contained in the photosensitive colored composition.

Still another embodiment of the present invention relates to the above-described photosensitive coloring composition, wherein the polymerizable compound includes a polymerizable compound having a lactone-derived structure.

Still another embodiment of the present invention relates to the photosensitive coloring composition as described above, further comprising a sensitizer.

Still another embodiment of the present invention relates to a color filter including a substrate and a filter segment formed using the photosensitive coloring composition.

Still another embodiment of the present invention relates to an image display device including the color filter.

[ Effect of the invention ]

According to one embodiment of the present invention, there can be provided a photosensitive coloring composition which can suppress a watermark of a film after development, has a good residual film ratio, and can form a pattern having a good shape, a color filter including the photosensitive coloring composition, and an image display device including the color filter.

Drawings

Fig. 1 is a schematic cross-sectional view of a liquid crystal display device.

Description of the symbols

10: liquid crystal display device having a plurality of pixel electrodes

11. 21: transparent substrate

12: TFT array

13. 23: transparent electrode layer

14. 24: alignment layer

15. 25: polarizing plate

22: color filter

30: backlight unit

31: white LED light source

LC: liquid crystal display device

Detailed Description

In the present specification, "(meth) acryloyl group", "(meth) acrylic acid", "(meth) acrylate" or "(meth) acrylamide" means "acryloyl group and/or methacryloyl group", "acrylic group and/or methacrylic group", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless otherwise specified. "C.I." means The color Index (Colour Index) (C.I.; issued by The Society of Dyers and Colourists). The colorant may include pigments and dyes. The monomer and the polymerizable unsaturated group may include a vinyl group and a (meth) acryloyl group. The monomer is a monomer containing a polymerizable unsaturated group.

< photosensitive coloring composition >

The photosensitive coloring composition of the embodiment contains: a photopolymerization initiator (A) represented by the following general formula (1), a binder resin (B), a photopolymerizable compound (C), and a colorant (D). The photosensitive coloring composition can be applied to a substrate to form a coating film, for example. The coating film can be patterned into a desired shape by photolithography. The pattern is preferably post-baked to harden. The film formed of the photosensitive coloring composition is preferably used for a filter segment and a black matrix (black matrix) constituting a color filter.

The photosensitive colored composition of the present embodiment contains a photopolymerization initiator (a) represented by the following general formula (1), and the photo-curability of the composition is improved, whereby the water mark of the coating film can be remarkably suppressed. Further, by efficient photo-curing, the residual film ratio is good, and a pattern having a good shape can be formed.

[ photopolymerization initiator (A) ]

The photosensitive coloring composition comprises a photopolymerization initiator (A) represented by a general formula (1).

General formula (1)

In the formula, R₁And R₂Each independently represents R₁₁Or COR₁₁，R₁₁R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₁₁The alkyl part of the alkyl, aryl, arylalkyl or heterocyclic radical may be a branched side chain or a cyclic alkyl radical, R₃Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R₄Represents a hydroxyl group, a cyano group (-CN), a nitro group or a halogen atom,n represents 0 or 1.

In addition, R₃The alkyl, aryl, arylalkyl or heterocyclic group represented by may have a substituent, which may be, for example, an alkyl group, at R₃When the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the above has an alkyl group as a substituent, the alkyl moiety may be a branched side chain or a cyclic alkyl group, and R is₃The hydrogen atom of the aryl, arylalkyl or heterocyclyl radical represented may furthermore be interrupted by R₂₁、OR₂₁、COR₂₁、SR₂₁、NR₂₂R₂₃、CONR₂₂R₂₃、-NR₂₂-OR₂₃、-NCOR₂₂-OCOR₂₃、NR₂₂COR₂₁、OCOR₂₁、SCOR₂₁、OCSR₂₁、COSR₂₁、CSOR₂₁Hydroxy, nitro, cyano (-CN), halogen atom or COOR₂₁Substituted, R₂₁、R₂₂And R₂₃Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R₂₁、R₂₂And R₂₃The hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may be further substituted with a hydroxyl group, nitro group, cyano group (-CN), halogen atom or carboxyl group, in the R₂₁、R₂₂And R₂₃In the alkyl moiety or alkylene moiety of the alkyl, aryl, arylalkyl or heterocyclic group represented by-O-, -S-, -COO-, -OCO-, -NR-₂₄-、-NR₂₄CO-、-NR₂₄COO-、-OCONR₂₄-, -SCO-, -COS-, -OCS-or-CSO-may contain 1 to 5 under conditions where the oxygen atoms are not adjacent (no peroxy group is formed);

R₂₄r represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₂₄The alkyl moiety of the alkyl, aryl, arylalkyl, or heterocyclic group may be a branched side chain or may be a cyclic alkyl group.

R in the general formula (1)₃、R₁₁、R₂₁、R₂₂、R₂₃And R₂₄Examples of the alkyl group having 1 to 20 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

R in the general formula (1)₃、R₁₁、R₂₁、R₂₂、R₂₃And R₂₄Examples of the aryl group having 6 to 30 carbon atoms include: and alkyl groups substituted with one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl, biphenyl, naphthyl, anthryl, and the like.

R in the general formula (1)₃、R₁₁、R₂₁、R₂₂、R₂₃And R₂₄Examples of the arylalkyl group having 7 to 30 carbon atoms include: benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and the like.

R in the general formula (1)₃、R₁₁、R₂₁、R₂₂、R₂₃And R₂₄Examples of the heterocyclic group having 2 to 20 carbon atoms include: and 5-to 7-membered heterocycles such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidyl, piperazinyl, and morpholinyl.

The photopolymerization initiator (a) represented by the general formula (1) may include, for example, a photopolymerization initiator (a') represented by the following general formula (3).

General formula (3)

As R₄And R₅The alkyl group having 1 to 20 carbon atoms in (b) may be linear, branched or cyclic, or a group formed by bonding them, and examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl and the like.

As R₄And R₅Examples of the aryl group having 6 to 30 carbon atoms in (A) include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, and the like.

As R₄And R₅Examples of the arylalkyl group having 7 to 30 carbon atoms in (A) include: benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and the like.

As R₄And R₅Examples of the heterocyclic group having 2 to 20 carbon atoms in (A) include: pyridyl, pyrimidinyl, furanyl, tetrahydrofuryl, dioxolanyl, imidazolidinyl, oxazolidinyl, piperidinyl, morpholinyl, and the like. Among them, from the viewpoint of suppressing the watermark of the coating film, R₄Preferably an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms. From the viewpoint of reactivity, R₅Preferably methyl, ethyl or phenyl, more preferably methyl or ethyl.

The photopolymerization initiator (A') may be used singly or in combination of two or more.

The method for producing the photopolymerization initiator (a') is not particularly limited, and a conventional method can be used.

Specific examples of the photopolymerization initiator (a) include the following compounds nos. 1 to 8, and the following structural formulae (1) to (4). The present embodiment is not limited to these.

The photopolymerization initiator (a) has high sensitivity, and particularly can form a film having a high residual film ratio and suppress the watermark of the film after development, thereby obtaining a photosensitive coloring composition capable of forming a color filter of good quality. In addition, the photosensitive coloring composition containing the photopolymerization initiator can form a filter segment and a black matrix with excellent heat resistance, pattern shape, developing resistance and chemical resistance.

From the viewpoint of suppressing the watermark or pattern shape of the coating film, the content of the photopolymerization initiator (a) is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 2 to 15 parts by mass, based on 100 parts by mass of the colorant (D). When the amount is 100 parts by mass or less, linearity and resolution in forming a pattern are further improved. When the amount is 1 part by mass or more, the water mark of the coating film can be further suppressed.

[ photopolymerization initiator (Y) ]

In the photosensitive colored composition, a photopolymerization initiator (Y) different from the photopolymerization initiator (a) may be used in combination with the photopolymerization initiator (a) in addition to the photopolymerization initiator (a). Thus, a more favorable pattern can be formed.

The photopolymerization initiator (Y) may include, for example, a photopolymerization initiator (Y') represented by the following general formula (2).

General formula (2)

As R₁Examples of the alicyclic hydrocarbon group in (1) include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Among them, cyclopentyl and cyclohexyl are preferable from the viewpoint of reactivity, and cyclohexyl is more preferable from the viewpoint of suppressing watermarks.

As R₂The alkyl group having 1 to 20 carbon atoms in (b) may be linear, branched or cyclic, or a group formed by bonding them, and examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl and the like.

As R₂Examples of the aryl group having 6 to 30 carbon atoms in (A) include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, and the like.

As R₂Examples of the arylalkyl group having 7 to 30 carbon atoms in (A) include: benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and the like.

As R₂Examples of the heterocyclic group having 2 to 20 carbon atoms in (A) include: pyridyl, pyrimidinyl, furanyl, tetrahydrofuryl, dioxolanyl, imidazolidinyl, oxazolidinyl, piperidinyl, morpholinyl, and the like.

Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or an ethyl group is more preferable.

At R₃To display aromaticsIn the case of an aromatic group, the aromatic ring may be monocyclic or condensed. Further, the compound may be a hydrocarbon ring or a heterocyclic ring. Particularly preferably R₃Has a structure in which rings are bonded to each other via a carbonyl group. Examples of the group having aromatic character include groups having a benzene ring, a furan ring, a thiophene ring, a naphthalene ring, a benzofuran ring, a benzothiophene ring, and an indole ring. From the viewpoint of reactivity, R₃Preferably a hydrogen atom or a nitro group, more preferably a hydrogen atom.

The photopolymerization initiator (Y') may be used alone or in combination of two or more.

The method for producing the photopolymerization initiator (Y') is not particularly limited, and a conventional method can be used. For example, the method described in Japanese patent laid-open publication No. 2012 and 526185 can be used.

Specific examples of the photopolymerization initiator (Y') include the following structural formulae (5) to (10). The present embodiment is not limited to these.

Structural formula (9)

Structural formula (10)

Examples of the photopolymerization initiator (Y) include: 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, acetophenone-based compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) phenyl ] -2- (benzyl) -1-butanone, or 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, and 3,3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone, and 2, 4-diethylthioxanthone; 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphtho-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxy-naphtho-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, Or triazine compounds such as 2, 4-trichloromethyl- (4' -methoxystyryl) -6-triazine; oxime ester compounds such as 1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], or ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime); phosphine compounds such as bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and diphenyl-2, 4, 6-trimethylbenzoyl phosphine oxide; quinone compounds such as 9, 10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; a borate ester compound; a carbazole-based compound; 2,2' -bis (o-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (o-bromophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (o, p-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (o-chlorophenyl) -4,4',5,5' -tetrakis (m-methoxyphenyl) biimidazole, 2' -bis (o, o ' -dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (o-nitrophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (o-methylphenyl) -4,4', imidazole compounds such as 5,5 '-tetraphenyl biimidazole and 2,2' -bis (o-trifluorophenyl) -4,4',5,5' -tetraphenyl biimidazole; or titanocene-based compounds. Among these, at least one or more compounds selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds, and oxime ester compounds are preferable, and oxime ester compounds are more preferable.

The content of the photopolymerization initiator (Y) is preferably 0.5 to 200 parts by mass, and more preferably 1 to 100 parts by mass, based on 100 parts by mass of the colorant (D).

The content of the photopolymerization initiator (Y) is preferably 1 to 3000 parts by mass, more preferably 5 to 2000 parts by mass, based on 100 parts by mass of the photopolymerization initiator (a). When the amount is contained in an appropriate amount, the pattern shape is further improved.

The photopolymerization initiator (Y) may be used alone or in combination of two or more.

In addition, when the photosensitive coloring composition contains the photopolymerization initiator (a ') and the photopolymerization initiator (Y '), the content of the photopolymerization initiator (Y ') is preferably 5 to 95 parts by mass, more preferably 25 to 85 parts by mass, relative to 100 parts by mass of the total content of the photopolymerization initiator (a ') and the photopolymerization initiator (Y '), from the viewpoint of suppressing watermarks, pattern shapes, and residual film ratios.

From the viewpoint of suppressing the watermark, pattern shape, and residual film ratio of the coating film, the total content of the photopolymerization initiator (a ') and the photopolymerization initiator (Y') is preferably 30 parts by mass or more, more preferably 30 to 90 parts by mass, and particularly preferably 50 to 80 parts by mass, relative to 100 parts by mass of the photopolymerization initiator contained in the photosensitive colored composition.

From the viewpoint of the pattern shape, the photosensitive colored composition preferably further contains a photopolymerization initiator (Z) different from the photopolymerization initiator (a ') and the photopolymerization initiator (Y').

The photopolymerization initiator (Z) is not particularly limited, and a conventional photopolymerization initiator can be used. Specifically, there may be mentioned: acetophenone compounds exemplified as photopolymerization initiators (Y); a benzophenone-based compound; a triazine-based compound; an acylphosphine oxide-based compound; imidazole-based compounds, and the like. Among these compounds, acetophenone compounds, acylphosphine oxide compounds and imidazole compounds are preferable, and acetophenone compounds are more preferable from the viewpoint of pattern shape.

Commercially available acetophenone compounds include: "Omnirad) 907" (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one), "Omnirad (369" (2- (dimethylamino) -1- [4- (4-morpholino) phenyl ] -2- (benzyl) -1-butanone), "Omnirad (379 EG" (2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone), which are manufactured by IGM Resins (IGM Resins) Inc., commercially available products of acylphosphine oxide series include: "Omnirad 819" (bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide) "and" Omnirad (TPO) "manufactured by IGM Resins (IGM Resins) and the like.

The photopolymerization initiator (Z) may be used alone or in combination of two or more.

[ Binder resin (B) ]

The binder resin (B) has a transmittance of 80% or more in the entire wavelength range of 400nm to 700nm when a coating film having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin (B) is preferably an alkali-soluble resin. Thus, an object film formed of the photosensitive coloring composition can be patterned by photolithography. The binder resin (B) may have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetane group.

(alkali-soluble resin)

The alkali-soluble resin may be an existing resin. For example, the alkali-soluble resin is preferably selected from the following (I), (II), and (III) and has a carboxyl group and a polymerizable unsaturated group in a side chain. This improves the photocurability of the coating.

(I) An alkali-soluble resin (hereinafter referred to as alkali-soluble resin (I)) which is obtained by reacting a polybasic acid or polybasic acid anhydride with a reaction product of an epoxy group and a carboxyl group-containing monomer in an epoxy group-containing polymer and further contains a polycyclic alicyclic monomer unit.

(II) is a reaction product of a carboxyl group and an epoxy group-containing monomer in a polymer having a carboxyl group, and further comprises an alkali-soluble resin of a polycyclic alicyclic monomer unit (hereinafter referred to as alkali-soluble resin (II)).

(III) is an alkali-soluble resin (hereinafter referred to as alkali-soluble resin (III)) which is a reaction product of a hydroxyl group and a monomer containing an isocyanate group in a polymer having a hydroxyl group and a carboxyl group.

[ alkali-soluble resin (I) ]

As an example of the method for producing the alkali-soluble resin (I), an epoxy group-containing monomer and other monomer polymers are synthesized first. In addition, the other monomers include one or more polycyclic alicyclic monomers. Then, a monomer containing a monocarboxylic group is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. In addition, a monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[ alkali-soluble resin (II) ]

As an example of the method for producing the alkali-soluble resin (II), first, a carboxyl group-containing monomer and another monomer polymer are synthesized. In addition, the other monomers include one or more polycyclic alicyclic monomers. Then, an epoxy group-containing monomer having a smaller amount of carboxyl groups is added to the carboxyl groups of the polymer to obtain an alkali-soluble photosensitive resin.

Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 3, 4-epoxycyclohexyl (meth) acrylate. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity.

Examples of the monocarboxylic group-containing monomer include: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and a halogenated alkyl group, alkoxy group, halogen, nitro group, and cyano-substituted form at the α -position of (meth) acrylic acid.

Examples of the polybasic acid anhydrides include: aromatic and alicyclic acid anhydrides such as tetrahydrophthalic anhydride, phthalic anhydride and hexahydrophthalic anhydride; fatty acid anhydrides such as succinic anhydride and maleic anhydride; phosphoric anhydride, sulfonic anhydride, and the like. Further, the polybasic acid anhydride may have a carboxyl group which does not form an acid anhydride.

Examples of other monomers include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and the like, Or (meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate; (meth) acrylamide-based styrenes such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine, or styrenes such as α -methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

Among these, polycyclic alicyclic monomers are preferable, and monomers containing the following formula (a) and/or formula (b) are more preferable.

Further, there may be mentioned: cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1, 2-bismaleimidoethane, 1, 6-bismaleimidohexane, 3-maleimidopropionic acid, 6, 7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4' -bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N ' -1, 3-phenylenedimaleimide, N ' -1, 4-phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4, 6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N-maleimido, N-substituted maleimides such as N- (4-nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2, 3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl ] maleimide and 9-maleimidoacridine; ethylene Oxide (EO) modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, Ethylene Oxide (EO) modified (meth) acrylate of phenol, EO or Propylene Oxide (PO) modified (meth) acrylate of p-cumylphenol, EO modified (meth) acrylate of nonylphenol, PO modified (meth) acrylate of nonylphenol, and the like.

[ alkali-soluble resin (III) ]

As an example of the method for producing the alkali-soluble resin (III), first, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are polymerized to synthesize a polymer. Then, an alkali-soluble photosensitive resin can be obtained by reacting hydroxyl groups of the polymer with isocyanate groups of a monomer containing an isocyanate group.

Examples of the hydroxyl group-containing monomers include: hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate. Further, polyether mono (meth) acrylates obtained by addition polymerization of ethylene oxide, propylene oxide and/or butylene oxide to hydroxyalkyl (meth) acrylates, and polyester mono (meth) acrylates obtained by addition polymerization of poly-gamma-valerolactone, poly-epsilon-caprolactone and/or poly-12-hydroxystearic acid, and the like, are exemplified. Of these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable, and glycerol mono (meth) acrylate is more preferable.

Examples of the isocyanate group-containing monomer include: 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, or 1, 1-bis [ methacryloyloxy ] ethyl isocyanate, and the like.

Examples of the other monomers include monomers containing a phosphate group, in addition to the above-mentioned examples. The monomer containing a phosphate group is, for example, a compound obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with a hydroxyl group of the monomer containing a hydroxyl group.

[ alkali-soluble resin (IV) ]

The binder resin (B) may contain an alkali-soluble resin (IV) other than the alkali-soluble resin (I), the alkali-soluble resin (II), and the alkali-soluble resin (III).

The alkali-soluble resin (IV) may be used alone or in combination of two or more.

Examples of the alkali-soluble resin having no photosensitivity include: polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic acid copolymer resins, styrene/maleic acid copolymer resins, α -olefin/(anhydrous) maleic acid copolymer resins, acrylamide resins, (meth) acrylic acid/acrylamide copolymers, and the like, and the resins have a group that promotes alkali dissolution. Among them, preferred are a copolymer with an ethylenically unsaturated monomer copolymerizable with (meth) acrylic acid and a styrene/styrene sulfonic acid copolymer. Specific examples of the base-solubilizing group include: carboxyl group, phosphoric group, sulfonic group, hydroxyl group, phenolic hydroxyl group, etc., preferably carboxyl group. These groups may be used alone or in combination of two or more.

The alkali-soluble resin has a weight average molecular weight (Mw) of 2,000 to 40,000, preferably 3,000 to 300,00, more preferably 4,000 to 20,000, from the viewpoint of developability. The Mw/Mn ratio is preferably 10 or less. When the weight average molecular weight (Mw) is 2,000 or more, the decrease in adhesion to the substrate and the difficulty in leaving an exposed pattern can be suppressed. When the content is 40,000 or less, the decrease in solubility in alkali development, the generation of residue, and the deterioration of linearity of the pattern can be suppressed.

From the viewpoint of developability, the acid value of the alkali-soluble resin is preferably 50(KOHmg/g) to 200(KOHmg/g), more preferably 60 to 180, and particularly preferably 70 to 170. When the acid value is 50 or more, the decrease in solubility in alkali development, the generation of residue, and the deterioration of linearity of the pattern can be suppressed. When the amount is 200 or less, the decrease in adhesion to the substrate can be suppressed, and the exposure pattern is less likely to remain.

The binder resin (B) may be used alone or in combination of two or more.

The content of the binder resin (B) is preferably 1 to 400 parts by mass, more preferably 1 to 300 parts by mass, per 100 parts by mass of the colorant (D).

[ photopolymerizable Compound (C) ]

The photopolymerizable compound (C) is a compound having a polymerizable unsaturated group. The photopolymerizable compound (C) includes a monomer and an oligomer that are cured by ultraviolet light, heat, or the like to form a transparent resin. Examples of the photopolymerizable compound (C) include: a polymerizable compound having a lactone-derived structure, an acid group-containing polymerizable compound, a urethane bond-containing polymerizable compound, another polymerizable compound, and the like.

(polymerizable Compound (C-1) having a caprolactone-derived Structure)

From the viewpoint of suppressing the water mark of the coating film, the photosensitive coloring composition preferably contains a polymerizable compound (C-1) having a caprolactone structure as the polymerizable compound (C).

The polymerizable compound (C-1) having a caprolactone-derived structure is not particularly limited as long as it has a caprolactone-derived structure in a molecule, and can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylolmelamine with (meth) acrylic acid and epsilon-caprolactone. Among them, a compound represented by the following general formula (4) is preferable.

General formula (4)

Wherein 6R's are all a group represented by the following general formula (5), or 1 to 5 of the 6R's are a group represented by the following general formula (5), and the remainder is a group represented by the following general formula (6).

General formula (5)

In the formula, R¹Represents a hydrogen atom or a methyl group, m is a number of 1 or 2, and is a bond.

General formula (6)

In the formula, R¹Represents a hydrogen atom or a methyl group, and is a bond.

The polymerizable compound (C-1) having a structure derived from caprolactone is commercially available as, for example, the KAYARAD (KAYARAD) DPCA series manufactured by japan chemical company, and includes: DPCA-20 (in the general formulae (4) to (6), m is 1, the number of groups represented by the general formula (5) is 2, and R¹All being hydrogenAtomic compound), DPCA-30 (in the general formulae (4) to (6), m is 1, the number of groups represented by the general formula (5) is3, and R¹All hydrogen atoms), DPCA-60 (in the general formulae (4) to (6), m is 1, the number of groups represented by the general formula (5) is 6, and R is¹All hydrogen atoms), DPCA-120 (in the general formulae (4) to (6), m is 2, the number of groups represented by the general formula (5) is 6, and R is¹Compounds all of which are hydrogen atoms), and the like.

From the viewpoint of suppressing the water mark of the coating, the polymerizable compound (C-1) having a caprolactone-derived structure is preferably represented by general formulae (4) to (6), wherein m is 1, the number of groups represented by general formula (5) is 2 to 6, and R is¹The compounds having all hydrogen atoms are more preferably represented by general formulae (4) to (6) wherein m is 1 and the number of groups represented by general formula (5) is 2 or 3, and R is¹All are hydrogen atoms.

From the viewpoint of suppressing the water mark of the coating film, the content of the polymerizable compound (C-1) having a caprolactone-derived structure is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and particularly preferably 20 to 60 parts by mass, relative to 100 parts by mass of the polymerizable compound (C).

(polymerizable Compound (C-2) having acid group)

The photosensitive coloring composition preferably contains the polymerizable compound (C-2) containing an acid group from the viewpoint of the pattern shape. Examples of the acid group-containing polymerizable compound (C-2) include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Examples of the acid group-containing polymerizable compound (C-2) include: esters of poly (meth) acrylates containing free hydroxyl groups of polyhydric alcohols and (meth) acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth) acrylates, and the like. Specific examples thereof include: monoesters of monohydroxy oligoacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate with free carboxyl groups of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1, 2, 3-tricarboxylic acid (tricarballylic acid), butane-1, 2, 4-tricarboxylic acid, benzene-1, 2, 3-tricarboxylic acid, benzene-1, 3, 4-tricarboxylic acid, and benzene-1, 3, 5-tricarboxylic acid with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

Commercially available products of the acid group-containing polymerizable compound (C-2) include Bisco (Viscoat) #2500P manufactured by Osaka organic Co., Ltd, Aronix (Aronix) M-5300 manufactured by Toyo Synthesis Co., Ltd, Aronix (Aronix) M-5400, Aronix (Aronix) M-5700, Aronix (Aronix) M-510, Aronix (Aronix) M-520, and Aronix (Aronix) M-521.

From the viewpoint of the pattern shape, the content of the acid group-containing polymerizable compound (C-2) is preferably 20 to 80 parts by mass, more preferably 25 to 75 parts by mass, and still more preferably 35 to 70 parts by mass, relative to 100 parts by mass of the polymerizable compound (C).

(urethane bond-containing polymerizable Compound)

The urethane bond-containing polymerizable compound contains a urethane bond. Examples of the urethane bond-containing polymerizable compound include: a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with an alcohol, and a (meth) acrylate having a hydroxyl group.

Examples of the (meth) acrylate having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy-containing compound and carboxy (meth) acrylate, a hydroxyl-containing polyol polyacrylate, and the like.

Examples of polyfunctional isocyanates include: toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

(other polymerizable Compound (C-3))

Examples of the other polymerizable compounds include: methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethyleneglycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol acrylate, ethylene glycol acrylate, and ethylene glycol acrylate, and ethylene glycol acrylate, and the like, Various acrylates and methacrylates such as di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, etc., (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, ethylene glycol divinyl ether, ethylene glycol, and the like, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like.

Examples of commercially available products of these include: kaarard (KAYARAD) R-128H, KayaRAD (KAYARAD) R526, KayaRAD (KAYARAD) PEG400DA, KayaRAD (KAYARAD) MAND, KayaRAD (KAYARAD) NPGDA, KayaRAD (KAYARAD) R-167, KayaRAD (KAYARAD) HX-220, KayaRAD (KAYARAD) R-551, Kayarad (KARAD) R712, Kayarad (KAYA) R-604, Kayarad (KARAD) R-684, Kayad (KAYA) GPO-303, Kayad (KAYA) TMPTA, Kayarad (KAYA) DPHA, Kayara (KAYA) DPEA 12, KayaRAD (KAYAD) 2-12, KayaRARAD-330, and AryaRAD (ARYARAD) KARAD 310 manufactured by NiraD, KAYARAD (KARAD) R-309, and ARYARAD-12, Aronia (Aronix) M-310, Aronix (Aronix) M-321, Aronix (Aronix) M-325, Aronix (Aronix) M-350, Aronix (Aronix) M-360, Aronix (Aronix) M-313, Aronix (Aronix) M-315, Aronix (Aronix) M-400, Aronix (Aronix) M-402, Aronix (Aronix) M-403, Aronix (Aronix) M-404, Aronix (Aronix) M-405, Aronix (Aronix) M-406, Aronix (Aronix) M-450, Aronix (Aronix) M-452, Aronix (Aronix) M-408, Aronix (Aronix) M-211, Vixox (Aronix) HP-310, Vixox) M-335, and Vixox (Aronix) HP, Biscat (Viscoat) #700, Biscat (Viscoat) #295, Biscat (Viscoat) #330, Biscat (Viscoat) #360, Biscat (Viscoat) # GPT, Biscat (Viscoat) #400, Biscat (Viscoat) #405, Biscat (Viscoat) UV-4108F, Biscat (Viscoat) UV-4117F, NK esters A-9300, NK esters UA-160TM manufactured by Mitsugami chemical, AH-600, AT-306H, UA-T, UA-306-3632-510-80036-8001-G, DAUA-167, and so on.

The photopolymerizable compound (C) may be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the colorant (D).

The mass ratio [ Ia/M ] of the mass [ Ia ] of the photopolymerization initiator (A) to the mass [ M ] of the photopolymerizable compound (C) is preferably 0.01 to 3.00, more preferably 0.15 to 2.00.

When the photosensitive coloring composition contains the sensitizer (E) or the photopolymerization initiator (Y), the mass ratio [ Ib/M ] of the total mass [ Ib ] of the photopolymerization initiator (a), the sensitizer (E) and the photopolymerization initiator (Y) to the mass [ M ] of the photopolymerizable compound (C) is preferably 0.01 to 3.00, more preferably 0.15 to 2.00. The development resistance, chemical resistance, pattern shape, linearity, and resolution can be improved in a well-balanced manner by an appropriate mass ratio [ Ia/M ].

[ colorant (D) ]

As the colorant (D), an organic pigment or an inorganic pigment can be cited. The pigment is preferably a pigment having high color-developing properties and high heat resistance, and is usually preferably an organic pigment. Further, the colorant (D) may contain a dye within a range not to lower the heat resistance.

(pigment)

Specific examples of the organic pigment are shown below by color index numbers. Examples of the red pigment include: c.i. pigment red (pigment red)1, 2,3,4, 5, 6,7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57 and 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 287, 284, 285, 286, 287, 291, 295, 2014, 134, the pigment disclosed in japanese patent publication No. 283, 6368844, and the pigment disclosed in japanese patent publication No. jp-a-42, 296, and No. 6368844. Among these, c.i. pigment red 48: 1. 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment disclosed in japanese patent application laid-open No. 2014-134712, the pigment disclosed in japanese patent No. 6368844, and more preferably c.i. pigment red 177, 254, 291, 295, 296, the pigment disclosed in japanese patent application laid-open No. 2014-134712, and the pigment disclosed in japanese patent No. 6368844.

In addition, an orange pigment or a yellow pigment such as c.i. pigment orange 36, 38, 43, 51, 55, 59, 61, 64, 71, or 73 may be used in combination as the red pigment.

Examples of the blue pigment include: c.i. pigment blue (pigment blue)1, 1: 2.9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56: 1.60, 61: 1. 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. or 15: 6, more preferably c.i. pigment blue 15: 6. alternatively, a blue pigment may be used in combination with a violet pigment.

Examples of violet pigments include: c.i. pigment violet (pigment violet)1, 1: 1.2, 2: 2. 3, 3: 1. 3: 3.5, 5: 1. 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, c.i. pigment violet 19 or 23 is preferable, and c.i. pigment violet 23 is more preferable, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment.

Examples of the green pigment include: c.i. pigment green (pigment green)1, 2,4, 7, 8,10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, the pigment disclosed in japanese patent laid-open publication No. 2017-111398, and the like. Among these, c.i. pigment green 36, 58, 59, 62, 63 and the pigment described in japanese patent laid-open publication No. 2017-111398 are preferable from the viewpoint of transmittance.

Examples of the yellow pigment include: c.i. pigment yellow (pigment yellow)1, 2,3,4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 233, 231 disclosed in japanese patent laid-open No. 2012-open No. 231, and the like. Preferred are pigments described in c.i. pigment yellow 138, 139, 150, 185, 231, 233, and japanese patent laid-open No. 2012-226110.

Examples of the cyan coloring composition include: c.i. pigment blue 15: 1. 15: 2. 15: 4. 15: 3. 15: 6. 16, 81, and the like.

Examples of the magenta coloring composition include: violet pigments and red pigments such as c.i. pigment violet 1, 19 and c.i. pigment red 144, 146, 177, 169 and 81. The magenta composition can incorporate a yellow pigment.

Examples of the inorganic pigment include: titanium oxide, barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, red iron oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, umber (umber), synthetic iron black, and the like.

The black photosensitive coloring composition for forming a black matrix preferably contains, for example, carbon black, aniline black, anthraquinone-based black pigment, perylene-based black pigment, and specifically includes: c.i. pigment black (pigment black)1, 6,7, 12, 20, 31 and the like. The black photosensitive coloring composition may further contain a red pigment, a blue pigment, and a green pigment in combination. Carbon black is preferred from the viewpoint of low cost and light-shielding properties. Carbon black may also be surface-treated with a resin or the like. In addition, a blue pigment and a violet pigment may be used in combination in the black photosensitive coloring composition for the purpose of adjusting the color tone.

(dyes)

Examples of dyes include: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like. Further, a derivative of a dye, a lake pigment obtained by laking a dye, or the like can be used.

Further, as the dye, there can be mentioned: a salt-forming compound of an acid dye having an acid group such as a sulfonic acid group or a carboxylic acid group, or an inorganic salt of the acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound of a resin component having such an amino group and an acid dye, and the like. The salt-forming compound of the acid dye and the compound having an onium salt group is also preferable because of its excellent fastness. The compound having an onium salt group is preferably a resin having a cationic group in a side chain.

Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among these, the basic dye is preferable because it is excellent in resistance to a salt-forming compound and in combination with a pigment, and more preferably a salt-forming compound obtained by forming a salt with the basic dye and an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing group phosphorus anion compound, a fluorine-containing group boron anion compound, a cyano-containing group nitrogen anion compound, an anion compound containing a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye, which are counter components acting as counter ions (counter ions).

Further, when the dye skeleton has a polymerizable unsaturated group, it is preferable because a dye having excellent resistance can be produced.

Examples of the chemical structure of the dye include: azo dyes, bisazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, indocyanine dyes), quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylene (arylidene) dyes, styryl dyes, cyanine dyes, squarylium dyes, ketanium (croconium) dyes, etc.), quinophthalone dyes, suphthalone dyes, subphthalocyanine dyes, indocyanine dyes, indigo dyes, thiocyanine dyes, etc.), quinophthalone dyes, and cyanine dyes, Quinoline dyes, nitro dyes, nitroso dyes, rhodamine (rhodamine) dyes, and the like. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes are preferable from the viewpoint of color characteristics such as hue, color separation, color unevenness, and the like, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine dyes are more preferable. Specific structures of dyes are described in "New edition of dye review" (edited by The Society of organic Synthesis chemistry; Tanshan, 1970), "color index" (The Society of dyeing workers and colorists)), and "pigment handbook" (edited by Daihuan et al; lecture Society, 1986).

The colorant (D) may be used alone or in combination of two or more.

The content of the colorant (D) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the nonvolatile component of the photosensitive coloring composition. When the content of the colorant (D) is 5% by mass or more, the color reproducibility in the use of the color filter is improved, and when it is 70% by mass or less, the sensitivity and the pattern formability are further improved.

(micronization of pigment)

When an organic pigment is used as the colorant (D), it is preferably mixed with other raw materials after the micronization treatment. Examples of the micronizing treatment include wet grinding, dry grinding, and dissolution and precipitation. Among these, salt milling (salt milling) treatment by a kneader method which is one of wet milling is preferable. The average primary particle diameter of the organic pigment after the micronization treatment is preferably 5nm to 90nm, more preferably 10nm to 80nm, still more preferably 10nm to 70nm, and particularly preferably 15nm to 70 nm. The dispersion property is further improved by an appropriate particle diameter, and the contrast ratio of the coating film is further improved. The average primary particle size is an average value of about 20 particles arbitrarily selected from an enlarged image of a Transmission Electron Microscope (TEM). In the case where the length of the vertical axis and the length of the horizontal axis of the particle are present, the length of the vertical axis is used.

The salt milling treatment means the following treatment: a mixture of the pigment, the water-soluble inorganic salt and the water-soluble organic solvent is mechanically kneaded while heating using a batch or continuous mixer such as a kneader (kneader), a two-roll mill (two-roll mill), a three-roll mill (three-roll mill), a ball mill (ball mill), an attritor, a sand mill (sand mill) or a planetary mixer (planetary mixer), and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution can be obtained.

Examples of the water-soluble inorganic salt include: sodium chloride, potassium chloride, sodium sulfate, and the like. Among these, sodium chloride (salt) is preferable from the viewpoint of price. From the viewpoint of processing efficiency and production efficiency, the amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, relative to 100 parts by mass of the pigment.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound which is dissolved (mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120 ℃ or higher, from the viewpoint of being less likely to volatilize due to an increase in temperature during salt milling. Examples of the water-soluble organic solvent include: 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, and more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

When the salt milling treatment is performed, a resin may be added as necessary. Examples of the resin include: natural resins, modified natural resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

(dispersing agent)

The dispersant is used to uniformly disperse the pigment in the dispersion medium and stably maintain the state, and a pigment derivative, a resin type dispersant, or the like is generally used.

[ pigment derivative ]

The pigment derivative is adsorbed on the surface of the organic pigment, so that the surface of the organic pigment has polarity, and the pigment derivative is likely to have affinity with the binder resin (B) and a resin-type dispersant described later, thereby further improving the dispersibility of the organic pigment. The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Examples of the pigment derivative include: compounds having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphoric acid group, and amine salts thereof; a compound having a sulfonamide group or a basic substituent such as a tertiary amino group at the terminal; compounds having a neutral substituent such as phenyl or phthalimidoalkyl. Examples of the organic pigment include: indole pigments such as diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzindole pigments; isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, reduction pigments, metal complex pigments, azo pigments such as azo, bisazo, and polyazo pigments, and the like.

Specifically, the conventional dye derivatives described in the following publications and the like can be mentioned, and the diketopyrrolopyrrole-based dye derivatives include: japanese patent laid-open Nos. 2001-220520, 2009/081930, 2011/052617, 2012/102399, 2017-156397; examples of the phthalocyanine-based coloring matter derivative include: japanese patent laid-open Nos. 2007 and 226161, 2016/163351, 2017 and 165820, 5753266; examples of the anthraquinone-based pigment derivative include: japanese patent laid-open publication No. 63-264674, Japanese patent laid-open publication No. 09-272812, Japanese patent laid-open publication No. 10-245501, Japanese patent laid-open publication No. 10-265697, Japanese patent laid-open publication No. 2007-079094, International publication No. 2009/025325; as quinacridone pigment derivatives, there can be mentioned: japanese patent laid-open Nos. 48-54128, 03-9961, 2000-273383; examples of dioxazine dye derivatives include those disclosed in Japanese patent laid-open publication Nos. 2011-162662; examples of thiazine indigo-based pigment derivatives include those disclosed in Japanese patent laid-open Nos. 2007-314785; examples of the triazine-based dye derivative include: japanese patent laid-open Nos. 61-246261, 11-199796, 2003-165922, 2003-168208, 2004-217842 and 2007-314681; examples of the benzisoindole dye derivatives include Japanese patent laid-open No. 2009-57478; examples of the quinophthalone pigment derivative include: japanese patent laid-open Nos. 2003-167112, 2006-291194, 2008-31281, 2012-226110; examples of the naphthol-based pigment derivative include: japanese patent laid-open Nos. 2012-208329 and 2014-5439; examples of the azo dye derivative include: japanese patent laid-open Nos. 2001-172520 and 2012-172092; as the acidic substituent, there can be mentioned Japanese patent laid-open No. 2004-307854; as the basic substituent, there may be mentioned: japanese patent laid-open Nos. 2002-201377, 2003-171594, 2005-181383 and 2005-213404. In these documents, the pigment derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic pigment residue has the same meaning as the pigment derivative.

The pigment derivatives may be used alone or in combination of two or more.

The content of the pigment derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and still more preferably 5 to 50 parts by mass, for example, 1 to 15 parts by mass, and may be 2 to 10 parts by mass, based on 100 parts by mass of the colorant (D).

By adding a pigment derivative to the pigment and subjecting the pigment to a micronization treatment such as acid dissolution (acid bleeding), acid slurrying (acid slurry), dry milling, salt milling, or solvent salt milling, the pigment derivative is adsorbed on the pigment surface, and the primary particles of the pigment can be micronized more than in the case where the pigment derivative is not added.

[ resin type dispersant ]

The resin type dispersant has: a colorant affinity site adsorbed to the colorant (D); and a relaxation site having a high affinity with a component other than the colorant and causing steric repulsion between the dispersed particles. The resin type dispersant is not particularly limited, and a conventional resin type dispersant can be used. Examples of the resin type dispersant include: urethane dispersants such as polyurethane; polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; oily dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group; water-soluble resins or water-soluble high molecular compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; polyester, modified polyacrylate, ethylene oxide/propylene oxide adduct, phosphate ester, and the like.

From the viewpoint of dispersion stability, it is preferable to have a group to be adsorbed to the colorant (hereinafter referred to as an adsorption group). The adsorption group is preferably a resin having a cationic group and/or an anionic group.

The resin having a cationic group is not particularly limited, and conventional resins can be used. Specifically, examples of the cationic group include a group containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group, and a nitrogen-containing heterocyclic ring.

The resin having an anionic group is not particularly limited, and a conventional resin can be used. Specifically, examples of the anionic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, carboxyl groups and phosphoric groups are preferable from the viewpoint of adsorption to the colorant.

The structure of the resin type dispersant is not particularly limited, and examples thereof include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among them, a block structure or a comb structure is preferable from the viewpoint of dispersion stability.

Specific examples of the resin-type dispersant usable for the photosensitive coloring composition include: disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-110, Disperbyk-111, Disperbyk-116, Disperbyk-130, Disperbyk-140, Disperbyk-154, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-168, Disperbyk-167, Disperbyk-170, Disperbyk-166, Disperbyk-168, Disperbyk-170, Disperbyk-101, Disperbyk-103, Disperbyk-167, Disperbyk-170, Disperbyk-108, Disperbyk-103, Disperbyk-170, Disperbyk-170, and Disperbyk-108, Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-181, Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-190, Disperbyk-2000, Disperbyk-2001, Disperbyk-2009, Disperbyk-2010, Disperbyk-2009, Disperbyk-2050, Disperbyk-2095, Disperbyk-2025, Disperbyk-2050, Disperbyk-2152090, Disperbyk-2075, Disperbyk-2050, Disperbyk-2072090, Disperbyk-2075, Disperbyk-2050, Disperbyk-2150, Disperbyk-2072095, Disperbyk-2075, Disperbyk-2050, Disperbyk-2072095, and the like, Sorperbyk-2163, Sorperbyk-2164, or Antitara (Anti-Terra) -U203, Antita (Anti-Terra) -U204, or BYK-P104, BYK-P104S, BYK-220S, or Latiumu Murina (Lactomon), Latiumon (Lactomon) -WS or Bickman (Bykumen), etc., Sorparse (SOLSPERSE) -3000, Sorparse (SOLSPERSE) -9000, Sorparse (SOLSPERSE) -13000, Sorparse (SOLSPERSE) -13240, SORPAU (SOLSPERSE) -13650, SORPAU (SORPAU) -13900, SOLSR-LSR-16000, SORPAU-LSR-102, SORPE-200, SORPAU-LSR-R-S (SOLSR-R-S-R-, Sonopause (SOLSPERSE) -26000, Sonopause (SOLSPERSE) -27000, Sonopause (SOLSPERSE) -28000, Sonopause (SOLSPERSE) -31845, Sonopause (SOLSPERSE) -32000, Sonopause (SOLSPERSE) -32500, Sonopause (SOLSPERSE) -32550, Sonopause (SOLSPERSE) -33500, Sonopause (SOLSPERSE) -32600, Sonopause (SOLSPERSE) -34750, Sonopause (SOLSPERSE) -35100, Sonopause (SOLSPERSE) -36600, Sonopause (SOLSPERSE) -38500, Sonopause (SOLSPERSE) -41000, SOLSPERSE-5602, Sonopause-SPE-55095, Sorpause-LSE) -53000, Sorpause-765 (SOLSPERSE) -46, Solspesse-5, Sorpause-41000, Sorpause-55046, Sorpause (SOLLSE) -55046, Sorpause-5, Sorpause-r-5, Sorpe-sp-34750, Sorpe-sp-4105, Sorpe-sp-35, Sols-sp-sp, Afv card (EFKA) -48, afv card (EFKA) -452, afv card (EFKA) -4008, afv card (EFKA) -4009, afv card (EFKA) -4010, afv card (EFKA) -4015, afv card (EFKA) -4020, afv card (EFKA) -4047, afv card (EFKA) -4050, afv card (EFKA) -4055, afv card (EFKA) -4060, afv card (EFKA) -4080, afv card (EFKA) -4400, afv card (EFKA) -4401, afv card (EFKA) -4402, afv card (EFKA) -4403, afv card (EFKA) -4406, afv card (EFKA) -4408, afv card (EFKA) -4300, EFKA) -4310, afv card (EFKA) -4320, EFKA) -4330, EFKA-43450, Aff card (EFKA) -451, Aff card (EFKA) -453, Aff card (EFKA) -4540, Aff card (EFKA) -4550, Aff card (EFKA) -4560, Aff card (EFKA) -4800, Aff card (EFKA) -5010, Aff card (EFKA) -5065, Aff card (EFKA) -5066, Aff card (EFKA) -5070, Aff card (EFKA) -7500, Aff card (EFKA) -7554, Aff card (EFKA) -1101, Aff card (EFKA) -120, Aff card (EFKA) -150, Aff card (EFKA) -1501, Aff card (EFKA) -1502, Aff card (EFKA) -1503, etc., ajino Fine precision technology (Ajiippa) PA111, Afjpap (Ajjs) 821, Afjjs) 822, Afp.822, Afp.k., and resin-type dispersants described in Japanese patent laid-open Nos. 2008-029901, 2009-155406, 2010-185934, 2011-157416. These resin-type dispersants may be used alone or in combination of two or more.

The resin type dispersant includes, as the kind of the functional group, a resin type dispersant containing an acidic functional group and a resin type dispersant containing a basic functional group. The resin-type dispersant having an acidic functional group is preferably a resin-type dispersant having an aromatic carboxylic acid structure, and is described in, for example, International publication No. 2008/007776, Japanese patent laid-open No. 2008-029901, Japanese patent laid-open No. 2009-155406, Japanese patent laid-open No. 2010-185934, Japanese patent laid-open No. 2011-157416, Japanese patent laid-open No. 2009-251481, Japanese patent laid-open No. 2007-23195, Japanese patent laid-open No. 1996-143651, and the like.

Examples of the resin type dispersant containing a basic functional group include: a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer having a functional group such as a tertiary amino group, a quaternary ammonium salt group or a nitrogen-containing heterocycle in a side chain, a urethane polymer dispersant, and the like. Further, a resin type dispersant containing an acidic functional group and a resin type dispersant containing a basic functional group may be used in combination.

The dispersant may be used alone or in combination of two or more.

The content of the dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant (D).

[ sensitizer (E) ]

The photosensitive coloring composition preferably contains a sensitizer (E) from the viewpoint of reactivity and pattern shape. The sensitizer (E) is more preferably used in combination with the polymerization initiator (C-3). The sensitizer (E) is not particularly limited, and conventional sensitizers can be used.

Examples of the sensitizer (E) include: unsaturated ketones such as chalcone (chalcone) derivatives and dibenzylideneacetone (dibenzalacetone); 1, 2-dione derivatives represented by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thianthrene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine pigments such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene (azulene) derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetraphenylporphyrin derivatives, tetrapyrazino porphyrazine (tetrapyrazino porphyrazine) derivatives, phthalocyanine derivatives, tetraazaporphyrazine (tetraazaporhyrazine) derivatives, tetraquinoxalinone derivatives, naphthalocyanine derivatives, naphthocyanine derivatives, naphthoquinone derivatives, and the like, Subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetrapyrolin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, benzophenone derivatives, and the like. Among these, thioxanthone derivatives, michael's ketone derivatives, and carbazole derivatives are preferable. Specific examples of the sensitizer (E) include: 2, 4-diethylthioxanthone, 2-chlorothianthrone, 2, 4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioanthone, α -acyloxy ester, acylphosphine oxide, methyl benzoylformate, benzil, 9, 10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4' -diethylisophthalophenone (4,4' -diethyl isophthalophenone), 3' -tetrakis (t-butylperoxycarbonyl) benzophenone or 4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -bis (ethylmethylamino) benzophenone, 2-aminobenzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3, 6-dibenzoyl-N-ethylcarbazole and the like. Among these, thioxanthone derivatives and benzophenone derivatives are preferable from the viewpoint of the pattern shape.

The sensitizer (E) may be used alone or in combination of two or more.

From the viewpoint of achieving both the suppression of watermarks and the pattern shape, the content of the sensitizer (E) is preferably 1 to 200 parts by mass, may be 3 to 60 parts by mass, or may be 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (a).

[ polyfunctional mercaptan (F) ]

The photosensitive coloring composition may contain a polyfunctional thiol (F). The polyfunctional thiol (F) is a compound having two or more thiol (SH) groups, and more preferably has four or more SH groups. When the number of functional groups increases, the film tends to be hardened by light from the surface to the deepest part of the film. The polyfunctional thiol (F) acts as a chain transfer agent in the radical polymerization process after light irradiation by using the photopolymerization initiator (a) in combination, and generates a sulfur radical (thio chemical) which is less likely to be inhibited by polymerization by oxygen, thereby having high sensitivity. In particular, polyfunctional aliphatic thiols in which an SH group is bonded to an aliphatic group such as a methylene group or an ethylene group are preferable.

Examples of the polyfunctional thiol (F) include: hexane dithiol, decane dithiol, 1, 4-butanediol bisthiopropionate, 1, 4-butanediol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1, 4-dimethylmercaptobenzene, 2,4, 6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4, 6-dimercapto-s-triazine, etc., and preferable examples thereof include: ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate.

The polyfunctional mercaptan (F) may be used alone or in combination of two or more.

The content of the polyfunctional thiol (F) is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass, per 100 parts by mass of the colorant (D). When the content of the polyfunctional thiol (F) is 0.05 parts by mass or more, crosslinking of the coating film after light irradiation is promoted, and in addition to improvement in development resistance, watermarks of the coating film can be further suppressed.

The content of the polyfunctional thiol (F) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile component of the photosensitive coloring composition. When the amount is properly determined, the light sensitivity is improved and the surface of the film is less likely to be wrinkled.

[ thermosetting Compound (G) ]

The photosensitive colored composition may contain a thermosetting compound (G). Thus, the thermosetting compound (G) is heat-cured in the post-baking step to increase the crosslinking density of the coating film, thereby improving the heat resistance. In addition, the aggregation of the colorant (D) in the post-baking step is suppressed, and the contrast ratio is improved. The thermosetting compound (G) may be a low molecular weight compound or a high molecular weight compound such as a resin.

Examples of the thermosetting compound (G) include: an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferable.

(epoxy compound)

The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the epoxy compound include: polycondensates of bisphenols (bisphenol a, bisphenol F, bisphenol S, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.), and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polymers of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polycondensates of phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols with aromatic dimethanol (benzene dimethanol, α, α, α ', α' -benzene dimethanol, biphenyl dimethanol, α, α, α ', α' -biphenyl dimethanol, etc.); polycondensates of phenols with aromatic dichloromethyl groups (α, α' -dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of bisphenols with various aldehydes; glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidylester epoxy resins obtained by glycidylating alcohols and the like.

Examples of commercially available products include: ipecotate (EPICOAT)807, Ipecotate (EPICOAT)815, Ipecotate (EPICOAT)825, Ipecotate (EPICOAT)827, Ipecotate (EPICOAT)828, Ipecotate (EPICOAT)190P, Ipecotate (EPICOAT)191P (trade name; manufactured by Ovalnema Seisaku K.K.; supra), Ipecotate (EPOAT) 1004, Ipecotate (EPICOAT)1256 (trade name; manufactured by Nippon epoxy Co., Ltd.), Techmour (TECHMore) VG3101L (trade name; manufactured by Mitsui Chemicals Co., Ltd.), EPPN-501-502H (trade name; manufactured by Nippon Chemicals Co., Ltd.), JER 1032H60 (trade name; manufactured by Nippon epoxy Co., Ltd.), 86157S 65, JER S70 (trade name; manufactured by Nippon epoxy resin Co., Ltd., EPPN-201; manufactured by Nippon Chemicals., Japan; trade name JER; manufactured by Nippon epoxy Co., Japan) (trade name; 36157; 35154; manufactured by Nippon epoxy Co., Japan), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (trade name; manufactured by Nippon chemical Co., Ltd.), Celluoside (CELLOXIDE)2021, EHPE-3150 (trade name; manufactured by Daicel chemical industry Co., Ltd.), minonochol (DENACOL) EX-211, minonochol (DENACOL) EX-212, minonochol (DENACOL) EX-252, minonochol (DENACOL) EX-313, minonochol (DENACOL) EX-314, minonochol (DENACOL) EX-321, minonochol (DENACOL) NACOL-411, minocole (DENACOL) EX-421, minocole (DENACOL) EX-512, minocole (DENACOL) EX-521, minocole (DENACOL) EX-612, DENACOL (DENACOL) EX-611, DENACOL (DENACOL) EX-612, DENACOL (DENACOL) EX-614, DENACOL-612, DENACOL (DENACOL) EX-612, DENACOL (DENACOL) EX-614, DENACOL-220, DENACOL (DENACOL) EX-212, DENACOL) EX-33, DENACOL (DENACOL) EX-33, DENACOL, and DENACOL (DENACOL ) EX-33, DENACOL, DENACOR, DENACOL, DENACOR, DENACOL, DENACOR, DENACOL, and the NACOL, DENACOL, NACOR, NACOL, NACOR, NACOL, NACOR, and the NACOL, NACOR, NACOL, NACOR, NACOL, and the NACOL, and the NACOL, NACORE, NACOR, NACOL, and the NACOL, NACOR, and the NACOL, NACORE, NACOL, Danacol (DENACOL) EX-622, Danacol (DENACOL) EX-711, Danacol (DENACOL) EX-721 (tradename, manufactured by Nagase ChemteX corporation), Tegick (TEPIC) -L, Tegick (TEPIC) -H, Tegick (TEPIC) -S (manufactured by daily chemical industry), and the like.

The content of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the colorant (a). When the amount is properly adjusted, the contrast ratio and heat resistance are improved.

(Oxetane Compound)

The oxetane compound is a conventional compound having an oxetanyl group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and oxetane compounds having three or more functions.

Examples of monofunctional oxetane compounds are: (3-Ethyloxetan-3-yl) methyl acrylate, (3-ethyloxetan-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloyloxymethyl) oxetane, 3-ethyl-3- { [3- (triethoxysilyl) propoxy ] methyl } oxetane, and the like.

Specific examples thereof include OXE-10 and OXE-30 manufactured by Osaka organic chemical industries, and OXT-101 and OXT-212 manufactured by east Asia Synthesis.

Examples of difunctional oxetane compounds include: 4,4' -bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] biphenyl), 1, 4-bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] benzene, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, bis [ 1-ethyl (3-oxetanyl) ] methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3, 7-bis (3-oxetanyl) -5-oxa-nonane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Ethylene Oxide (EO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, Propylene Oxide (PO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.

Specific examples thereof include: OXBP and OXTP manufactured by Uyu Kyowa company, OXT-121 and OXT-221 manufactured by east Asia synthetic company, and the like.

Examples of the trifunctional or higher oxetane compound include: pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxetanyl group-containing resins (for example, an oxetane-modified phenol novolak resin described in japanese patent No. 3783462, etc.) or a (meth) acrylic monomer such as OXE-30 described above.

The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the nonvolatile component of the photosensitive coloring composition. When the content of the oxetane compound is within the above range, a coating film excellent in water mark and high in chemical resistance can be obtained, and therefore, it is preferable.

The melamine compound means a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Preferred in the present invention is a melamine compound of the methylol type or the ether type, in which the number of methylol groups and/or ether groups per melamine ring is 5.0 or more on average. If the number of methylol groups and/or ether groups per melamine ring is less than 5.0 on average, the number of reaction sites is small, and the crosslinked structure at the time of curing is not sufficiently dense, so that the effect of suppressing the decrease in contrast ratio or improving the N-methylpyrrolidone resistance by the heat treatment step may be small.

Examples of commercially available products include: NICALAC (NIKALAC) MW-30HM, NICALAC (NIKALAC) MW-390, NICALAC (NIKALAC) MW-100LM, NICALAC (NIKALAC) MX-750LM, NICALAC (NIKALAC) MW-30M, NICALAC (NIKALAC) MW-30, NICALAC (NIKALAC) MW-22, NICALAC (NIKALAC) MS-21, NICALAC (NIKALAC) MS-11, NICALAC (NIKALAC) MW-24X, NICALAC (NIKALAC) MS-001, NICALAC (NIKALAC) MX-002, NICALAC (NIKALAC) MX-730, NICALAC (NIKALAC) MX-750, NICALAC (NIKALAC) NIKALAC, NICALAC (NIKALAC) MX-520, NICALAC (NIKALAC) MX-04LAC), NICALC (NIKALAC) MX-520, NICALC (NIKALAC) MX-500, NICA-500, NICALC (NIKALAC) MW-24X, NICA-M-500, NICA-M-500 NICA-C, NICA-LAC (NIKALAC) MS-M-24X, NICA LAC, NICA-M-24X, NICALC, NICA-M, NICALC, NICA-M-C, NICA-M-C, NICALC, NICA-M-C, NICA-M-C, NICA-M-C, NICALC, NICA-M, NICALC, NICA-M, NICA-C, NICA-M, NICALC, NICA-C, NICA-M, NICA-C, NICA-M, NICA-C, NICA-M, NICA-C, NICA-M, NICA-, Nicarback (NIKALAC) MX-43, Nicarback (NIKALAC) MX-417, Nicarback (NIKALAC) MX-410 (manufactured by sanhe chemical company), Cimel (CYMEL)232, Cimel (CYMEL)235, Cimel (CYMEL)236, Cimel (CYMEL)238, Cimel (CYMEL)285, Cimel (CYMEL)300, Cimel (CYMEL)301, Cimel (CYMEL)303, Cimel (CYMEL)350, Cimel (CYMEL)370 (manufactured by Japan cyanote Industries, inc.) and the like.

Among these, the average number of methylol and/or ether groups per melamine ring is 5.0 or more of Nicardak (NIKALAC) MW-30HM, Nicardak (NIKALAC) MW-390, Nicardak (NIKALAC) MW-100LM, Nicardak (NIKALAC) MX-750LM, Nicardak (NIKALAC) MW-30M, Nicardak (NIKALAC) MW-30, Nicardak (NIKALAC) MW-22, Nicardak (NIKALAC) MS-21, Nicardak (NIKALAC) MS-11, Nicardak (NIKALAC) MW-24X, Nicardak (NIKALAC) MW-45 (Sanko chemical Co.), seimel (CYMEL)232, Seimel (CYMEL)235, Seimel (CYMEL)236, Seimel (CYMEL)238, Seimel (CYMEL)300, Seimel (CYMEL)301, Seimel (CYMEL)303, Seimel (CYMEL)350 (manufactured by Japan cyanote Industries, Inc.) and the like are preferable in terms of increasing the crosslinking density.

The thermosetting compound (G) may be used alone or in combination of two or more.

[ hardening agent ]

In order to assist the curing of the thermosetting compound, a curing agent (curing accelerator) may be used in combination with the photosensitive coloring composition as necessary. Examples of the curing agent include: amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Examples of the hardening accelerator include: amine compounds (e.g., dicyandiamide, benzyldimethylamine (benzyldimethylamine), 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), and the like, Phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2, 4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4, 6-diamino-S-triazine/isocyanuric acid adduct, 2, 4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.), and the like.

The curing agent may be used alone or in combination of two or more.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (G).

[ antioxidant (H) ]

The photosensitive coloring composition may contain an antioxidant (H). The antioxidant (H) can prevent the film formed from the photosensitive coloring composition from yellowing due to oxidation due to thermal curing or a thermal process during annealing of Indium Tin Oxide (ITO), and can suppress a decrease in the transmittance of the film. In particular, when the concentration of the colorant in the photosensitive coloring composition is high, the content of the polymerizable compound is relatively reduced, and therefore, when the content is adjusted by increasing the amount of the photopolymerization initiator or by blending the thermosetting compound, the coating film is easily yellowed. Therefore, by including the antioxidant (H), yellowing due to oxidation during the heating step can be prevented, and a decrease in transmittance of the coating film can be suppressed.

The antioxidant (H) is a compound having a radical trapping function or a peroxide decomposing function. Examples of the antioxidant (H) include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. Further, the antioxidant (H) is preferably a compound containing no halogen atom. Among these, from the viewpoint of satisfying both the transmittance and sensitivity of the coating film, a hindered phenol compound, a hindered amine compound, a phosphorus compound, and a sulfur compound are preferable.

Examples of the hindered phenol antioxidant include: 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 1, 3-tris- (2 '-methyl-4' -hydroxy-5 '-tert-butylphenyl) -butane, 4' -butylidene-bis- (2-tert-butyl-5-methylphenol), stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4, 6-trimethylbenzene, 1,3, 5-tris (3-hydroxy-4-tert-butyl-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2 '-methylenebis (6-tert-butyl-4-ethylphenol), 2' -thiodiethylbis- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydroxycinnamide), Isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4, 6-bis (dodecylthiomethyl) -o-cresol, the calcium salt of monoethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 4, 6-bis (octylthiomethyl) -o-cresol, bis [3- (3- (methyl-4-hydroxy-5-tert-butylphenyl) propanoic acid ] ethylenedioxydiethylene ester, 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylaniline) -1,3, 5-triazine, 2' -thio-bis- (6-tert-butyl-4-methylphenol), 2, 5-di-tert-amyl-hydroquinone, 2, 6-di-tert-butyl-4-nonylphenol, 2' -isobutylidene-bis- (4, 6-dimethyl-phenol), 2' -methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2, 4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, and the like.

Examples of commercially available products include: addiskota wave (Adekastab) AO-20, Addiskota wave (Adekastab) AO-30, Addiskota wave (Adekastab) AO-40, Addiskota wave (Adekastab) AO-50, Addiskota wave (Adekastab) AO-60, Addiskota wave (Adekastab) AO-80, Addiskota wave (Adekastab) AO-330, Kaixos (Ke Minox)101, Kaixno (Ke NOx)179, Kaixno (Ke NOx)76, Kaixno (Ke NOx)9425, Kaixno (Ka Nox Ne) 780, Gaixo Ro) (IR Negaku) (IR Nox Negazel) 1135, IR Nox Ne (IR) 1075, IRGAIxol 5, IRGAIxol 1135, IRGAIxol (IRGANOx)1330, IRGANOx Negax Negao, Io-Luo-Nuo (IRGANOX)245, Io-Luo-Nuo (IRGANOX)259, Io-Luo-Nuo (IRGANOX)3114, Io-Luo-Nuo (IRGANOX)5057, Io-Luo-Nuo (IRGANOX)565, Sea-Nuo (CYANOX) CY-1790 manufactured by Sun Chemical, Sea-Nuo (CYANOX) CY-2777, and the like.

Examples of the hindered amine antioxidant include: tetrakis (1,2,2,6, 6-pentamethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-undecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6, 6-pentamethyl-4-piperidyl methacrylate, 2,2,6, 6-tetramethyl-4-piperidyl methacrylate, bis (1-undecyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) methacrylate, A polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amino ] -s-triazine-2, 4-diyl ] - [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] -hexamethylene- [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] ], an ester of 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol and 3,5, 5-trimethylhexanoic acid, N' -4, 7-tetrakis [4, 6-bis { N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino } -1,3, 5-triazin-2-yl ] -4, 7-diazepane-1, 10-diamine, the reaction product of bis (2,2,6, 6-tetramethyl-1- (octyloxy) -4-piperidyl) sebacate and 1, 1-dimethylethyl hydroperoxide with octane, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] butyl malonate, methyl 1,2,2,6, 6-pentamethyl-4-piperidyl sebacate, poly [ [ 6-morpholinyl-s-triazine-2, 4-diyl ] - [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] -hexamethylene- [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] ], an unsaturated fatty acid ester of 2,2,6, 6-tetramethyl-4-piperidyl-C12-21 or C18, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexamethylenediamine, 2-methyl-2- (2,2,6, 6-tetramethyl-4-piperidyl) amino-N- (2,2,6, 6-tetramethyl-4-piperidyl) propionamide, and the like.

Examples of commercially available products include: adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-81, Adekastab LA-82, Adekastab LA-87, Adekastab LA-402F, Adekastab LA-502, and Cheekastab TAB (Mikataca Tab) K-249, Kamiyab KAI-29, Kamiyab KAMITAB KAI, Kamiyab KAMITAB K-249, Kamiyab KAMITAB KAI, Kamiyab KAMITAB-249, Kamiyab KAMITAB, KAMITAB TAB K-249, KAMITAB KAI, KAMITAB, KAMITAB KAI-249, KAMITAB, KAMITAB KAI, KAMITAB, KAMITAB, KAI, KAMITAB BII, KAMITAB, KAI, KAMITAB, KAI, KAMITAB, KAI, KAMITAB, KAI, KAMITAB, NABII, KAMITAB, NABII, KAMITAB, NAB, NABII, NABIA, KAMITAB, NAB, NATAB, NABIB, NABIA BIB, NAB, NATAB, NAB, NABII, NABIB, NABII, NABIB, NATAB, NAB, NABII, NAB, NATAB, NABII, NABIB, NAB, NATAB, NAB, NA, Bin (TINUVIN)111FDL, Bin (TINUVIN)123, Bin (TINUVIN)144, Bin (TINUVIN)292, Bin (TINUVIN)5100, Cyasorb (CYASORB) UV-3346, Cyasorb (CYASORB) UV-3529, Cyasorb (CYASORB) UV-3853, etc., manufactured by Sun Chemical.

Examples of the phosphorus-containing antioxidant include: bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2 '-methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (C12-C15 alkyl) -4,4' -isopropylidenediphenyl phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4-biphenylyl diphosphonate, tris (tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, distearyl phosphite, Phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4 '-isopropylidenediphenol alkyl phosphite, trinonylphenyl phosphite, tris-dinonylphenyl phosphite, tris (biphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra-tridecyl 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, hexa-tridecyl 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphite, bisphenol A, tris (p-butyl) phosphite, bis (2, 4-isopropylidenediphenyl) pentaerythritol diphosphite, tris (p-butyl) phosphite, bis (3, bis (p-butyl) phosphite, 4-butyl) phosphite, bis (p-butyl) phosphite, bis (3, 4-tert-butyl) phosphite, bis (p-butyl) phosphite, bis (2, 4-butyl) phosphite, bis (p) phosphite, bis (2, bis (p-butyl) phosphite, bis (2-butyl) phosphite, bis (p) phosphite, bis (2-butyl) bis (p-butyl) phosphite, bis (p) bis (p-bis (p) phosphite, p-butyl) bis (p-butyl) phosphite, p-bis (p-butyl ) phosphite, p-butyl, and (p-butyl) bis (p-butyl) phosphite, Sodium bis (4-tert-butylphenyl) phosphite, sodium 2, 2-methylene-bis (4, 6-di-tert-butylphenyl) -phosphite, 1, 3-bis (diphenoxyphosphonoxy) -benzene, ethylbis (2, 4-di-tert-butyl-6-methylphenyl) phosphite, and the like.

Examples of commercially available products include: adekastab PEP-36, Adekastab PEP-8, Adekastab HP-10, Adekastab 2112, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Idekastab IREFOSTAT (IRGAFOS)168, and Ho-O Q manufactured by Claryanodica Clarias, and so on.

Examples of the sulfur-based antioxidant include: 2, 2-bis { [3- (dodecylthio) -1-oxopropoxy ] methyl } propane-1, 3-diylbis [3- (dodecylthio) propionate ], ditridecyl 3,3' -thiodipropionate, 2-thio-diethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2, 4-bis [ (octylthio) methyl ] -o-cresol, 2, 4-bis [ (laurylthio) methyl ] -o-cresol and the like.

Examples of commercially available products include Adekastabo (Adekastab) AO-412S manufactured by Adekata (ADEKA), Adekastab (Adekastab) AO-503, and Keminox (KEMINOX) PLS manufactured by Chemipro Kasei (Chemipro).

The antioxidant (H) may be used alone or in combination of two or more.

The content of the antioxidant (H) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile component of the photosensitive coloring composition. When contained in an appropriate amount, the transmittance, spectroscopic properties and sensitivity are improved.

[ ultraviolet absorber (I) and polymerization inhibitor (J) ]

The photosensitive coloring composition may contain an ultraviolet absorber (I) and a polymerization inhibitor (J). By containing the ultraviolet absorber (I) and the polymerization inhibitor (J), the shape and resolution of the pattern are improved. Examples of the benzotriazole compounds useful as the ultraviolet absorber (I) include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 5 parts of 2-methoxy-1-methylethyl acetate and 95 parts of phenylpropionic acid and a mixture of 3- (2H-benzotriazol-2-yl) - (1, 1-dimethylethyl) -4-hydroxy and C7-9 side chains and linear alkyl esters The compound is selected from 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, a reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate/polyethylene glycol 300, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol ], 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole, octyl-3 [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, and mixtures thereof, 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate.

Examples of commercially available products include: bin (TINUVIN) P, Bin (TINUVIN) PS, Bin (TINUVIN)234, Bin (TINUVIN)326, Bin (TINUVIN)329, Bin (TINUVIN)384-2, Bin (TINUVIN)900, Bin (TINUVIN)928, Bin (TINUVIN)99-2, Bin (TINUVIN)1130, available from Abidekata (MIS-Tab) LA-29, available from Aikota (ADEKA), Adekab (Adekab) LA-31, Adekab (MIS-Tab) LA-32, MIS-Tab (MIS-Tab) LA-36, available from Kamikekub corporation, Kamike ORkurg 73, available from Kamikurbu-chekuba corporation, Kamike-73, available from Kamikurbu-93, Kamikurbu-chemike (Kamike-kurb-73, available from Aikota-Kamikumi-K corporation, kawa (TINUVIN) 93, Kamike-32, kawa, available from Aikota (Adkawa), Kamikawa, available from Aimike, Inc.

Examples of the triazine compound that can be used as the ultraviolet absorber (I) include: 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3, 5-triazine, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and (2-ethylhexyl) -glycidic acid ester, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- (hexyloxy) phenol, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy ] phenol, 2,4, 6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3, 5-triazine and the like.

Examples of commercially available products include: camisole (KEMISORB)102 manufactured by Chemipro Kasei, Inula (TINUVIN)400 manufactured by BASF, Inula (TINUVIN)405, Inula (TINUVIN)460, Inula (TINUVIN)477, Inula (TINUVIN)479, Inula (TINUVIN)1577ED, Adzida ta (Adeka) LA-46 manufactured by Adeka, Adzita (Adekab) LA-F70, Adzia Soxhlet (CYORB) UV-1164 manufactured by Sun Chemical, and the like.

Examples of benzophenone-based compounds useful as the ultraviolet absorber (I) include: 2, 4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2' -di-hydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecylbenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2',4,4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2 ' -carboxybenzophenone and the like.

Examples of commercially available products include: kemisoh cloth (KEMISORB)10, kemisoh cloth (KEMISORB)11S, Kemiorb (KEMISORB)12, Kemiorb (KEMISORB)111, kemiorb (SEESORB)101, semisorb (semisorb) 107, idecolat (ADEKA) 1413, and UV-12 manufactured by Sun Chemical (Sun Chemical).

Examples of the salicylate-based compound usable as the ultraviolet absorber (I) include: phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

Examples of the polymerization inhibitor (J) include: alkyl catechol-based compounds such as catechol, resorcinol, 1, 4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3, 5-di-tert-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, t-butyl hydroquinone, and 2, 5-di-t-butyl hydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, and the like; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol, phloroglucin, and the like.

The ultraviolet absorber (I) and the polymerization inhibitor (J) may be used alone or in combination of two or more.

The content of the ultraviolet absorber (I) and the polymerization inhibitor (J) is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass, respectively, with respect to 100 parts by mass of the colorant (D). The resolution is improved by using a proper amount.

The content of the ultraviolet absorber (I) is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When the amount is contained in an appropriate amount, a good pattern shape can be easily obtained.

The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile component of the photosensitive coloring composition. When the amount is contained in an appropriate amount, a good pattern shape can be easily obtained.

[ solvent ]

The photosensitive coloring composition may contain a solvent. Examples of the solvent include: 1,2, 3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol (1, 3-butandiol), 1,3-butanediol (1,3-butylene glycol), 1,3-butanediol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1, 3-propanediol, 3,5, 5-trimethyl-2-cyclohexene-1-one, 3, 5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1, 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N-dimethylacetamide, N-dimethylformamide, N-butyl alcohol, N-butylbenzene, N-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, gamma-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, N-diethylbenzene, N-dichlorobenzene, N-dimethylacetamide, N-dimethylformamide, N-butyl alcohol, N-butylbenzene, N-butyl alcohol, gamma-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, isobutyl alcohol, isopropyl alcohol, butyl ether, isopropyl alcohol, butyl ether, isopropyl alcohol, butyl ether, methyl ether, isopropyl alcohol, butyl ether, methyl ether, isopropyl alcohol, methyl ether, butyl ether, methyl ether, butyl ether, methyl ether, butyl ether, methyl ether, butyl ether, methyl ether, butyl ether, Diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glyceryl triacetate (triacetin), tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether acetate, propylene glycol monobutyl ether, methyl alcohol, propylene glycol monobutyl ether, methyl alcohol, butyl acetate, methyl alcohol, butyl ether acetate, methyl alcohol, butyl ether acetate, butyl ether acetate, butyl ether, and butyl ether acetate, butyl ether, propylene glycol, butyl ether, and butyl ether, propylene glycol, and butyl ether, propylene glycol ether, propylene glycol ether, propylene glycol ether acetate, propylene glycol ether, propylene glycol, Isobutyl acetate, propyl acetate, dibasic acid esters, and the like. Of these, from the viewpoints of dispersibility of the colorant and solubility of the binder resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable; alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

The solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 100 to 10000 parts by mass, more preferably 500 to 5000 parts by mass, per 100 parts by mass of the colorant (D).

[ silane coupling agent (K) ]

The photosensitive coloring composition may contain a silane coupling agent (K). This improves the adhesion to the substrate.

Examples of the silane coupling agent (K) include: vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane; (meth) acryloxysilanes such as γ -methacryloxypropyltrimethoxysilane; epoxysilanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) methyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) methyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane; aminosilanes such as N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, and N-phenyl-gamma-aminopropyltriethoxysilane; and thiosilanes (thiosilanes) such as gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane.

The content of the silane coupling agent (K) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (D).

The photosensitive coloring composition may contain an amine compound having an action of reducing dissolved oxygen. Examples of the amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, and the like.

[ leveling agent (L) ]

The photosensitive coloring composition may contain a leveling agent (L). This further improves the wettability to the transparent substrate and the drying property of the coating film during the formation of the coating film. Examples of the leveling agent (L) include: silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

Examples of the silicone surfactant include: a linear polymer containing a siloxane bond, or a modified siloxane polymer having an organic group introduced into a side chain or a terminal thereof.

Examples of commercially available products include: BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-UV3570, FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191, FZ-5609, made by Nikko chemical industries, X-22-4952, X-22-4272, X-22-351-6232, KF-35354-L-351A, KF, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain and a leveling agent.

Examples of commercially available products include: sanflon (Surflon) S-242, Sanflon (Surflon) S-243, Sanflon (Surflon) S-420, Sanflon (Surflon) S-611, Sanflon (Surflon) S-651, Sanflon (Surflon) S-386, Meijia (Megafac) F-253, Meijia (Megafac) F-477, Meijiafa (Megafac) F-551, Meijiafa (Megafac) F-552, Meijia (Megafac) F-555, Meijiafac (Megafac) F-558, Meijiafac (Megafac) F-560, Meijiafac (Megafac) F-570, Megafac) F-575, Meijiafac (Megafac) S-576, Megafac (Megafac) R-41, Megafac (Megafac) S-386, Megafac) F-576, Megafac (Megafac) F-72, Megafac) F-576, Meijia method (Megafac) DS-21, FC-4430 and FC-4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1 and EF-PP32C1 manufactured by Mitsubishi Material electronics, Forgejt (Ftergent)602A manufactured by Nioces (NEOS), and the like.

Examples of the nonionic surfactant include: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene diphenylstyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monolaurate, and the ester, polyoxyethylene sorbitan monolaurate, and the like, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hardened castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

Examples of commercially available products include: the Aiyugen (Emulgen)103, Aiyugen (Emulgen)104P, Aiyugen (Emulgen)106, Aiyugen (Emulgen)108, Aiyugen (Emulgen)109P, Aiyugen (Emulgen)120, Aiyugen (Emulgen)123P, Aiyugen (Emulgen)130K, Aiyugen (Emulgen)147, Aiyugen (Emulgen)150, Aiyugen (Emulgen)210P, Aiyugen (Emulgen)220, Aiyugen (Emulgen)306P, Aiyugen (Emulgen)320P, Aiyugen (Emulgen)350, Aiyugen (Emulgen)404, Aiyugen (Emulgen)408, Emulgen (Emulgen)705, Aiyugen (Emulgen)70, Aiyugen (Emulgen) 55, Aiyugen-70, Aiyugen (Emulgen) 55, Aiyugen) 70, Aiyugen (Emulgen) 55, Aiyugen (Emulgen)70, Aiyugen (Emulgen) 60, Aiyugen (Emulgen)70, Aiyugen) 60, Aiyugen (Emulgen) 60, Aiyugen) 140, Aiyugen (Emulgen)123, Aiyugen) 123, Aimu (Emulgen) 140, Aimu (Emulgen) and Edugen, Amur primrose root (Emulgen)2025G, Amur primrose root (Emulgen) LS-106, Amur primrose root (Emulgen) LS-110, Amur primrose root (Emulgen) LS-114, Amur primrose root (Emulgen) MS-110, Amur primrose root (Emulgen) A-60, Amur primrose root (Emulgen) A-90, Amur primrose root (Emulgen) B-66, Amur primrose root (Emulgen) PP-290, Latemul (Latemul) PD-420, Latemul (Latemul) PD-430S, Latemul (Latemul) PD-450, Latemul (Latemul) SP-L10, Orodul (Rheopol) SP-P-56, Latemul (Latemul) SP-L10, Latemul (Latemul) SP-10, Latemul (Latemul) SP-29, Raodul (Rheodul) SP-3, Raodul) SP-L10, Raodul (Raodul) SP-3, Raodul (Raodul) SP-3, Raodul) SP-3, Raodul (Raddul) SP-3, Raddul (Raddul) SP-30, Raddul, Raodul (Raddul) SP-10, Raddul (Raddul) SP-10, Raddul) SP-3, Raddul (Raddul, and Raddul (Raddul) SP-10-d, LyodeRou (Rheodol) AS-10V, LyodeRou (Rheodol) AO-15V, LyodeRou (Rheodol) TW-L120, LyodeRou (Rheodol) TW-L106, LyodeRou (Rheodol) TW-P120, LyodeRou (Rheodol) TW-S120V, LyodeRou (Rheodol) TW-S320V, Lyodero (Rheodol) TW-O120V, LyodeRou (Rheodol) TW-O106V, LyodeRou TW (Rheodol) IS-399C, Lyodero (Rheodol) TW-L120, Lyodero (Rheodol)430V, Lyodero (Rheodol) MS-440, Rheodol (Rheodol) TW-L-120, Lyodero (Rheodol) MS-S120, Rheodol (Rheodol) 120, Rheodol) MS-S-120, Rheodol (Rheodol) 120, Rheodol-S-, Amur concentrate (Emanon)3299V, Amur concentrate (Emanon)3299RV, Amur concentrate (Emanon)4110, Amur concentrate (Emanon) CH-25, Amur concentrate (Emanon) CH-40, Amur concentrate (Emanon) CH-60(K), Amite (Amiet)102, Amite (Amiet)105A, Amite (Amiet)302, Amite (Amiet)320, Aminon (Aminon) PK-02S, Aminon (Aminon) L-02, fire Motonenol (Homogennol) L-95, Amideco (ADEKA) manufactured by Aikoponicu Pluronic (Adeka) Inc. (Adeka Pluronic) L-23, Aikoponic (Adeka) L-31, Aikoponic (Adeka) L-64, Adeka Plukenic (Adeka) L-61, Adeka L-31, Adeka L-64, Adeka-60, Adeka-61, and Adeka L-31, Adeka Pluronic L-71, Adeka Pluronic L-72, Adeka Pluronic L-101, Adeka Pluronic L-121, Adeka Pluronic TR-701, Adeka Pluronic TR-702, Adeka Pluronic TR-704, Adeka Pluronic TR-913R, (meth) acrylic (co) polymer (co) Popffer No.75, PolyFreon (Polyfreon) 90, PolyFreon (Polyfreon) 95, etc. manufactured by Coco chemical company.

Examples of the cationic surfactant include: alkyl quaternary ammonium salts such as alkylamine salts, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.

Examples of commercially available products include asethamine (Acetamin)24, cortolamine (Quartamin)24P, cortolamine (Quartamin)60W, cortolamine (Quartamin)86P CONC, and the like, which are manufactured by Kao corporation.

Examples of the anionic surfactant include: polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphate, and the like.

Examples of commercially available products include: fojirt (Ftergent)100 and 150 manufactured by Nios (NEOS), Adekoup (ADEKA HOPE) YES-25 manufactured by Adekou (ADEKA), Adekou (ADEKA COL) TS-230E, Adekou (ADEKA COL) PS-440E, and Adekou (ADEKA COL) EC-8600.

Examples of amphoteric surfactants include: alkyl betaines such as lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; alkyl amine oxides such as lauryl dimethyl amine oxide, and the like.

Examples of commercially available products include Amphiol (AMPHITOL)20AB, Amphiol (AMPHITOL)20BS, Amphiol (AMPHITOL)24B, Amphiol (AMPHITOL)55AB, Amphiol (AMPHITOL)86B, Amphiol (AMPHITOL)20Y-B, and Amphiol (AMPHITOL)20N manufactured by Kao corporation.

The leveling agents (L) may be used alone or in combination of two or more.

The content of the leveling agent (L) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile component of the photosensitive coloring composition. Thus, the coating property, pattern adhesion and transmittance of the photosensitive coloring composition can be improved in a well-balanced manner.

[ other ingredients ]

(storage stabilizer)

The photosensitive coloring composition may contain a storage stabilizer. The viscosity of the composition with time can be stabilized by containing a storage stabilizer. Examples of the storage stabilizer include: hindered phenol systems such as 2, 6-bis (1, 1-dimethylethyl) -4-methylphenol, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylaniline) 1,3, 5-triazine; organic phosphines such as t-butyl catechol, tetraethyl phosphine, triphenylphosphine, and tetraphenylphosphine; phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, and molybdenum dibutyldithiophosphate; sulfur systems such as dodecyl sulfide and benzothiophene; quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof.

The storage stabilizer may be used alone or in combination of two or more.

The content of the storage stabilizer is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the colorant (D). When contained in an appropriate amount, the stability with time is improved.

(Adhesives)

The photosensitive coloring composition may contain an adhesion improving agent. This further improves the adhesion between the coating and the substrate. In addition, a pattern having a narrow width is easily formed by photolithography.

Examples of the adhesion improver include a silane coupling agent. Specific examples thereof include: vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.; aminosilanes such as hydrochloride of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto groups such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureido groups such as 3-ureidopropyltriethoxysilane; thioethers such as bis (triethoxysilylpropyl) tetrasulfide; and isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane.

The adhesion improver may be used alone or in combination of two or more.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (D). When the photosensitive coloring composition is contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the coating film is further improved, and a good pattern shape can be obtained.

< method for producing photosensitive coloring composition >

The method for producing the photosensitive coloring composition is not particularly limited, and a conventional method can be used. As an example of a method for producing a photosensitive coloring composition, for example, a colorant dispersion is first prepared by performing a dispersion treatment using the colorant (D), a dispersant, a solvent, and the like. In addition, when the solubility of the colorant (D) in the solvent is high, the dispersion treatment may not be necessary. In the case where two or more colorants (D) are used in combination, a colorant dispersion may be prepared separately for each colorant (D) and then mixed. Alternatively, a colorant dispersion may be prepared using a plurality of colorants (D) together. Next, a photopolymerization initiator (a), a binder resin (B), and a photopolymerizable compound (C) are blended with the colorant dispersion, and mixed to obtain a photosensitive colored composition. The timing of blending the materials is, of course, arbitrary.

The dispersion treatment may use a dispersion apparatus such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring type (annular type) bead mill, or an attritor.

The average dispersed particle diameter (secondary particle diameter) of the colorant (D) in the dispersion is preferably 30 to 200nm, more preferably 40 to 200 nm. Within this range, a photosensitive coloring composition having high dispersion stability can be obtained, and when a color filter is produced using the composition, a high-quality color filter can be obtained.

Examples of the method for measuring the average dispersed particle diameter (secondary particle diameter) include the following methods: the particle transmittance was set to the absorption mode, the particle shape was set to the aspherical shape, and D50 was set to the average diameter using micro track UPA-EX150 of japanese mechanical engineers (fast Fourier transform (FFT) power spectroscopy) using dynamic light scattering. The organic solvents used for dispersion are preferably used as the diluting solvents for measurement, and when a sample treated with ultrasonic waves is measured immediately after sample adjustment, the result of small variations is easily obtained.

[ removal of coarse particles ]

The photosensitive coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000G to 25000G, filtration with a sintered filter or a membrane filter, or the like. Thus, the photosensitive coloring composition preferably does not substantially contain particles of 0.5 μm or more. More preferably 0.3 μm or less.

< color filter >

The color filter comprises a substrate and a filter section formed by the photosensitive coloring composition. The color filter segment (hereinafter also referred to as a filter segment) may have a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the kind of the colorant (D) used. In addition, the color filter may further have a magenta filter segment, a cyan filter segment, and a yellow filter segment as the color filter segments. The substrate is preferably a transparent substrate or a reflective substrate. The transparent substrate may be, for example, a glass substrate. Examples of the reflective substrate include substrates using aluminum electrodes or metal thin films as reflective surfaces.

< method for manufacturing color filter >

As an example of a method for manufacturing a color filter, for example, the following steps can be used: the method comprises a step of applying a photosensitive coloring composition on a substrate to form a colored layer, a step of exposing the colored layer in the form of a pattern through a mask, and a step of developing and removing the unexposed portion to form a colored pattern.

Further, a step of drying the colored layer (pre-baking step) and a step of thermally curing the colored pattern (post-baking) may be provided as necessary.

Hereinafter, the method for manufacturing the color filter of the present invention will be described in detail.

(Process for Forming colored layer)

In the process of forming the colored layer, first, a black matrix is formed on a substrate, and then a filter segment is formed. In addition, a black matrix may be formed after a Thin Film Transistor (TFT) is formed in advance on a substrate. Examples of the black matrix include: chromium, a chromium/chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed.

Next, a coating film is formed by applying a photosensitive coloring composition containing a colorant of a certain color tone onto a substrate by an application method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, for example, by photolithography so that the dry film thickness becomes about 0.2 μm to 5 μm. If necessary, drying (prebaking) at a temperature of 50 to 120 ℃ for 10 to 120 seconds using an oven, a hot plate, or the like.

(step of exposing to light in a Pattern)

In the exposure step, the first coating film formed in the step of forming the colored layer is exposed to a specific pattern through a mask using an exposure apparatus such as a photolithography machine (stepper). Thereby obtaining a hardened film.

As the radiation usable for the exposure, for example, ultraviolet rays such as g-ray, h-ray, i-ray and the like are preferably used.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.2 to 0.8. mu.m, and particularly preferably 0.2 to 0.6. mu.m.

(developing step)

By performing the alkali development treatment, the colored layer in the non-irradiated portion in the exposure step is eluted into the alkali aqueous solution, and only the hardened portion remains.

The developer may be, for example, an existing developer without particular limitation. Specifically, there may be mentioned an alkaline aqueous solution having a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass%, obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, 8-diazabicyclo- [5.4.0] -7-undecene, or the like. In addition, a defoaming agent or a surfactant may be added to the developer.

The alkali developing solution is preferably an alkaline aqueous solution in which the alkali concentration is adjusted to preferably pH11 to pH13, and more preferably pH11.5 to pH12.5, and when the alkali concentration is within the above range, the pattern roughening and peeling can be more effectively suppressed, the residual film rate can be further increased, and the reduction in the developing speed and the generation of development residue can be more effectively suppressed.

The developing method may use an existing method. For example, the dipping method, the spraying method, the liquid coating method, etc. are used, and the temperature is preferably 15 to 40 ℃. After the alkali development, washing with pure water is preferably performed.

Next, after drying, it is preferable to perform a heat treatment (post-baking) in order to sufficiently cure the cured film. The heating temperature for the post-baking is preferably 100 to 300 ℃, and more preferably 150 to 250 ℃. The heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

Further, a second coating film (oxygen barrier film) may be formed on the coating film before exposure by further using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from contacting oxygen, thereby further improving exposure sensitivity. In addition, the color filter may be heated in order to cure the uncured photopolymerizable compound in the filter segment.

< image display device >

The image display device includes a color filter. The image display device preferably further comprises a light source. A liquid crystal display device will be described as an example of an image display device. The liquid crystal display device comprises a color filter and a light source. Examples of the Light source include a Cold Cathode tube (Cold Cathode Fluorescent Lamp (CCFL)) and a white-Emitting Diode (LED), and in the present embodiment, a white LED is preferably used in terms of a wide red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including a color filter. The device 10 shown in fig. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and a liquid crystal LC is sealed between the substrates.

The liquid crystal LC is aligned In accordance with a driving mode such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an In-Plane switching (IPS) mode, a Vertical Alignment (VA) mode, an Optically Compensated Birefringence (OCB) mode, or the like.

A TFT (thin film transistor) array 12 is formed on an inner surface of the first transparent substrate 11, and a transparent electrode layer 13 including, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filters constituting the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 including, for example, ITO is formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Further, a backlight unit 30 is disposed below the polarizing plate 15.

The white LED light source 31 includes a blue LED having a fluorescent filter formed on a surface thereof or a blue LED containing a phosphor in a resin package, and is preferably a white LED light source (LED 1) and a white LED light source (LED 2) in which the white LED light source (LED 1) has the following spectral characteristics: a wavelength (λ 3) in which the emission intensity is extremely large in the range of 430nm to 485nm, a wavelength (λ 4) in which the emission intensity is extremely large in the range of 530nm to 580nm, and a wavelength (λ 5) in which the emission intensity is extremely large in the range of 600nm to 650nm, wherein the ratio (I4/I3) of the emission intensity I3 at the wavelength λ 3 to the emission intensity I4 at the wavelength λ 4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at the wavelength λ 3 to the emission intensity I5 at the wavelength λ 5 is 0.1 or more and 1.3 or less; the white LED light source (LED 2) has the following spectral characteristics: the light-emitting device has a wavelength (lambda 1) at which the emission intensity is maximized in the range of 430nm to 485nm, and a peak wavelength (lambda 2) at which the emission intensity is second in the range of 530nm to 580nm, and the ratio (I2/I1) of the emission intensity I1 at the wavelength lambda 1 to the emission intensity I2 at the wavelength lambda 2 is 0.2 to 0.7.

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nissan chemical Co., Ltd.), and NSSW304D-HG-V1 (manufactured by Nissan chemical Co., Ltd.).

Specific examples of the LED 2 include NSSW440 (manufactured by riya chemical corporation) and NSSW304D (manufactured by riya chemical corporation).

As an example of a method for manufacturing a liquid crystal display device, for example, first, after a filter segment is formed, a color filter is bonded to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in a sealing portion, the injection port is sealed, and a polarizing film and a retardation film are bonded to the outer side of the substrate as necessary. Thus, a liquid crystal display device can be manufactured.

The image display device can be used for applications such as a solid-state imaging element, an organic EL display device, a quantum dot display device, electronic paper, a head-mounted display, and the like, in addition to a liquid crystal display device.

< example of embodiment >

Examples of embodiments of the present invention are listed below. The embodiments of the present invention are not limited to the following examples.

[1] A photosensitive coloring composition contains a first photopolymerization initiator represented by the following general formula (1), a binder resin, a photopolymerizable compound and a colorant.

General formula (1)

(in the formula, R₁And R₂Each independently represents R₁₁Or COR₁₁，R₁₁R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₁₁The alkyl part of the alkyl, aryl, arylalkyl or heterocyclic radical may be a branched side chain or a cyclic alkyl radical, R₃Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R₃The alkyl part of the alkyl, aryl, arylalkyl or heterocyclic radical may be a branched side chain or a cyclic alkyl radical, R₃The hydrogen atom of the aryl, arylalkyl or heterocyclyl radical represented may furthermore be interrupted by R₂₁、OR₂₁、COR₂₁、SR₂₁、NR₂₂R₂₃、CONR₂₂R₂₃、-NR₂₂-OR₂₃、-NCOR₂₂-OCOR₂₃、NR₂₂COR₂₁、OCOR₂₁、SCOR₂₁、OCSR₂₁、COSR₂₁、CSOR₂₁Hydroxy, nitro, cyano (-CN), halogen atom or COOR₂₁Substituted, R₂₁、R₂₂And R₂₃Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R₂₁、R₂₂And R₂₃The hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may be further substituted with a hydroxyl group, nitro group, cyano group (-CN), halogen atom or carboxyl group, in the R₂₁、R₂₂And R₂₃In the alkylene moiety of the alkyl, aryl, arylalkyl or heterocyclic group represented by, -O-, -S-, -COO-, -OCO-, -NR-, -₂₄-、-NR₂₄CO-、-NR₂₄COO-、-OCONR₂₄-, -SCO-, -COS-, -OCS-, or-CSO-may contain 1 to 5 atoms under the condition that oxygen atoms are not adjacent,

R₂₄r represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₂₄The alkyl moiety of the alkyl, aryl, arylalkyl, or heterocyclyl group may be a branched side chain or may be a cyclic alkyl group, R₄Represents a hydroxyl group, a cyano group (-CN), a nitro group or a halogen atom, and n represents 0 or 1)

[2] The photosensitive coloring composition as described above, wherein the binder resin (B) comprises an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in a side chain, selected from the following (I) and (II).

(I) An alkali-soluble resin obtained by reacting a polybasic acid or a polybasic acid anhydride with a reaction product of an epoxy group and a carboxyl group-containing monomer in an epoxy group-containing polymer.

(II) an alkali-soluble resin which is a reaction product of a carboxyl group in a polymer having a carboxyl group and an epoxy group-containing monomer.

[3] The photosensitive coloring composition as described above, further comprising a polyfunctional thiol (F).

[4] The photosensitive coloring composition as described above further contains a photopolymerization initiator (Y).

[5] The photosensitive coloring composition as described above, wherein the photopolymerization initiator (Y) comprises at least one compound selected from the group consisting of an oxime ester compound, an acetophenone compound, a phosphine compound and an imidazole compound.

[6] A color filter comprises a substrate, and a filter segment or a black matrix formed by the photosensitive coloring composition.

[7] An image display device comprising the color filter as described above.

[8] A photosensitive coloring composition comprises a coloring agent (D), an alkali-soluble resin, a photopolymerizable compound (C) and a photopolymerization initiator (A), wherein the photopolymerization initiator (A) comprises a photopolymerization initiator (Y ') represented by the following general formula (2) and a photopolymerization initiator (A') represented by the following general formula (3).

General formula (2)

(in the formula, R₁Represents an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group, R₂R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms₃Represents a hydrogen atom, a nitro group, a group having an ether bond or a group exhibiting aromatic character)

General formula (3)

(in the formula, R₄And R₅Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms)

[9] The photosensitive colored composition as described above, wherein the content of the photopolymerization initiator (Y ') is 5 to 95 parts by mass based on 100 parts by mass of the total content of the photopolymerization initiator (a ') and the photopolymerization initiator (Y ').

[10] The photosensitive colored composition as described above, wherein the photopolymerization initiator (a) further comprises a photopolymerization initiator (a ') and a photopolymerization initiator (Z) other than the photopolymerization initiator (Y').

[11] The photosensitive coloring composition as described above, wherein the photopolymerization initiator (Z) is at least one selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds and imidazole compounds.

[12] The photosensitive colored composition as described above, wherein the total content of the photopolymerization initiator (a ') and the photopolymerization initiator (Y') is 30 parts by mass or more per 100 parts by mass of the content of the photopolymerization initiator (a) contained in the photosensitive colored composition.

[13] The photosensitive colored composition as described above, wherein the photopolymerizable compound (C) comprises a polymerizable compound (C-1) having a caprolactone-derived structure.

[14] The photosensitive coloring composition as described above, wherein the photopolymerizable compound (C) comprises a polymerizable compound (C-2) having an acidic group.

[15] The photosensitive coloring composition as described above, further comprising a sensitizer (E).

[16] A color filter comprises a substrate and a filter segment formed by using the photosensitive coloring composition.

[17] An image display device comprising the color filter as described above.

The present invention is related to the subject matter of japanese patent application No. 2020-.

[ examples ]

Hereinafter, an embodiment of the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. Hereinafter, "part" means mass part, "%" means mass%.

Hereinafter, PGMAc means propylene glycol monomethyl ether acetate.

The method of calculating the average molecular weight of the resin, and the acid value, amine value and ammonium salt value of the resin will be described.

(average molecular weight of resin)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin were measured by Gel Permeation Chromatography (GPC) equipped with a Refractive Index (RI) detector. HLC-8220GPC (Tosoh corporation) was used as a device, two separation columns were connected in series, two "TSK GEL SUPER HZM-N (TSK-GEL SUPER HZM-N)" were connected to each other in the packing material, and measurement was carried out at an oven temperature of 40 ℃ and a flow rate of 0.35ml/min using a THF solution as an eluent. The sample was dissolved in a solvent containing 1 wt% of the eluent, and 20. mu.l was injected. The molecular weights are all in terms of polystyrene.

(acid value of resin)

To 0.5g to 1g of the resin solution, 80ml of acetone and 10ml of water were added and uniformly dissolved by stirring, and an automatic titrator ("COM-555", manufactured by Ponga hirsuta industries) was used to titrate a 0.1mol/L potassium hydroxide (KOH) aqueous solution as a titrating solution, and the acid value (mgKOH/g) of the resin solution was measured. Then, the acid value per unit nonvolatile component of the resin is calculated from the acid value of the resin solution and the nonvolatile component concentration of the resin solution.

(amine number of basic resin type dispersant)

The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mgKOH/g) measured by the method of American Society for Testing Materials (ASTM) D2074 into a nonvolatile matter.

(ammonium salt value of resin having cationic group in side chain)

The ammonium salt value of the resin having a cationic group in the side chain is a value obtained by titrating a 5% potassium chromate aqueous solution as an indicator with a 0.1N silver nitrate aqueous solution and converting the result into an equivalent of potassium hydroxide, and represents the ammonium salt value of the nonvolatile component.

(Experimental example 1)

< method for producing fine pigment >

(micronized pigment (PB-1))

Copper phthalocyanine-based Blue Pigment c.i. Pigment Blue (Pigment Blue) 15: 6 (100 parts of "Lionol BLUE ES" manufactured by Toyo color Ltd.), 1000 parts of pulverized salt and 100 parts of diethylene glycol were charged in a stainless 1 gallon kneader (manufactured by Toyo Seisaku Co., Ltd.), and kneaded at 50 ℃ for 12 hours. The mixture was poured into 3000 parts of warm water, stirred by a high-speed mixer for about 1 hour while being heated to about 70 ℃ to prepare a slurry, and the slurry was repeatedly filtered and washed with water to remove common salt and the solvent, and then dried at 80 ℃ for 24 hours to obtain a micronized pigment (PB-1).

(micronized pigment (PB-2))

Except for mixing a copper phthalocyanine-based Blue Pigment of a micronized Pigment (PB-1), C.I. Pigment Blue (Pigment Blue) 15: the micronized pigment (PB-2) was obtained in the same manner as the micronized pigment (PB-1) except that the pigment BLUE (COSMOS BLUE) ASF manufactured by Toyobo beauty Co., Ltd., Zhuhai) was changed to a copper phthalocyanine-based BLUE pigment C.I. pigment BLUE 15.

(micronized pigment (PV-1))

200 parts of dioxazine VIOLET pigment C.I. pigment Violet 23 ("Lionogen Violet RL" manufactured by Toyo color Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless 1-gallon kneader (manufactured by Toyo Seisaku Co., Ltd.), and kneaded at 80 ℃ for 6 hours. Subsequently, the kneaded mixture was put into 8000 parts of warm water, stirred for 2 hours while being heated to 80 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 85 ℃ for a whole day and night to obtain a micronized pigment (PV-1).

(Fine pigment (PG-1))

In a reaction vessel, 1250 parts of n-pentanol were added 225 parts of phthalonitrile (phthalonitrile) and 78 parts of aluminum chloride anhydride, and the mixture was stirred. 266 parts of 1,8-Diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene, DBU) were added thereto, and the mixture was heated and refluxed at 136 ℃ for 5 hours. The reaction solution cooled to 30 ℃ was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring while maintaining stirring, thereby obtaining a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. Stirred at 40 ℃ for 3 hours and sulfuric acid solution was injected into 24000 parts of cold water at 3 ℃. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following structural formula (11).

Structural formula (11)

In a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the structural formula (11) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ℃ and reacted for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following structural formula (12). 100 parts of the aluminum phthalocyanine pigment represented by the structural formula (12) obtained, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Shanghai Co., Ltd.), and kneaded at 70 ℃ for 6 hours. The kneaded mixture was put into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 80 ℃ for a whole day and night to obtain a pulverized pigment (PG-1). The volume average primary particle diameter was 31.2 nm.

Structural formula (12)

(Fine pigment (PG-2))

In a reaction vessel, to 1000 parts of methanol were added 100 parts of an aluminum phthalocyanine pigment represented by the structural formula (11) and 43.2 parts of diphenylphosphinic acid, and the mixture was heated to 40 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following structural formula (13).

The aluminum phthalocyanine pigment represented by the structural formula (13) thus obtained is treated in the same manner as for the microfine pigment (PG-1), whereby the microfine pigment (PG-2) is obtained. The volume average primary particle diameter was 29.5 nm.

Structural formula (13)

(Fine pigment (PG-3))

An aluminum phthalocyanine pigment represented by the following structural formula (14) is obtained according to the synthesis method described in Japanese patent application laid-open No. 2010-79247. The aluminum phthalocyanine pigment represented by the structural formula (14) thus obtained is treated in the same manner as for the microfine pigment (PG-1), whereby a microfine pigment (PG-3) is obtained. The volume average primary particle diameter was 33.0 nm.

Structural formula (14)

(Fine pigment (PG-4))

Into a three-necked flask were charged 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following structural formula (15), and 104.4 parts of 1,3-dibromo-5,5-dimethylhydantoin (1,3-dibromo-5,5-dimethylhydantoin, DBDMH) and stirred to react at 20 ℃ for 4 hours. Then, 5000 parts of ice water at 3 ℃ was poured into the reaction mixture, and the precipitated solid was separated by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution was added to a beaker, and the residue was separated by filtration and stirred at 80 ℃ for 1 hour. Then, the mixture was separated by filtration, washed with water, and dried, thereby obtaining a pigment having an average substitution of 8.0 bromine atoms in the phthalocyanine ring.

Subsequently, 500 parts of N-methylpyrrolidone, 50 parts of the obtained pigment having phthalocyanine rings substituted with 8.0 bromine atoms on average, and 18.2 parts of diphenyl phosphate were charged into a three-necked flask, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a microfine pigment (PG-4) represented by the following structural formula (16). The volume average primary particle diameter of the obtained colorant was 27 nm.

Structural formula (15)

Structural formula (16)

(Fine pigment (PG-5))

Into a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having phthalocyanine rings substituted with 8.0 bromine atoms on average, which was produced in the production of a micronized pigment (PG-4), and 13.8 parts of diphenylphosphinic acid were charged, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a microfine pigment (PG-5) represented by the following structural formula (17). The volume average primary particle diameter of the obtained colorant was 31 nm.

Structural formula (17)

(Fine pigment (PG-6))

Into a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having phthalocyanine rings substituted with an average of 8.0 bromine atoms, which was prepared in the production of a micronized pigment (PG-4), and 21.5 parts of bis (4-nitrophenyl) phosphate were charged, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a fine pigment (PG-6) represented by the following structural formula (18). The volume average primary particle diameter of the obtained colorant was 32 nm.

Structural formula (18)

(Fine pigment (PG-7))

Into a three-necked flask were charged 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the structural formula (15), and 129.3 parts of 1,3-dibromo-5,5-dimethylhydantoin (1,3-dibromo-5,5-dimethylhydantoin, DBDMH) and stirred to react at 20 ℃ for 6 hours. Then, 5000 parts of ice water at 3 ℃ was poured into the reaction mixture, and the precipitated solid was separated by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution was added to a beaker, and the residue was separated by filtration and stirred at 80 ℃ for 1 hour. Then, the mixture was separated by filtration, washed with water, and dried, thereby obtaining a pigment having an average substitution of 10.1 bromine atoms in the phthalocyanine ring.

Subsequently, 500 parts of N-methylpyrrolidone, 50 parts of the obtained pigment having an average of 10.1 bromine atoms substituted in the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were charged into a three-necked flask, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a microfine pigment (PG-7) represented by the following structural formula (19). The volume average primary particle diameter of the obtained colorant was 27 nm.

Structural formula (19)

(Fine pigment (PG-8))

203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferrous bromide are heated and melted, and 50 parts of phthalocyanine pigment represented by the structural formula (15) is added at 140 ℃. The reaction mixture was heated to 160 ℃ and reacted at 160 ℃ for 7 hours while blowing 215.4 parts of bromine. The reaction mixture was poured into 2500 parts of ice water at 3 ℃, and the precipitated solid was separated by filtration and washed with water. The residue was washed with 1% aqueous hydrochloric acid, warm water, 1% aqueous sodium hydroxide, and warm water in this order, and then dried to obtain 98 parts of aluminum bromide phthalocyanine. The obtained crude aluminum phthalocyanine bromide was dissolved in 980 parts of concentrated sulfuric acid, and stirred at 50 ℃ for 3 hours. Then, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ℃, and the precipitated solid was separated by filtration, washed with water, and dried. Subsequently, 500 parts of a 2.5% aqueous sodium hydroxide solution was added to the beaker, and the separated residue was filtered and stirred at 80 ℃ for 1 hour. Then, the mixture was separated by filtration, washed with water, and dried, thereby obtaining a pigment having an average substitution of 15.0 bromine atoms in the phthalocyanine ring.

Subsequently, 500 parts of N-methylpyrrolidone, 50 parts of the obtained pigment having an average of 11.9 bromine atoms substituted in the phthalocyanine ring, and 10.8 parts of diphenyl phosphate were charged into a three-necked flask, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a fine pigment (PG-8) represented by the following structural formula (20). The volume average primary particle diameter of the obtained colorant was 31 nm.

Structural formula (20)

(Fine pigment (PG-9))

250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were put in a three-necked flask, and stirred at 150 ℃ for 30 minutes. 50 parts of an aluminum phthalocyanine pigment represented by the structural formula (11) was added thereto, and stirred at 155 ℃ for 30 minutes to dissolve it. Further, 58.5 parts of trichloroisocyanuric acid was added thereto, and the mixture was stirred at 190 ℃ for 5 hours. Then, 5000 parts of ice water at 3 ℃ was poured into the reaction mixture, and the precipitated solid was separated by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution was added to a beaker, and the residue was separated by filtration and stirred at 80 ℃ for 1 hour. Then, the mixture was separated by filtration, washed with water, and dried, thereby obtaining a pigment having an average substitution of 8.1 chlorine atoms in the phthalocyanine ring.

Subsequently, 500 parts of N-methylpyrrolidone, 50 parts of the obtained pigment having an average of 11.9 bromine atoms substituted in the phthalocyanine ring, and 22.6 parts of diphenyl phosphate were charged into a three-necked flask, and the mixture was heated to 90 ℃ to react for 8 hours. After cooling to room temperature, the resultant was filtered, washed with methanol, and dried to obtain a fine pigment (PG-9) represented by the following structural formula (21). The volume average primary particle diameter of the obtained colorant was 29 nm.

Structural formula (21)

(Fine pigment (PY-1 to PY-3))

The quinophthalone pigment fine pigments (PY-1 to PY-3) of the following structural formulae (22) to (24) were produced according to the examples of Japanese patent laid-open No. 2012-226110. The structure thereof is shown below.

(Fine pigment (PY-1)) (fine pigment (PY-2)) (fine pigment (PY-3))

(micronized pigment (PY-4))

100 parts of C.I. pigment Yellow 138(PY138) (Paliottolu (Paliotol Yellow) K0960-HD) manufactured by BASF corporation, 700 parts of sodium chloride and 180 parts of diethylene glycol were charged in a stainless 1-gallon kneader (manufactured by UK corporation) and kneaded at 80 ℃ for 6 hours. The above mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating to 80 ℃ to prepare a slurry, and the slurry was repeatedly filtered and washed with water to remove common salt and the solvent, and then dried at 80 ℃ for a whole day and night to obtain a micronized pigment (PY-4).

(micronized pigment (PY-5))

100 parts of isoindoline-based Yellow pigment C.I. pigment Yellow 139 ("Irgaphower Yellow (IRGAPHOR Yellow) 2R-CF" manufactured by BASF corporation, Japan), 1600 parts of sodium chloride and 190 parts of diethylene glycol were charged into a stainless 1 gallon kneader, and kneaded at 60 ℃ for 10 hours. Subsequently, the mixture was put into 3 parts of heated water, stirred by a high-speed mixer for about 1 hour while being heated to about 80 ℃ to prepare a slurry, and the slurry was repeatedly filtered and washed with water to remove sodium chloride and the solvent, and then dried at 80 ℃ for 1 day and night to obtain a milled pigment (PY-5).

(micronized pigment (PY-6))

Pigment Yellow (Pigment Yellow)185 ("paliott Yellow (Paliotol Yellow) D1155" manufactured by BASF corporation of japan) was prepared as a Yellow Pigment c.i.: 500 parts, sodium chloride: 500 parts and diethylene glycol: 250 parts were charged into a1 gallon kneader made of stainless steel and kneaded at 120 ℃ for 8 hours. Subsequently, the kneaded mixture was put into 5-DEG C heated water, stirred for 1 hour while being heated to 70 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 80 ℃ for a whole day and night to obtain a milled pigment (PY-6).

(micronized pigment (PY-7))

A metal complex-based Yellow Pigment (c.i. Pigment Yellow 150 parts, "Yellow Pigment (E4 GN") manufactured by Lansheng (LANXESS) corporation 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a stainless steel 1-gallon kneader (manufactured by uphole manufacturing corporation), and kneaded at 60 ℃ for 10 hours. Subsequently, the mixture was put into 3 parts of heated water, stirred by a high-speed mixer for about 1 hour while being heated to about 80 ℃ to prepare a slurry, and the slurry was repeatedly filtered and washed with water to remove sodium chloride and the solvent, and then dried at 80 ℃ for 1 day and night to obtain a milled pigment (PY-7).

< method for producing dye >

(resin having cationic group in side chain 1)

67.3 parts of methyl ethyl ketone was charged in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a cooler, and the temperature was raised to 75 ℃ under a nitrogen stream. Further, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized and charged into a dropping funnel, and the dropping funnel was mounted in a four-necked separable flask and dropped over 2 hours. After the completion of the dropwise addition for 2 hours, the polymerization yield was 98% or more and the weight-average molecular weight (Mw) was 6830, as confirmed from nonvolatile components, and the mixture was cooled to 50 ℃. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50 ℃ for 2 hours, and then heated to 80 ℃ for 1 hour, followed by reaction for 2 hours. Thus, resin 1 having a cationic group in a side chain having an ammonium group was obtained with a resin component of 47 mass%. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(dye (RD-1))

A dye (RD-1) as a salt-forming compound including c.i. acid red (acid red)52 and resin 1 having a cationic group in a side chain was produced in the following order.

2000 parts of water was added with 30 parts of resin 1 having a cationic group in a side chain, in terms of nonvolatile content, sufficiently stirred and mixed, and then heated to 60 ℃. On the other hand, an aqueous solution in which 10 parts of c.i. acid red 52 was dissolved in 90 parts of water was prepared, and this was added dropwise to the resin solution immediately before. After the dropwise addition, the mixture was stirred at 60 ℃ for 120 minutes to sufficiently react. As the end point of the reaction, the reaction solution was dropped on the filter paper, and it was judged that the salt-forming compound was obtained at the end point when the bleeding disappeared. After leaving to cool to room temperature with stirring, the mixture was suction-filtered and washed with water, and then the salt-forming compound remaining on the filter paper was dried by removing water with a dryer to obtain 32 parts of a dye (RD-1) which is a salt-forming compound of c.i. acid red 52 and resin 1 having a cationic group in a side chain. In this case, the content of the effective coloring matter component derived from c.i. acid red 52 in the dye (RD-1) was 25 mass%.

< pigment derivative >

The dye derivatives used in the photosensitive coloring composition of this example are shown in the following structural formulae (a1-1) to (a 1-3).

Pigment derivative (a1-1)

Pc represents a phthalocyanine skeleton.

Pigment derivative (a1-2)

Pigment derivative (a1-3)

(solution of resin type dispersant (a 2-1))

A reaction vessel equipped with a gas inlet, a thermometer, a condenser and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc, and the mixture was replaced with nitrogen gas. The reaction vessel was heated to 50 ℃ with stirring, and 12 parts of 3-mercapto-1, 2-propanediol was added. The reaction mixture was heated to 90 ℃ and reacted for 7 hours while adding a solution prepared by adding 0.1 part of 2,2' -azobisisobutyronitrile to 90 parts of PGMAc. The nonvolatile content measurement confirmed that 95% of the reaction had occurred. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1, 8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added thereto, and the mixture was reacted at 100 ℃ for 7 hours. It was confirmed by acid value measurement that 98% or more of acid anhydride was half-esterified, the reaction was terminated, and PGMAc was added thereto and diluted so that the nonvolatile matter became 30%, thereby obtaining a solution of the resin type dispersant (a2-1) having an acid value of 70mgKOH/g and a weight average molecular weight of 8500.

(solution of resin type dispersant (a 2-2))

A reaction apparatus equipped with a gas inlet, a condenser, a stirring blade and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ℃ for 1 hour while flowing nitrogen gas, thereby substituting nitrogen gas in the system. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ℃ under a nitrogen stream to start polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of nonvolatile content.

Subsequently, 61 parts of PGMAc and 20 parts of 1,2,2,6, 6-pentamethylpiperidine methacrylate (FANCRYL FA-711MM, manufactured by Hitachi chemical Co., Ltd.) as a second block (A block) monomer were charged into the reaction apparatus, and the reaction was continued by stirring while maintaining the temperature at 110 ℃ under a nitrogen atmosphere. After 2 hours from the charging of 1,2,2,6, 6-pentamethylpiperidine methacrylate, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion of the second block (A block) was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization. Then, PGMAc was added and diluted so that the nonvolatile content became 30%, thereby obtaining a solution of a resin type dispersant (a2-2) having a piperidine skeleton and an amine value of 57mgKOH/g per nonvolatile content and a number average molecular weight of 4,500 (Mn).

(solution of resin type dispersant (a 2-3))

[3- (a quaternary product of 3- (N, N-dimethylamino) propylacrylamide/methoxypolyethylene glycol methacrylate copolymer (23/77 mass%); quaternary degree of 27 mol%) ] was synthesized by the method for producing the pigment dispersant (1) described in production example 1 of Japanese patent application No. 5513691, and a solution of the resin dispersant (a2-3) was prepared by diluting with PGMAc so that the nonvolatile matter becomes 30%.

< method for producing alkali-soluble resin >

(preparation of alkali-soluble resin (B-1))

Into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device in a separable four-necked flask was charged 196 parts of cyclohexanone, the temperature was raised to 80 ℃ and the inside of the reaction vessel was replaced with nitrogen, and then, over 2 hours, a mixture of 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of p-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toyao synthesis Co., Ltd.) and 1.1 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution.

After cooling to room temperature, PGMAc was added so that the nonvolatile content became 20% by mass to prepare an alkali-soluble resin (B-1) solution. The weight-average molecular weight (Mw) was 26,000, and the acid value of the nonvolatile matter was 91 mgKOH/g.

(preparation of alkali-soluble resin (B-2) (alkali-soluble resin (III))

A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable four-necked flask was charged with 207 parts of cyclohexanone, heated to 80 ℃, and the inside of the reaction vessel was replaced with nitrogen, and then a mixture of 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of p-cumylphenol ethylene oxide-modified acrylate (arinix (Aronix) M110 manufactured by east asia synthesis corporation), 25 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (karez MOI manufactured by showa electric corporation), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ℃ over 3 hours after cooling to room temperature while injecting 1 hour of dry gas with stopping nitrogen gas with respect to the total amount of the obtained copolymer solution. After the completion of the dropwise addition, the reaction was further continued for 1 hour to obtain a resin solution. Cyclohexanone was added so that the nonvolatile content became 20% by mass, to prepare an alkali-soluble resin (B-2) solution. The weight-average molecular weight (Mw) was 18,000, and the acid value of the nonvolatile matter was 130 mgKOH/g.

(preparation of alkali-soluble resin (B-3) (alkali-soluble resin (I)))

100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirrer in a separable four-necked flask, and heated to 120 ℃ while injecting nitrogen into the vessel, and a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping tube at the above temperature over 2.5 hours to conduct polymerization. Subsequently, the flask was purged with air, and 17.0 parts of acrylic acid were charged with 0.3 part of tris-dimethylaminomethylphenol and 0.3 part of hydroquinone, and the reaction was continued at 120 ℃ for 5 hours, and terminated when the nonvolatile acid value was 0.8, to obtain a resin solution having a weight average molecular weight of about 12,000 (measured by GPC). Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added thereto, and the reaction was completed after 4 hours at 120 ℃. PGMAc was added so that the nonvolatile content became 20%, thereby preparing an alkali-soluble resin (B-3) solution. The acid value of the nonvolatile matter was 88 mgKOH/g.

(preparation of alkali-soluble resin (B-4) (alkali-soluble resin (II))

After introducing 182g of PGMAc into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube and changing the atmosphere in the flask from air to nitrogen gas, the temperature was raised to 100 ℃ and then a solution prepared by adding 3.6g of azobisisobutyronitrile to a mixture containing 70.5g (0.40 mol) of benzyl methacrylate, 43.0g (0.5 mol) of methacrylic acid, 22.0g (0.10 mol) of monomethacrylate with tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., Ltd.) and 136g of PGMAc was dropped into the flask from the dropping funnel over 2 hours, and further, stirring was continued at 100 ℃ for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 35.5g [0.25 mol% (50 mol% based on the carboxyl group of methacrylic acid used in the present reaction) ] of glycidyl methacrylate, 0.9g of tris-dimethylaminomethylphenol and 0.145g of hydroquinone were charged into the flask, and the reaction was continued at 110 ℃ for 6 hours, whereupon the reaction was completed. Cyclohexanone was added so that the nonvolatile content became 20% by mass, to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight was 13,000, the molecular weight distribution (Mw/Mn) was 2.1, and the acid value of the nonvolatile matter was 79 mgKOH/g.

(preparation of alkali-soluble resin (B-5) (alkali-soluble resin (I)))

100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirrer in a separable four-necked flask, and a mixture of 7.6 parts of styrene, 35.7 parts of glycidyl methacrylate, 42.4 parts of dicyclopentenyloxyethyl methacrylate, and 0.6 part of azobisisobutyronitrile was added dropwise from a dropping tube at the above temperature over 2.5 hours while heating to 120 ℃ while injecting nitrogen into the vessel, thereby carrying out polymerization.

Subsequently, the flask was purged with air, 17.2 parts of acrylic acid was charged with 0.3 part of tris-dimethylaminomethylphenol and 0.3 part of hydroquinone, and the reaction was continued at 120 ℃ for 5 hours, and was terminated when the nonvolatile acid value was 0.8, whereby a resin solution having a weight average molecular weight of about 20,000 (measured by GPC) was obtained. Further, 22.7 parts of succinic acid and 0.6 part of triethylamine were added thereto, and the reaction was completed after 4 hours at 120 ℃. PGMAc was added so that the nonvolatile content became 20%, to prepare an alkali-soluble resin (B-5) solution. The acid value of the nonvolatile component is 98 mgKOH/g.

(preparation of alkali-soluble resin (B-6) (alkali-soluble resin (I)))

100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirrer in a separable four-necked flask, and the vessel was heated to 120 ℃ while injecting nitrogen gas, and a mixture of 8.1 parts of styrene, 30.1 parts of glycidyl methacrylate, 41.0 parts of isobornyl acrylate, and 1.3 parts of azobisisobutyronitrile was added dropwise from the dropping tube at the above temperature over 2.5 hours to conduct polymerization.

Subsequently, the flask was purged with air, and 0.3 part of tris-dimethylaminomethylphenol and 0.3 part of hydroquinone were added to 14.4 parts of acrylic acid, and the reaction was continued at 120 ℃ for 5 hours, and terminated when the nonvolatile acid value was 0.8, to obtain a resin solution having a weight average molecular weight of about 9,000 (measured by GPC). Further, 22.1 parts of tetrahydrophthalic anhydride and 0.4 part of triethylamine were added thereto, and the reaction was completed after 4 hours at 120 ℃. PGMAc was added so that the nonvolatile content became 20%, to prepare an alkali-soluble resin (B-6) solution. The acid value of the nonvolatile matter was 68 mgKOH/g.

(preparation of alkali-soluble resin (B-7) (alkali-soluble resin (I)))

100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirrer in a separable four-necked flask, and a mixture of 3.0 parts of styrene, 46.1 parts of glycidyl methacrylate, 29.3 parts of 1-adamantyl methacrylate, and 0.9 part of azobisisobutyronitrile was added dropwise from a dropping tube at the above temperature over 2.5 hours while heating to 120 ℃ while injecting nitrogen into the vessel, thereby carrying out polymerization.

Subsequently, the flask was purged with air, and 0.4 part of tris-dimethylaminomethylphenol and 0.4 part of hydroquinone were added to 22.6 parts of acrylic acid, and the reaction was continued at 120 ℃ for 5 hours, and terminated when the nonvolatile acid value was 0.8, to obtain a resin solution having a weight average molecular weight of about 14,000 (measured by GPC). Further, 45.7 parts of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added thereto, and the reaction was completed after 4 hours at 120 ℃. PGMAc was added so that the nonvolatile content became 20%, to prepare an alkali-soluble resin (B-7) solution. The acid value of the nonvolatile matter was 112 mgKOH/g.

(preparation of alkali-soluble resin (B-8))

100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirrer in a separable four-necked flask, and a mixture of 4.6 parts of styrene, 31.9 parts of glycidyl methacrylate, 36.7 parts of dicyclopentanyl methacrylate, and 0.9 part of azobisisobutyronitrile was added dropwise from a dropping tube at the above temperature over 2.5 hours while heating to 120 ℃ while injecting nitrogen into the vessel, thereby carrying out polymerization.

Subsequently, the flask was purged with air, and 0.3 part of tris-dimethylaminomethylphenol and 0.3 part of hydroquinone were added to 15.2 parts of acrylic acid, and the reaction was continued at 120 ℃ for 5 hours, and terminated when the nonvolatile acid value was 0.8, to obtain a resin solution having a weight average molecular weight of about 12,000 (measured by GPC). Further, 45.7 parts of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added thereto, and the reaction was completed after 4 hours at 120 ℃. PGMAc was added so that the nonvolatile content became 20%, to prepare an alkali-soluble resin (B-7) solution. The acid value of the nonvolatile matter was 112 mgKOH/g.

(preparation of alkali-soluble resin (B-9) (alkali-soluble resin (II))

After introducing 182g of PGMAc into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube and setting the atmosphere in the flask from air to nitrogen gas, the temperature was raised to 100 ℃, and then 3.3g of azobisisobutyronitrile was added to a mixture containing 20.5g of benzyl methacrylate, 89.5g of methacrylic acid, 24.6g of dicyclopentenyloxyethyl methacrylate and 136g of PGMAc to form a solution, which was dropped from the dropping funnel into the flask over 2 hours, and further, stirring was continued at 100 ℃ for 5 hours. Then, the atmosphere in the flask was changed from nitrogen to air, and 70.0g of glycidyl methacrylate, 1.8g of tris-dimethylaminomethylphenol and 0.3g of hydroquinone were charged into the flask, and the reaction was continued at 110 ℃ for 6 hours, whereupon the reaction was completed. Cyclohexanone was added so that the nonvolatile content became 20% by mass, to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight was 14,000, the molecular weight distribution (Mw/Mn) was 2.1, and the nonvolatile matter acid value was 148 mgKOH/g.

(preparation of alkali-soluble resin (B-10))

After introducing 182g of PGMAc into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube and setting the atmosphere in the flask from air to nitrogen gas, the temperature was raised to 100 ℃, and then 3.6g of azobisisobutyronitrile was added to a mixture containing 71.8g of benzyl methacrylate, 43.8g of methacrylic acid, 22.4g of cyclohexyl methacrylate and 136g of PGMAc to form a solution, which was dropped from the dropping funnel into the flask over 2 hours, and further, stirring was continued at 100 ℃ for 5 hours. Then, the atmosphere in the flask was changed from nitrogen to air, and 36.1g of glycidyl methacrylate, 0.9g of tris-dimethylaminomethylphenol and 0.2g of hydroquinone were charged into the flask, and the reaction was continued at 110 ℃ for 6 hours, whereupon the reaction was completed. Cyclohexanone was added so that the nonvolatile content became 20% by mass, to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight was 13,000, the molecular weight distribution (Mw/Mn) was 2.1, and the acid value of the nonvolatile matter was 79 mgKOH/g.

< method for producing pigment Dispersion >

[ preparation of blue pigment Dispersion (M-B1) ]

After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed for 5 hours by a hey grinder (eigermill) (mini model M-250MKII manufactured by Eiger Japan corporation) using zirconia beads having a diameter of 1mm, and then filtered by a5 μ M filter to prepare a blue pigment dispersion (M-B1).

[ preparation of blue pigment Dispersion (M-B2) ]

A blue pigment dispersion (M-B2) was produced in the same manner as the blue pigment dispersion (M-B1) except that the micronized pigment (PB-1) was replaced with the micronized pigment (PB-2).

[ preparation of Green pigment Dispersion (M-G1) ]

After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed for 5 hours by a hege mill (Eiger mill) (mini model M-250MKII manufactured by Eiger Japan, Japan) using zirconia beads having a diameter of 1mm, and then filtered by a5 μ M filter to prepare a green pigment dispersion (M-G1).

7.68 parts of pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIISON (DIC) CORPORATION)

1.92 parts by weight of an equal amount of a mixture of fine pigment (PY-1), fine pigment (PY-2), fine pigment (PY-3) and fine pigment (PY-4)

3.20 parts of resin type dispersant (a2-1) solution

3.20 parts of an equivalent mixture of the solution of the resin type dispersant (a2-2) and the solution of the resin type dispersant (a2-3)

22.40 parts of alkali-soluble resin (B-1) solution

PGMAc 61.60 parts

[ preparation of Green pigment Dispersion (M-G2) ]

The mixture having the following composition was uniformly stirred and mixed, and then dispersed for 5 hours by a hey mill (eigermill) (mini model M-250MKII manufactured by Eiger Japan) using zirconia beads having a diameter of 1mm, followed by filtration through a5 μ M filter to prepare a green pigment dispersion (M-G2).

5.76 parts by weight of an equal-amount mixture of fine pigment (PG-4), fine pigment (PG-5), fine pigment (PG-6), fine pigment (PG-7), fine pigment (PG-8) and fine pigment (PG-9)

3.84 parts of an equal-amount mixture of the microfine pigment (PY-1), the microfine pigment (PY-2), the microfine pigment (PY-3) and the microfine pigment (PY-4)

3.20 parts of resin type dispersant (a2-1) solution

3.20 parts of an equivalent mixture of the solution of the resin type dispersant (a2-2) and the solution of the resin type dispersant (a2-3)

22.40 parts of alkali-soluble resin (B-1) solution

PGMAc 61.60 parts

[ preparation of Green pigment Dispersion (M-G3) ]

7.68 parts by weight of an equal amount of a mixture of fine pigment (PG-1), fine pigment (PG-2) and fine pigment (PG-3)

Pigment Green 58 ("FASTOGEN GREEN A110") 1.92 parts by weight, manufactured by Diegon (DIC) Inc

3.20 parts of resin type dispersant (a2-1) solution

3.20 parts of an equivalent mixture of the solution of the resin type dispersant (a2-2) and the solution of the resin type dispersant (a2-3)

22.40 parts of alkali-soluble resin (B-1) solution

PGMAc 61.60 parts

[ preparation of yellow pigment Dispersion (M-Y1) ]

9.60 parts of micronized pigment (PY-7)

0.96 part of pigment derivative (a1-2)

3.20 parts of resin type dispersant (a2-1) solution

22.40 parts of an equal amount of a mixture of the alkali-soluble resin (B-1) solution and the alkali-soluble resin (B-2) solution

PGMAc 63.84 parts

[ preparation of yellow pigment Dispersion (M-Y2) ]

A yellow pigment dispersion (M-Y2) was produced in the same manner as the yellow pigment dispersion (M-Y1) except that the microfine pigment (PY-7) was replaced with a mixture of the same amounts of the microfine pigment (PY-5) and the microfine pigment (PY-6).

[ preparation of Red pigment Dispersion (M-R1) ]

8.96 parts of C.I. pigment Red 254 ("Irgaphor Red) B-CF" manufactured by BASF corporation of Japan

Pigment Red 177 (Cromophtal Red A2B manufactured by BASF corporation) 2.24 parts

1.12 parts of pigment derivative (a1-3)

3.73 parts of a resin-type dispersant (a2-1) solution

12.80 parts by weight of an equal amount of a mixture of the alkali-soluble resin (B-1) solution and the alkali-soluble resin (B-2) solution

71.15 parts of PGMAc

[ preparation of Black pigment Dispersion (M-BK1) ]

After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed for 5 hours by a hey mill (Eiger mill) (mini model M-250MKII manufactured by Eiger Japan, Japan) using zirconia beads having a diameter of 1mm, and then filtered by a5 μ M filter to prepare a black pigment dispersion (M-BK 1).

11.20 parts of carbon black ("MA 77" manufactured by Mitsubishi chemical corporation)

1.12 parts of pigment derivative (a1-2)

3.73 parts of a resin-type dispersant (a2-1) solution

12.80 parts by weight of an equal amount of a mixture of the alkali-soluble resin (B-1) solution and the alkali-soluble resin (B-2) solution

71.15 parts of PGMAc

Other materials used in the photosensitive coloring composition of this example are shown below.

[ photopolymerization initiator (A) ]

(A1) The method comprises the following steps The compound of No.3

(A2) The method comprises the following steps The compound of No.5

(A3) The method comprises the following steps The compound of No.6

(A4) The method comprises the following steps The compound of No.8

(A5) The method comprises the following steps (A1) Equal amount of mixture of (A4)

[ photopolymerization initiator (Y) ]

(Y-1): an equal amount of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one [ ohm ni (Omnirad)907 (manufactured by IGM Resins Co.) ]and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ ohm ni (Omnirad)369 (manufactured by IGM Resins Co.) ])

(Y-2): 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide [ Onny (Omnirad) TPO (manufactured by IGM Resins Co.) ]

(Y-3): 2,2 '-bis (o-chlorophenyl) -4,5,4',5 '-tetraphenyl-1, 2' -biimidazole [ biimidazole (manufactured by Heijin chemical Co.) ]

(Y-4): 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime) [ brilliant good solid (IRGACURE) OXE01 (manufactured by BASF corporation, Japan) ] and an equal amount of ethane-1-one, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ],1- (O-acetyloxime) [ brilliant good solid (IRGACURE) OXE02 (manufactured by BASF corporation, Japan) ].

[ photopolymerizable Compound (C) ]

An equivalent mixture of C1, Aronix M310 from Toyo Synthesis, Aronix M520 from Toyo Synthesis, and Kayarad DPCA-30 from Nippon Chemicals.

(production of photopolymerizable monomer (C1))

A2L four-necked flask was charged with 801 parts of dipentaerythritol pentaacrylate, 128 parts of hexamethylene diisocyanate, 1.0 part of N, N-dimethylbenzylamine, and 1.0 part of 4-methoxyphenol, and the mixture was reacted at 70 ℃ for 8 hours to confirm disappearance of the isocyanate absorption by IR analysis. After cooling to room temperature, 70.3 parts of mercaptopropionic acid was charged and reacted at a temperature of 50 to 60 ℃ for 6 hours to obtain a photopolymerizable monomer (C1). The photopolymerizable monomer (C1) had an acid value of 43, a number of urethane groups of 1.53mmol/g and a number of double bonds of 6.88 mmol/g.

[ sensitizer (E) ]

An equivalent mixture of 2, 4-diethylthianthrone [ Kayacure DETX-S (manufactured by Nippon Chemicals) ] and 4,4' -bis (diethylamino) benzophenone [ Chromocene (CHEMARK) DEABP (manufactured by Chemark Chemical Co.) ].

[ polyfunctional mercaptan (F) ]

An equivalent mixture of trimethylolpropane tris (3-mercaptobutyrate) [ TPMB (manufactured by SHO AND ELECTRICAL CO., LTD) ] and pentaerythritol tetrakis (3-mercaptopropionate) [ PEMP (manufactured by Sakai chemical industry Co., Ltd) ].

[ solution of thermosetting Compound ]

30 parts by mass of a mixture of an adduct of 1, 2-epoxy-4- (2-oxetanyl) cyclohexane of 2,2' -bis (hydroxymethyl) -1-butanol [ EHPE-3150 (manufactured by Daicel) Co. ]) and a glycidyl etherified epoxy compound of sorbitol [ Danacol (DENACOL) EX611 (manufactured by Nagase ChemteX) Co. ], in an amount equivalent to 70 parts by mass of PGMAc, was dissolved.

[ antioxidant (H) ]

An equivalent mixture of IRGANOX 1010 manufactured by BASF corporation, Adekastab LA-52 manufactured by ADEKA corporation, Adekastab PEP-36 manufactured by ADEKA corporation, and Adekastab AO-412S manufactured by ADEKA corporation.

[ ultraviolet absorber (I) ]

Equal amounts of Bin (TINUVIN) P manufactured by BASF, Bin (TINUVIN)405 manufactured by BASF, and Kemisorb (KEMISORB)10 manufactured by Chemipropro Kasei.

[ polymerization inhibitor (J) ]

3-methyl catechol, methyl hydroquinone and tert-butyl hydroquinone.

[ silane coupling agent (K) ]

3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane.

[ leveling agent (L) ]

A mixed solution was prepared by dissolving 1 part of BYK-330 (BYK-Chemie) manufactured by BYK chemical company, 0.5 part of Meijia method (Megafac) F-551 (Megafac) manufactured by Diesen (DIC) company, and 0.5 part of Emulgen 103 (Emulgen) manufactured by Kao corporation in 98 parts of PGMAc.

[ organic solvent ]

The mass ratio of PGMAc, cyclohexanone, ethyl 3-ethoxypropionate, 1,3-butanediol diacetate and 3-methoxy-1-butanol is 3: 1: 1: 1: 1.

[ examples 1 to 32 and comparative examples 1 to 3] (preparation of photosensitive coloring compositions (R-B1 to R-B27, R-G1 to R-G4, R-R1 to R-R3, R-BK 1)

The materials were mixed and stirred in the formulation ratios shown in tables 1 to 5, and filtered through a1 μm filter to obtain photosensitive coloring compositions of respective colors.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

The obtained photosensitive colored composition was evaluated by the following method. The results are shown in tables 6 to 10. The evaluation scale means as follows.

4: extremely good;

3: the method is good;

2: the utility model is practical;

1: is not suitable for practical use

[ Pattern formation ]

The obtained photosensitive coloring composition was applied to a glass substrate (easy open (EAGLE)2000 manufactured by Corning corporation) having a thickness of 100mm in the longitudinal direction × 100mm in the transverse direction and 0.7mm by spin coating, and then heated in a clean oven at 70 ℃ for 15 minutes to remove the solvent, thereby obtaining a coating film having a thickness of about 2 μm. Then, the substrate was cooled to room temperature, and then, a high-pressure mercury lamp was used to irradiate at an illuminance of 20mW/cm through a photomask having a stripe pattern of 100 μm wide (pitch 200 μm) and 10 μm wide (pitch 20 μm)²、50mJ/cm²And (6) carrying out exposure. Then, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ℃, and then the resultant was subjected to spray developmentThe mixture was washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ℃ for 30 minutes. The spray development is performed in the shortest time for forming a pattern without any development residue on the film in each photosensitive coloring composition, and the appropriate development time is set as the time.

The film thickness of the coating was measured using a surrogate library (Dektak)3030 (manufactured by Nippon vacuum technology Co., Ltd.).

[ evaluation of straightness ]

4: the difference between the maximum value and the minimum value of the line width is less than 1 μm

3: the difference between the maximum value and the minimum value of the line width is 1 μm or more and less than 2 μm

2: the difference between the maximum value and the minimum value of the line width is more than 2 μm and less than 3 μm

1: the difference between the maximum value and the minimum value of the line width is more than 3 μm

[ evaluation of resolution ]

The pattern formed by the method was observed and evaluated using an optical microscope Model (Model) of Model LV100POL (ECLIPSE) manufactured by Nikon (Nikon). The evaluation criteria are as follows. The term "poor resolution" means that adjacent stripe patterns are connected or missing. The evaluation criteria are as follows.

4: without pattern-bound or missing parts

3: the connected or missing part of the patterns is less than 5 percent of the whole

2: the part connected or missing with the pattern is more than 5 percent and less than 20 percent of the whole

1: the connected or missing part of the pattern is more than 20% of the whole

[ evaluation of residual film ratio ]

In the patterning, the film was cleaned with spray development and ion-exchanged water, and the film thickness after air drying was measured. The film thickness was set as a post-development film thickness. Then, the film was heated at 230 ℃ for 30 minutes in a clean oven, and the film thickness at the same position as that before development was measured. The film thickness was taken as the post-baking film thickness. The residual film ratio was calculated from the two film thicknesses by the following equation. Evaluation was performed as follows.

The mathematical formula is as follows: residual film ratio (%). film thickness after baking ÷ film thickness after development × 100

4: the residual film rate is more than 90 percent

3: the residual film rate is more than 85 percent and less than 90 percent

2: the residual film rate is more than 80 percent and less than 85 percent

1: the residual film rate is less than 80 percent

[ watermark evaluation ]

The obtained photosensitive coloring composition was coated on a glass substrate (easy open circuit (EAGLE)2000) having a thickness of 100mm in the vertical direction × 100mm in the horizontal direction and 0.7mm, and prebaked at 95 ℃ for 2 minutes using a hot plate ("EC-1200N (trade name)") manufactured by ASONE corporation, to obtain a coating film having a thickness of 3.4 μm. Next, a mask having a stripe pattern of 100 μm width was placed at an illuminance of 20mW/cm using a high pressure mercury lamp²、40mJ/cm²Ultraviolet exposure was performed under the conditions of (1). Then, the resultant was developed by immersing the substrate in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ℃ for 40 seconds, and then washed with pure water, and the obtained pattern was observed with an optical microscope of Model 100POL LV of ECLIPSE (ECLIPSE) manufactured by Nikon (Nikon). The evaluation criteria are as follows.

4: and no watermark.

3: the watermark is less than 10% of the entire surface portion.

2: the watermark is more than 10% to less than 30% of the whole surface.

1: the watermark is more than 30% of the whole surface.

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

From the results in the table, the photosensitive coloring compositions of examples 1 to 32 were all evaluated at a level not lower than a practical level.

(Experimental example 2)

< colorant (D) >)

(micronized blue pigment (D-1))

As the micronized blue pigment (D-1), the micronized pigment (PB-1) of Experimental example 1 was used.

(micronized purple pigment (D-2))

As the micronized violet pigment (D-2), the micronized pigment (PV-1) of Experimental example 1 was used.

(dye (D-3))

As the dye (D-3), the dye (RD-1) of Experimental example 1 was used.

< production example of resin type dispersant >

(resin type dispersant solution)

As the resin type dispersant solution, the resin type dispersant (a2-1) of Experimental example 1 was used.

< example of production of alkali-soluble resin (B')

(alkali-soluble resin (B' -1) solution)

A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable four-necked flask was charged with 196 parts of cyclohexanone, the temperature was raised to 80 ℃, the interior of the reaction vessel was replaced with nitrogen, and then a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-cumylphenol ethylene oxide-modified acrylate ("Aronix (aroix) M110" manufactured by east asia corporation) and 1.1 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180 ℃ for 20 minutes, and the nonvolatile components were measured, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile components became 20%, thereby preparing an alkali-soluble resin (B' -1) solution. The weight average molecular weight (Mw) was 26,000.

(alkali-soluble resin (B' -2) solution)

A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable four-necked flask was charged with 207 parts of cyclohexanone, heated to 80 ℃, and the inside of the reaction vessel was replaced with nitrogen, and then a mixture of 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide-modified acrylate (Aronix (r) M110 manufactured by east asia synthesis corporation), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (karez MOI manufactured by showa electric corporation), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ℃ over 3 hours after stirring the obtained copolymer solution while stopping nitrogen and injecting dry air for 1 hour. After the completion of the dropwise addition, the reaction was further continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ℃ for 20 minutes, and the nonvolatile components were measured, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile components became 20%, thereby preparing an alkali-soluble resin (B' -2) solution. The weight average molecular weight (Mw) was 18,000.

(alkali-soluble resin (B' -3) solution)

370 parts of cyclohexanone was charged into a separable four-neck flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device, the flask was heated to 80 ℃ and then purged with nitrogen, and a mixture of 18 parts of cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toyata laboratories Inc.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After dropwise addition, the mixture was reacted at 100 ℃ for 3 hours, and then 1.0 part of azobisisobutyronitrile (azobisisobutyronitrile) dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100 ℃ for 1 hour. Subsequently, the inside of the vessel was replaced with air, and 9.3 parts (100% of glycidyl groups) of acrylic acid was charged with 0.5 part of tris-dimethylaminophenol and 0.1 part of hydroquinone in the vessel, and the reaction was continued at 120 ℃ for 6 hours, and was terminated when the acid value of nonvolatile matter became 0.5, to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were further added and reacted at 120 ℃ for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2g of the resin solution was sampled, heated and dried at 180 ℃ for 20 minutes, and the nonvolatile components were measured, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile components became 20% by mass, thereby preparing an alkali-soluble resin (B' -3) solution. The weight average molecular weight (Mw) was 19,000.

(alkali-soluble resin (B' -4) solution)

A separable flask equipped with a cooling tube was prepared as a reaction tank, while a monomer dropping tank was prepared by sufficiently stirring and mixing 40 parts of dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-propionate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("PERBUTYL (p) O" manufactured by japan fat and oil) and 40 parts of PGMAc, and a chain transfer agent dropping tank was prepared by sufficiently stirring and mixing 8 parts of n-dodecanethiol and 32 parts of PGMAc.

395 parts of PGMAc was charged into the reaction vessel, and after nitrogen substitution, the reaction vessel was heated to 90 ℃ in an oil bath with stirring. After the temperature of the reaction tank was stabilized at 90 ℃, dropwise addition was started from the monomer dropwise addition tank and the chain transfer agent dropwise addition tank. The dropwise addition was carried out over a period of 135 minutes while keeping the temperature at 90 ℃. After 60 minutes from the completion of the dropwise addition, the temperature was raised to 110 ℃. After maintaining 110 ℃ for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of 5/95 (volume ratio) oxygen/nitrogen was started. Then, 70 parts of glycidyl methacrylate, 0.4 part of 2,2' -methylenebis (4-methyl-6-tert-butylphenol) and 0.8 part of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 ℃ for 12 hours while maintaining the above conditions. Then, 150 parts of PGMAc was added and cooled to room temperature, about 2g of the resin solution was sampled, dried by heating at 180 ℃ for 20 minutes and the nonvolatile content was measured, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass, to thereby obtain an alkali-soluble resin (B' -4) solution. The weight-average molecular weight of the resin was 18,000, and the acid value per unit nonvolatile matter was 2 mgKOH/g.

< production of Dispersion >

(Dispersion 1)

The following raw materials were stirred and mixed to be uniform, and then dispersed for 3 hours using zirconia beads having a diameter of 0.5mm by a hege mill (Eiger mill) (mini model M-250MKII manufactured by Eiger Japan corporation), and then filtered by a filter having a pore size of 1.0 μ M to prepare a dispersion 1.

< method for producing photosensitive coloring composition >

[ example 1]

(photosensitive coloring composition 1)

The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.

[ examples 2 to 33, comparative examples 1 to 5] (photosensitive coloring composition 2 to photosensitive coloring composition 38)

Photosensitive color compositions 2 to 38 were prepared in the same manner as in example 1, except that the photosensitive color composition 1 of example 1 was changed to the raw materials and amounts shown in tables 11 to 14.

[ Table 11]

[ Table 12]

[ Table 13]

[ Table 14]

The respective raw materials are as follows.

[ alkali-soluble resin (B') solution ]

The alkali-soluble resin (B ' -2) to alkali-soluble resin (B ' -4) solutions were mixed in the same amounts, respectively, to prepare alkali-soluble resin (B ') solutions.

[ photopolymerizable Compound (C) ]

(polymerizable Compound (C-1) having a caprolactone-derived Structure)

C-1-1: kayalard (KAYARAD) DPCA-20 (manufactured by Nippon chemical Co., Ltd.)

C-1-2: kayalard (KAYARAD) DPCA-30 (manufactured by Nippon chemical Co., Ltd.)

C-1-3: kayalard (KAYARAD) DPCA-60 (manufactured by Nippon chemical Co., Ltd.)

(polymerizable Compound (C-2) having acid group)

C-2-1: aronix M-520 (manufactured by Toya Synthesis Co., Ltd.)

(other polymerizable Compound (C-3))

C-3-1: aronix M-402 (manufactured by Toya Synthesis Co., Ltd.)

[ photopolymerization initiator (A) ]

(photopolymerization initiator (A-1))

A-1-1: the compound of the formula (1)

A-1-2: the compound of the formula (2)

A-1-3: the compound of the formula (3)

A-1 to 4: the compound of the formula (4)

A-1 to 5: the compound of the formula (5)

A-1 to 6: the compound of the formula (6)

(photopolymerization initiator (A-2))

A-2-1: the compound of the formula (7)

A-2-2: the compound of the formula (8)

A-2-3: the compound of the formula (9)

A-2-4: the compound of the formula (10)

A-2-5: the compound of the formula (11)

(photopolymerization initiator (A-3))

A-3-1: "Onniad (Omnirad) 369" (acetophenone-based compound manufactured by IGM Resins (IGM Resins))

A-3-2: "Ohmanid (Omnirad) TPO" (manufactured by IGM Resins (IGM Resins) Inc., acylphosphine oxide-based Compound)

A-3-3: 2,2' -bis (o-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole (imidazole compound)

A-3-4: brilliant (IRGACURE) OXE01 (oxime-based compound available from BASF corporation)

A-3-5: brilliant (IRGACURE) OXE02 (oxime-based compound available from BASF corporation)

A-3-6: brilliant (IRGACURE) OXE04 (oxime-based compound available from BASF corporation)

[ sensitizer (E) ]

E-1-1: cayacure (KAYACURE) DETX-S (a thioxanthone-based compound, manufactured by Nippon Chemicals Co., Ltd.)

E-2-1: youmeng (CHEMARK) DEABP (manufactured by Youmeng (Chemark Chemical Co., Ltd., benzophenone series compound)

(antioxidant (H))

H-1: iollonus (IRGANOX)1010 (hindered phenol antioxidant, manufactured by BASF corporation, Japan)

H-2: adekastab 2112 (Adekastab, manufactured by Adekata corporation, phosphorus antioxidant)

As described above, antioxidant (L) was prepared by mixing antioxidant (H-1) and antioxidant (H-2) in the same amounts.

(leveling agent (L))

A solution prepared by dissolving 2 parts of BYK-330 manufactured by BYK-Chemie, Inc. in 98 parts of PGMAc.

(Adhesives)

1: silane coupling agent KBM-403 (manufactured by shin-Etsu chemical industries Co., Ltd.)

2: silane coupling agent KBE-503 (manufactured by shin-Etsu chemical industries Co., Ltd.)

In the above, the adhesion improver (1) and the adhesion improver (2) were mixed in the same amount to prepare an adhesion improver.

[ evaluation of photosensitive coloring composition ]

The obtained photosensitive colored composition was subjected to linearity evaluation, cross-sectional shape evaluation, and residual film ratio evaluation as watermark evaluation and pattern shape evaluation by the following methods. The evaluation results are shown in tables 11 to 14.

[ Pattern formation ]

The pattern was formed by the same conditions as in experimental example 1.

(evaluation of Pattern shape 1: evaluation of straightness)

The pattern formed by the above method was evaluated by measuring the maximum portion and the minimum portion of the line width of the fringe pattern at 10 spots using an optical microscope Model (Model) Model LV100POL (ECLIPSE) manufactured by Nikon (Nikon) and averaging the maximum portion and the minimum portion. It is considered that 3 or more is practical.

5: the difference between the maximum value and the minimum value of the line width is less than 0.5 μm

4: the difference between the maximum value and the minimum value of the line width is 0.5 μm or more and less than 1.5 μm

3: the difference between the maximum value and the minimum value of the line width is 1.5 μm or more and less than 2.5 μm

2: the difference between the maximum value and the minimum value of the line width is more than 2.5 μm and less than 3.5 μm

1: the difference between the maximum value and the minimum value of the line width is 3.5 μm or more

(evaluation of Pattern shape 2: evaluation of Cross-sectional shape)

For the pattern formed by the method, the pattern shape was confirmed by a scanning electron microscope ("S-3000H" manufactured by hitachi high and new technologies). Evaluation was carried out by taking an SEM image of a cross section of a stripe pattern 100 μm wide and measuring the taper angle between the substrate and the end of the pattern cross section. It is considered that 3 or more is practical.

5: the taper angle is more than 30 degrees and less than 50 degrees

4: the cone angle is more than 50 degrees and less than 60 degrees

3: the taper angle is less than 30 degrees or more than 60 degrees and less than 70 degrees

2: the taper angle is more than 70 degrees and less than 90 degrees

1: the cone angle is more than 90 degrees

(evaluation of residual film ratio)

The residual film ratio was calculated under the same conditions as in experimental example 1. It is considered that 3 or more is practical. The film thickness was measured using a surrogate library (Dektak)3030 (manufactured by Nippon vacuum technology Co.).

The mathematical formula is as follows: residual film ratio (%). film thickness after baking ÷ film thickness after development × 100

5: the residual film rate is more than 90 percent

4: the residual film rate is more than 85 percent and less than 90 percent

3: the residual film rate is more than 80 percent and less than 85 percent

2: the residual film rate is more than 75 percent and less than 80 percent

1: the residual film rate is less than 70 percent

(evaluation of watermark)

The surface of the pattern was observed under the same conditions as in experimental example 1, and the degree of the discolored portion was evaluated. It is considered that 3 or more is practical.

5: and no watermark.

4: the watermark is less than 10% of the whole.

3: the watermark is more than 10% and less than 20% of the whole watermark.

2: the watermark is more than 20% and less than 30% of the whole watermark.

1: the watermark is more than 30% of the whole watermark.

From the results in the table, the photosensitive colored compositions of examples 1 to 33 were all evaluated at a level not lower than a practical level.

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