CN115956223A

CN115956223A - Colored resin composition, color filter and image display device

Info

Publication number: CN115956223A
Application number: CN202180050424.7A
Authority: CN
Inventors: 东直人; 石井宏明
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2020-08-20
Filing date: 2021-07-20
Publication date: 2023-04-11
Also published as: TW202212490A; KR20230052275A; WO2022038948A1; JPWO2022038948A1

Abstract

A colored resin composition is provided which is less affected by the temperature change of prebaking on the solubility of a developing solution and patterning characteristics. The colored resin composition of the present invention is characterized by containing (a) a colorant comprising a phthalocyanine compound having a specific chemical structure, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer comprising a photopolymerizable monomer (E1) having a specific partial structure.

Description

Colored resin composition, color filter and image display device

Technical Field

The invention relates to a colored resin composition, a color filter and an image display device.

This application is based on the priority claims of Japanese patent application No. 2020-139037 filed in Japan on 8/20/2020 and Japanese patent application No. 2020-139038 filed in Japan on 8/20/2020, and the contents thereof are incorporated herein by reference.

Background

Conventionally, as a method for manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method have been known. Among them, the pigment dispersion method having well-balanced excellent characteristics is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, and the like.

In recent years, color filters are required to have higher brightness, higher contrast, and higher color gamut. As a coloring material for determining the color of a color filter, a pigment is generally used from the viewpoint of heat resistance, light resistance, and the like, but the market demand has been gradually unsatisfied particularly in terms of high brightness in terms of the pigment, and studies have been actively made to use a dye instead of the pigment as the coloring material.

For example, the use of phthalocyanine dyes for green pixels is being studied (for example, see patent document 1).

On the other hand, patent document 2 describes: by using a colored resin composition containing a specific photopolymerizable compound, it is possible to reduce the residue after development in the production of a color filter even when the pigment is contained at a high concentration.

Documents of the prior art

Patent document

Patent document 1 Japanese patent laid-open publication No. 2019-113732

Patent document 2 Japanese patent laid-open No. 2008-164886

Disclosure of Invention

Problems to be solved by the invention

The present inventors have conducted studies and found that the solubility of the colored resin composition described in patent document 1 in a developer greatly changes depending on the temperature at the time of prebaking (a drying step of a coating film performed before an exposure step), and particularly in a high-temperature region, the pattern size greatly changes. This indicates that there is a problem that a high-definition color filter represented by 4K8K, which requires a fine adjustment of the line width, cannot be stably manufactured.

Patent document 2 only evaluates a colored resin composition containing a pigment as a colorant, and it is not clear what properties are exhibited when a phthalocyanine-based dye is contained as a colorant.

Accordingly, an object of the present invention is to provide a colored resin composition having a small influence of the temperature change of prebaking on the solubility of a developer and patterning characteristics.

Means for solving the problems

The present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by using a specific photopolymerizable monomer in combination with a specific colorant, and have completed the present invention.

That is, the present invention has the following configurations [1] to [6 ].

[1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer,

the colorant (A) comprises a phthalocyanine compound having a chemical structure represented by the following general formula (1),

the photopolymerizable monomer (E) includes a photopolymerizable monomer (E1) having a partial structure represented by the following general formula (I).

(in the formula (1), A ¹ ～A ¹⁶ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Wherein A is ¹ ～A ¹⁶ Represents a fluorine atom, and A ¹ ～A ¹⁶ Wherein 1 or more of the above groups represent a group represented by the following general formula (2). )

( In the formula (2), X represents a linking group having a valence of 2. The benzene ring in the formula (2) may have an optional substituent. It represents a connecting bond. )

(in the formula (I), R ¹ Represents an alkylene group having 2 or more carbon atoms.

R ² Represents a hydrogen atom or a methyl group.

n represents an integer of 1 or more.

It represents a connecting bond. )

[2] The colored resin composition according to [1], wherein the photopolymerizable monomer (e 1) is a compound represented by the following general formula (II).

(in the formula (II), R ¹ 、R ² And n is as defined above for formula (I).

Z represents a direct bond, an oxygen atom, a sulfur atom, a 2-to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2-to 4-valent non-aromatic heterocyclic group, a 2-to 4-valent aromatic ring group, or a partial structure represented by the following general formula (III).

p represents an integer of 2 to 6.

In addition, a plurality of structures represented by the following general formula (II') contained in one molecule are optionally the same or different.

(in the formula (III), the symbol represents a bond.)

[3] The colored resin composition according to [1] or [2], wherein the content ratio of the colorant (A) is 10% by mass or more in the entire solid content.

[4] The colored resin composition according to any one of [1] to [3], wherein the content of the photopolymerizable monomer (e 1) is 1 mass% or more of the total solid content.

[5] A color filter having pixels produced using the colored resin composition according to any one of [1] to [4 ].

[6] An image display device has the color filter of [5 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a colored resin composition can be provided in which the influence of the temperature change of the prebaking on the solubility of the developer and the patterning property is small.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL display element having a color filter of the present invention.

Detailed Description

In the present invention, the "weight average molecular weight" refers to a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography).

In the present invention, "all solid components" refer to all components except the solvent in the colored resin composition. The components other than the solvent are not contained in the solvent but contained in all solid components even if the components are liquid at normal temperature.

In the present invention, unless otherwise specified, the "amine number" means an amine number in terms of an effective solid content, and is a value represented by the mass of KOH per 1g of the solid content of the dispersant.

In the present invention, "c.i." means the Color Index (Color Index).

[1] Constituent Components of colored resin composition

The colored resin composition of the present invention comprises (a) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer. Further, if necessary, other additives and the like other than the above components may be blended.

[1-1] (A) colorant

The colorant (a) contained in the colored resin composition of the present invention contains a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, may be referred to as "phthalocyanine compound (1)").

In the formula (1), A ¹ ～A ¹⁶ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Wherein, A ¹ ～A ¹⁶ Represents a fluorine atom, and A ¹ ～A ¹⁶ Wherein 1 or more of the above groups represent a group represented by the following general formula (2).

In the formula (2), X represents a 2-valent linking group. The benzene ring in the formula (2) may have an optional substituent. It represents a bond.

The colorant (a) in the colored resin composition of the present invention contains a phthalocyanine compound (1). In the phthalocyanine compound (1), 1 or more of the hydrogen atoms constituting the phthalocyanine skeleton are substituted with fluorine atoms having a small atomic radius, and the phthalocyanine compound (1) is a structure in which the association with each other is not easily inhibited, and therefore, an association is formed when the intermolecular distance is decreased by heating or the like, and it is considered that the decrease in luminance due to heating can be suppressed thereby. Further, it is considered that the particle diameter becomes smaller than that of the pigment after the association, and the brightness is increased in the pattern after the heat curing treatment.

It is considered that the phthalocyanine compound (1) is present densely as aggregates having small particle diameters in the coating film after the pre-baking of the colored resin composition of the present invention, and it is considered that the coating film is in a state in which the penetration and dissolution of the developer into the coating film are easily suppressed in the subsequent developing step. It is considered that the pattern shape thus obtained is likely to vary depending on the amount of the residual solvent, and, for example, the pre-baking temperature dependency of the pore diameter is likely to be deteriorated.

(A ¹ ～A ¹⁶ )

The above formula(1) In (A) ¹ ～A ¹⁶ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Wherein A is ¹ ～A ¹⁶ Represents a fluorine atom, and A ¹ ～A ¹⁶ Wherein 1 or more of the above groups represent a group represented by the following general formula (2).

In the formula (2), X represents a 2-valent linking group. The benzene ring in the formula (2) may have an optional substituent. It represents a connecting bond.

As A ¹ ～A ¹⁶ Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom and a bromine atom. From the viewpoint of increasing the brightness, a fluorine atom is preferred.

In addition, A ¹ ～A ¹⁶ Of these, preferably 6 or more, more preferably 7 or more, and still more preferably 8 or more are fluorine atoms, and further, 15 or less, preferably 12 or less, and more preferably 10 or less fluorine atoms are contained. When the lower limit value is not less than the above lower limit value, the stability of the phthalocyanine compound (1) tends to be improved, and when the upper limit value is not more than the above upper limit value, the affinity with a dispersant or a solvent in the colored resin composition tends to be improved. The above upper and lower limits may be arbitrarily combined. For example, A ¹ ～A ¹⁶ The number of the substituents representing a fluorine atom in (1) is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and further preferably 8 to 10.

(X)

X in the formula (2) represents a 2-valent linking group. The linking group having a valence of 2 is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom and-N (R) ^a1 ) -radical (R) ^a1 Represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ). From the viewpoint of stability during firing, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

(substituents optionally contained in benzene ring)

The benzene ring in the formula (2) may have an optional substituent. The substituent is not particularly limitedExamples thereof include a halogen atom and an alkyl group (-R) ^A Alkyl), alkoxy (-OR) ^A Group (wherein, R ^A Represents an alkyl group. ) - (COOR), alkoxycarbonyl (-COOR) ^A Group (wherein, R ^A Represents an alkyl group. ) (-), aryl (-R) ^B Aryl), aryloxy (-OR) ^B Group (wherein, R ^B Represents an aryl group. ) (-), aryloxycarbonyl (-COOR) ^B Group (wherein, R ^B Represents an aryl group. )). From the viewpoint of developing solubility and brightness, an alkoxycarbonyl group is preferable.

The alkyl group contained in these groups may be linear, branched or cyclic, and is preferably linear from the viewpoint of affinity for an organic solvent.

The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, further preferably 6 or less, further preferably 5 or less, and further preferably 4 or less. When the lower limit value is not less than the above-mentioned lower limit value, aggregation tends to be suppressed, and foreign matter tends to be suppressed, and when the upper limit value is not more than the above-mentioned upper limit value, affinity for a solvent tends to be improved, and stability with time tends to be improved. The above upper and lower limits may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 5, and further preferably 2 to 4.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and from the viewpoint of suppressing aggregation, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

The number of carbon atoms of the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, further preferably 12 or less, more preferably 10 or less, and further preferably 8 or less. When the amount is equal to or greater than the lower limit, aggregation tends to be suppressed by steric repulsion, and when the amount is equal to or less than the upper limit, the affinity for a solvent tends to be improved, and the stability with time tends to be improved. The upper limit and the lower limit may be arbitrarily combined, and for example, the carbon number of the aryl group is preferably 4 to 12, more preferably 4 to 10, and further preferably 6 to 8.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring having 1 free valence (free value).

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1, 3-oxazole ring, an isoxazole ring, a 1, 3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3, 5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-1-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinazoline ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a naphthodine ring, a 1, 8-naphthyridine ring, a purine ring, and a pteridine ring having 1 free valence.

When the benzene ring in the formula (2) has an arbitrary substituent, the number of substitutions is not particularly limited, and is preferably 1 with respect to1 benzene ring, from the viewpoint of improving heat resistance by pi-pi stacking of dye molecules and suppressing decrease in brightness due to decomposition of the dye.

When the benzene ring in the formula (2) has an arbitrary substituent, the substitution position may be ortho, meta or para, and para is preferred from the viewpoint of enabling the closest packing.

A ¹ ～A ¹⁶ Wherein 1 or more represents a fluorine atom, and A is preferably used from the viewpoint of forming an association between two molecules of the phthalocyanine compound (1) to improve the luminance ¹ ～A ⁴ At least 1 of which is fluorine atom, A ⁵ ～A ⁸ At least 1 of which is fluorine atom, A ⁹ ～A ¹² At least 1 of which is fluorine atom, and A ¹³ ～A ¹⁶ 1 or more of (A) are fluorine atoms; more preferably A ¹ ～A ⁴ At least 2 of which are fluorine atoms, A ⁵ ～A ⁸ At least 2 of which are fluorine atoms, A ⁹ ～A ¹² 2 or more of (A) are fluorine atoms, and A ¹³ ～A ¹⁶ 2 or more of them are fluorine atoms.

A ¹ ～A ¹⁶ Wherein 1 or more of the groups represented by the formula (2) are preferably A from the viewpoints of solubility in an organic solvent and brightness ¹ ～A ⁴ Wherein 1 or more are a group represented by the formula (2) A ⁵ ～A ⁸ Wherein 1 or more of the groups are represented by the formula (2), A ⁹ ～A ¹² Wherein 1 or more are a group represented by the formula (2) and A ¹³ ～A ¹⁶ 1 or more of (a) are groups represented by formula (2); more preferably A ¹ ～A ⁴ Wherein 2 or more are a group represented by the formula (2) A ⁵ ～A ⁸ Wherein 2 or more are a group represented by the formula (2) A ⁹ ～A ¹² Wherein 2 or more are a group represented by the formula (2) and A ¹³ ～A ¹⁶ Wherein 2 or more are groups represented by the formula (2).

From the viewpoint of suppressing the decrease in luminance by efficient accumulation, a is preferable ² 、A ³ 、A ⁶ 、A ⁷ 、A ¹⁰ 、A ¹¹ 、A ¹⁴ And A ¹⁵ Is a group of the formula (2) and A ¹ 、A ⁴ 、A ⁵ 、A ⁸ 、A ⁹ 、A ¹² 、A ¹³ And A ¹⁶ Is a halogen atom; particularly preferred is A ² 、A ³ 、A ⁶ 、A ⁷ 、A ¹⁰ 、A ¹¹ 、A ¹⁴ And A ¹⁵ Is a group of the formula (2) and A ¹ 、A ⁴ 、A ⁵ 、A ⁸ 、A ⁹ 、A ¹² 、A ¹³ And A ¹⁶ Is a fluorine atom.

Specific examples of the phthalocyanine compound (1) include the following compounds.

In the above formula, et represents an ethyl group.

The phthalocyanine compound (1) can be produced by a known method, for example, a method described in Japanese patent application laid-open No. H05-345861.

(A) The colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of the other coloring agents include pigments and dyes. For use in green pixel applications, it is preferable to use, for example, green pigments, green dyes, yellow pigments, yellow dyes.

Examples of the green pigment include c.i. pigment green 7, 36, 58, 59, 62, and 63, and c.i. pigment green 58 is preferable from the viewpoint of brightness.

As the green dye, among green dyes classified as dyes in the color index, c.i. solvent dyes include, for example, c.i. solvent green 1,3,4, 5, 7, 28, 29, 32, 33, 34, 35. Examples of the c.i. acid dye include c.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and c.i. medium green 1,3,4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. From the viewpoint of suppressing the decomposition of the dye during thermal firing, c.i. solvent green 1,3,4, 5, 7, 28, 29, 32, 33, 34, 35 is preferable.

Examples of the yellow pigment include c.i. pigment yellow 1, 1: 1.2, 3,4,5,6, 9,10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127: 1. 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191: 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and 1 of azobarbituric acid and nickel represented by the following formula (i): 1 complex or tautomer thereof (hereinafter, sometimes referred to as "nickel azo complex represented by formula (i)").

Examples of the other compounds in the nickel azo complex represented by the insertion formula (i) include compounds represented by the following formula (ii).

Among them, from the viewpoint of high brightness and high color gamut, the nickel azo complexes represented by c.i. pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and formula (i) are preferable, and the nickel azo complexes represented by c.i. pigment yellow 83, 138, 139, 180, 185 and formula (i) are more preferable.

Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include the specific compounds described in jp 2010-168531 a.

As the yellow dye, among yellow dyes classified as dyes in the color index, examples of the c.i. solvent dye include c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like. Examples of the c.i. acid dye include c.i. acid green 1,3,5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 238, 251, and derivatives thereof. Examples of the c.i. direct dye include c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141. Examples of the c.i. medium dye include c.i. medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65 dyes. C.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 243, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 238, and derivatives thereof can be preferably listed.

C.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 are preferable from the viewpoint of suppressing decomposition of the dye during thermal firing.

The average primary particle diameter of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. When the pigment is micronized, a solvent salt milling method is preferably used.

The content ratio of the colorant (a) in the colored resin composition of the present invention is not particularly limited, and is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, further preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less in the entire solid content of the colored resin composition. When the lower limit value is not less than the lower limit value, a wide range of hues tend to be reproduced, and when the upper limit value is not more than the upper limit value, stability with time tends to be ensured. The above upper and lower limits may be arbitrarily combined. For example, the content of the colorant (a) in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 60% by mass, even more preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass, of the total solid content of the colored resin composition.

The content of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, further preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less of the total solid content of the colored resin composition. When the lower limit value is set to be equal to or higher than the lower limit value, the luminance tends to be improved, and when the upper limit value is set to be equal to or lower than the upper limit value, the stability with time tends to be ensured. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the phthalocyanine compound (1) in the colored resin composition is preferably 3 to 50% by mass, more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, of the total solid content of the colored resin composition.

When the colored resin composition of the present invention contains another colorant, the content thereof is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 7% by mass or more, particularly preferably 10% by mass or more, further preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less of the total solid content of the colored resin composition. When the lower limit value is not less than the lower limit value, a wide range of hues tend to be reproduced, and when the upper limit value is not more than the upper limit value, stability with time tends to be ensured. The upper and lower limits mentioned above may be combined arbitrarily. For example, when the colored resin composition contains another colorant, the content thereof is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, even more preferably 5 to 25% by mass, even more preferably 7 to 25% by mass, and particularly preferably 10 to 29% by mass, of the total solid content of the colored resin composition.

[1-2] (B) solvent

(B) The solvent has a function of dissolving or dispersing the colorant, the alkali-soluble resin, the photopolymerization initiator, the photopolymerizable monomer, and other components in the colored resin composition and the pigment dispersion liquid of the present invention and adjusting the viscosity.

The solvent (B) is not particularly limited as long as it can dissolve or disperse the respective components.

Examples of such solvents include: glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;

alkyl acetates such as cyclohexyl acetate;

ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone;

1-or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;

alkoxy carboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents belonging to the above-mentioned group include mineral spirits, varsol #2, apco #18solvent, apco thin, locals solvent No.1 and No.2, solvesso #150, shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (both trade names). These solvents may be used alone in 1 kind, also can be used in 2 or more kinds combination.

When a pixel of a color filter is formed by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200 ℃ (pressure of 1013.25[ hPa ], hereinafter, the same applies to all boiling points). More preferably a solvent having a boiling point of 120 to 170 ℃.

Among the above solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like and high solubility of the constituent components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other solvents. Particularly preferred as the solvent used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of the constituent components in the composition. Since the polarity of the glycol monoalkylethers is high and the pigment tends to aggregate if the amount added is too large, and the storage stability tends to be lowered such that the viscosity of the resulting colored resin composition gradually increases thereafter, the proportion of the glycol monoalkylethers in the solvent (B) is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

Alternatively, a solvent having a boiling point of 150 ℃ or higher may be used in combination. By using a solvent having a boiling point of 150 ℃ or higher in combination, the colored resin composition is less likely to be dried, but the mutual relationship between the constituent components in the pigment dispersion liquid is less likely to be broken by rapid drying. When solvents having a boiling point of 150 ℃ or higher are used in combination, the content of the solvent having a boiling point of 150 ℃ or higher in the (B) solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. When the lower limit value is set to the above-mentioned lower limit value or more, for example, the deposition and solidification of coloring material components or the like at the tip of the slit nozzle tend to be easily avoided to cause foreign matter defects, and when the upper limit value is set to the above-mentioned upper limit value or less, problems such as a beat failure in a reduced pressure drying process and needle marks in prebaking due to a decrease in the drying speed of the composition tend to be easily avoided.

The solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, it is not necessary to additionally contain a solvent having a boiling point of 150 ℃ or higher.

Examples of the solvent having a boiling point of 150 ℃ or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin.

In the case of forming a pixel of a color filter by an ink jet method, a solvent having a boiling point of usually 130 ℃ or higher and 300 ℃ or lower, preferably 150 ℃ or higher and 280 ℃ or lower is suitable as the solvent. When the lower limit value is not less than the above-mentioned lower limit value, the uniformity of the obtained coating film tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the residual solvent at the time of firing tends to be easily reduced.

From the viewpoint of uniformity of the obtained coating film, a solvent having a vapor pressure of usually 10mmHg or less, preferably 5mmHg or less, more preferably 1mmHg or less can be used.

In the production of a color filter by the ink jet method, since the ink discharged from the nozzle is very fine, several pL to several tens pL, the solvent tends to evaporate before it falls around the nozzle opening or into the pixel array, and the ink tends to concentrate and dry. In order to avoid this, the solvent (B) preferably contains a solvent having a high boiling point, and more specifically, preferably contains a solvent having a boiling point of 180 ℃. More preferably, the solvent has a boiling point of 200 ℃ or higher, and particularly preferably, the solvent has a boiling point of 220 ℃ or higher. The content of the solvent having a boiling point of 180 ℃ or higher in the solvent (B) is preferably 50% by mass or higher, more preferably 70% by mass or higher, and most preferably 90% by mass or higher. When the amount is equal to or more than the lower limit, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

Examples of the solvent having a boiling point of 180 ℃ or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin.

The colored resin composition may contain a solvent having a boiling point of less than 180 ℃ for the purpose of adjusting the viscosity and the solubility of the solid component. As such a solvent, a solvent having a low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, and ketones are preferable, for example. Among them, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferable.

On the other hand, if the solvent contains an alcohol, the ejection stability may be deteriorated in the inkjet method. When alcohols are used in combination, the content of the alcohol in the solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The content of the solvent in the colored resin composition of the present invention is not particularly limited, and the upper limit thereof is usually 99 mass% or less, preferably 90 mass% or less, and more preferably 85 mass% or less. When the content is not more than the above upper limit, the coating film tends to be easily formed. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, in view of the viscosity suitable for coating and the like. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and still more preferably 80 to 85% by mass.

[1-3] (C) alkali-soluble resin

The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing the alkali-soluble resin (C), both of the film curability by photopolymerization and the solubility by a developer can be satisfied.

As the alkali-soluble resin (C), for example, publicly known polymer compounds described in Japanese patent application laid-open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118 and 2003-233179 can be used. Among them, the following resins (C-1) to (C-5) are preferred.

(C-1): a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer is a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of the copolymer or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter, sometimes referred to as "resin (C-1)")

(C-2) straight alkali-soluble resin having carboxyl group in the main chain (hereinafter, may be referred to as "resin (C-2)")

(C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)")

(C-4) (meth) acrylic resin (hereinafter, may be referred to as "resin (C-4)")

(C-5) epoxy (meth) acrylate resin having a carboxyl group (hereinafter, sometimes referred to as "resin (C-5)")

Among them, the resin (C-1) is particularly preferably used.

The resins (C-2) to (C-5) may have solubility to such an extent that the resins are dissolved in an alkaline developer to perform the target developing process, and the resins described in japanese patent application laid-open No. 2009-025813 can be preferably used as the resins.

(C-1) A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups formed by the addition reaction

One of preferred embodiments of the resin (C-1) includes "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of epoxy groups contained in a copolymer containing 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of hydroxyl groups generated by the addition reaction".

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. Among them, glycidyl (meth) acrylate is preferable. These epoxy group-containing (meth) acrylates may be used alone in 1 kind, or 2 or more kinds may be used in combination.

As another radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.

In the formula (V), R ⁹¹ ～R ⁹⁸ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R is ⁹⁶ And R ⁹⁸ Or R ⁹⁵ And R ⁹⁷ Optionally joined to each other to form a ring.

In the formula (V), R ⁹⁶ And R ⁹⁸ Or R ⁹⁵ And R ⁹⁷ The ring formed by the linkage is preferably an aliphatic ring, and may be either saturated or unsaturated, and the number of carbon atoms is preferably 5 to 6.

Among them, as the structure represented by formula (V), a structure represented by the following general formula (Va), (Vb) or (Vc) is preferable.

When the colored resin composition of the present invention is used for color filter formation, the heat resistance of the colored resin composition is improved and the strength of a pixel formed using the colored resin composition tends to be increased by introducing these structures into the alkali-soluble resin.

The mono (meth) acrylate having the structure represented by the formula (V) may be used alone in 1 kind, or 2 or more kinds may be used in combination.

As the mono (meth) acrylate having the structure represented by formula (V), various known mono (meth) acrylates can be used as long as the mono (meth) acrylate has the structure represented by formula (V), and a mono (meth) acrylate represented by the following general formula (VI) is particularly preferable.

In the formula (VI), R ⁸⁹ Represents a hydrogen atom or a methyl group, R ⁹⁰ The structure represented by formula (V).

When the repeating unit derived from the mono (meth) acrylate represented by the formula (VI) is contained in the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, the content of the repeating unit derived from the mono (meth) acrylate represented by the formula (VI) is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol% of the repeating units derived from the other radically polymerizable monomer.

The radical polymerizable monomer other than the mono (meth) acrylate represented by the formula (VI) is not particularly limited, and specific examples thereof include vinyl aromatic monomers such as styrene, α -, o-, m-, p-alkyl groups of styrene, nitro groups, cyano groups, amides, ester derivatives and the like; dienes such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthracenylnonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylphenol (meth) acrylate, (meth) acrylic acid esters such as 1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-N-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (meth) acrylamides such as (meth) acrylamide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-diisopropylamide, and (meth) acrylic acid anthracylamide; vinyl compounds such as (meth) acryloylaniline, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloylphthalimide.

Among these other radical polymerizable monomers, styrene, benzyl (meth) acrylate, and monomaleimide are preferable from the viewpoint of imparting excellent heat resistance and strength to the coloring resin composition.

When any repeating unit derived from styrene, benzyl (meth) acrylate, or monomaleimide is contained in the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, the total content of the repeating units derived from styrene, benzyl (meth) acrylate, and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%, based on the repeating units derived from the other radically polymerizable monomer.

In the copolymerization reaction of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer, a known solution polymerization method can be used. The solvent used is not particularly limited as long as it is a solvent inactive to radical polymerization, and a commonly used organic solvent can be used.

Examples of the solvent used in the solution polymerization method include: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate, and the like; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1, 4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha and the like; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide, N-methylpyrrolidone. These solvents may be used alone, or 2 or more of them may be used in combination.

The amount of the solvent used in the solution polymerization method is usually 30 to 1000 parts by mass, and preferably 50 to 800 parts by mass, based on 100 parts by mass of the copolymer to be obtained. When the amount of the solvent used is within the above range, the molecular weight of the copolymer tends to be easily controlled.

The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst can be used. Examples of the organic peroxide catalyst include known catalysts classified into ketone peroxides, peroxyketals, hydrogen peroxides, diallyl peroxides, diacylperoxides, peroxyesters, and peroxydicarbonates.

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Examples of the azo compound catalyst include: azobisisobutyronitrile, azodicarbonamide (azobiscarbonamide).

Among these, 1 or 2 or more radical polymerization initiators having a suitable half-life may be used depending on the polymerization temperature.

The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.

The copolymerization reaction may be carried out by dissolving the monomer and the radical polymerization initiator used in the copolymerization reaction in a solvent and heating the solution while stirring, or by dropping the monomer to which the radical polymerization initiator is added into the solvent which is heated and stirred, or by dropping the monomer while heating the solvent to which the radical polymerization initiator is added.

The reaction conditions may be set according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer is preferably composed of 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate and 10 to 95 mol% of repeating units derived from the other radically polymerizable monomer; more preferably, the resin composition is composed of 20 to 80 mol% of a repeating unit derived from an epoxy group-containing (meth) acrylate and 80 to 20 mol% of a repeating unit derived from another radically polymerizable monomer; particularly preferably, the epoxy group-containing (meth) acrylate resin composition is composed of 30 to 70 mol% of a repeating unit derived from an epoxy group-containing (meth) acrylate and 70 to 30 mol% of a repeating unit derived from another radically polymerizable monomer.

When the content ratio of the repeating unit of the epoxy group-containing (meth) acrylate is not less than the lower limit, the addition amount of the unsaturated monobasic acid or polybasic acid anhydride described later tends to be sufficient.

When the content of the repeating unit derived from another radically polymerizable monomer is not less than the lower limit, the heat resistance and strength tend to be sufficient.

Next, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) are reacted with an epoxy group of a copolymer of a (meth) acrylate containing an epoxy resin and another radical polymerizable monomer.

As the unsaturated monoacid added to the epoxy group, known unsaturated monoacids can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

Examples of the unsaturated monobasic acid added to the epoxy group include (meth) acrylic acid; crotonic acid; o-, m-, p-vinylbenzoic acid; monocarboxylic acids such as (meth) acrylic acid substituted at the α -position with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, or the like. Among them, (meth) acrylic acid is preferable. These unsaturated monobasic acids may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The resin (C-1) can be provided with polymerizability by adding an unsaturated monobasic acid to the epoxy group.

The unsaturated monoacid is added to usually 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol% of the epoxy group in the copolymer. When the content is not less than the lower limit, the colored resin composition tends to have good stability with time.

As a method for adding an unsaturated monobasic acid to an epoxy group of the copolymer, a known method can be used.

As the polybasic acid anhydride to be added to the hydroxyl group formed when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known polybasic acid anhydrides can be used.

Examples of the polybasic acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride and other anhydrides of acids of three or more valencies. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferable. These polybasic acid anhydrides may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The resin (C-1) can be rendered alkali-soluble by adding a polybasic acid anhydride to a hydroxyl group formed by addition of an unsaturated monobasic acid to an epoxy group of the copolymer.

The polybasic acid anhydride is added to the epoxy group of the copolymer in an amount of usually 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl group formed by addition of the unsaturated monobasic acid. When the upper limit value is less than the upper limit value, the residual film ratio during development tends to be good, and when the lower limit value is more than the lower limit value, the solubility tends to be sufficient.

As a method for adding a polybasic acid anhydride to a hydroxyl group formed by adding an unsaturated monobasic acid to an epoxy group of a copolymer, a known method can be used.

Further, in order to improve the photosensitivity, after the polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl groups.

In order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group.

In addition, both may be added.

Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group and an alkyl group.

Examples of commercially available products include those manufactured by Nagase ChemteX Corporation under the trade names "DENACOL EX-111", "DENACOL EX-121", "DENACOL EX-141", "DENACOL EX-145", "DENACOL EX-146", "DENACOL EX-171", and "DENACOL EX-192".

The structure of the resin (C-1) is described in, for example, japanese patent application laid-open Nos. 8-297366 and 2001-89533.

The weight average molecular weight of the resin (C-1) in terms of polystyrene measured by GPC is not particularly limited, and is preferably 3000 to 100000, and particularly preferably 5000 to 50000. When the lower limit value is not less than the above lower limit value, heat resistance and film strength tend to be good, and when the upper limit value is not more than the above upper limit value, solubility to a developer tends to be good.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight of the resin (C-1) is preferably 2.0 to 5.0 as a criterion of the molecular weight distribution.

Among the alkali-soluble resins (C), acrylic copolymer resins (C1) having an ethylenically unsaturated group in the side chain are preferable from the viewpoint of the curability of the coating film upon ultraviolet exposure.

(c1) The partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has, is not particularly limited, and preferably has a partial structure represented by the following general formula (CI), for example, from the viewpoint of compatibility between the coating film curability at the time of ultraviolet exposure and the alkali solubility at the time of alkali development.

In the formula (CI), R ¹ And R ² Each independently represents a hydrogen atom or a methyl group. It represents a connecting bond.

Among the partial structures represented by the formula (CI), a partial structure represented by the following general formula (CI') is preferable from the viewpoint of sensitivity and alkali developability.

In the formula (CI'), R ¹ And R ² Each independently represents a hydrogen atom or a methyl group. R ^X Represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.

These polybasic acids may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the formula (CI), (c 1) the content ratio of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, further preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, most preferably 70 mol% or less. When the lower limit value is not less than the above lower limit value, the coating film curability during ultraviolet ray exposure tends to be improved, and when the upper limit value is not more than the above upper limit value, the alkali solubility during alkali development tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, most preferably 65 to 70 mol%.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the formula (CI '), (c 1) the content of the partial structure represented by the formula (CI') contained in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, further preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. When the lower limit value is not less than the above lower limit value, the coating film curability during ultraviolet ray exposure tends to be improved, and when the upper limit value is not more than the above upper limit value, the alkali solubility during alkali development tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CI') contained in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, most preferably 65 to 70 mol%.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by formula (CI), the partial structure contained in addition is not particularly limited, and for example, from the viewpoint of alkali solubility at the time of alkali development, it preferably also has a partial structure represented by general formula (CII) below.

In the formula (CII), R ³ Represents a hydrogen atom or a methyl group, R ⁴ Represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent or an alkenyl group optionally having a substituent.

(R ⁴ )

In the formula (CII), R ⁴ Represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent or an alkenyl group optionally having a substituent.

As R ⁴ Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The carbon number thereof is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, and still more preferablyIs preferably 3 to 16, more preferably 5 to 14, and particularly preferably 8 to 12.

Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of developability, dicyclopentyl group and dodecyl group are preferred, and dicyclopentyl group is more preferred.

Examples of the substituent optionally contained in the alkyl group include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

As R ⁴ Examples of the aromatic ring group in (3) include a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group. The carbon number thereof is preferably 6 or more, more preferably 24 or less, still more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms of the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, further preferably 6 to 20, and particularly preferably 6 to 18.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, examples thereof include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

A ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

From the viewpoint of developability, a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable.

Examples of the substituent optionally contained in the aromatic ring group include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

As R ⁴ Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The carbon number thereof is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, a 3-penten-2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group. From the viewpoint of developability, a vinyl group and an allyl group are preferable, and a vinyl group is more preferable.

Examples of the substituent optionally contained in the alkenyl group include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

R ⁴ Represents an alkyl group optionally having a substituent, an alkyl group optionally having a substituentThe substituted aromatic ring group or optionally substituted alkenyl group is preferably an alkyl group or alkenyl group, and more preferably an alkyl group, from the viewpoint of developability and film strength.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the formula (CII), (c 1) the content ratio of the partial structure represented by the formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, and is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, further preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. When the lower limit is not less than the above-mentioned lower limit, the alkali solubility tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the storage stability of the colored resin composition tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

(c1) When the acrylic copolymer resin contains a partial structure represented by the formula (CI), it is preferable that the acrylic copolymer resin contains a partial structure represented by the following general formula (CIII) as a partial structure to be contained separately from the partial structure, from the viewpoint of suppressing a decrease in luminance by improving heat resistance.

In the formula (CIII), R ⁵ Represents a hydrogen atom or a methyl group, R ⁶ Represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group or an alkylsulfide group optionally having a substituent. t represents an integer of 0 to 5.

(R ⁶ )

In the formula (CIII), R ⁶ Represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group or an alkylsulfide group optionally having a substituent.

As R ⁶ Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The carbon number thereof is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 3 to 14, and particularly preferably 5 to 12.

Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of heat resistance, dicyclopentyl group and dodecyl group are preferred, and dicyclopentyl group is more preferred.

As R ⁶ Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The carbon number thereof is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The above upper and lower limits mayIn any combination. For example, the number of carbon atoms of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, a 3-penten-2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group. From the viewpoint of exposure sensitivity at the time of ultraviolet exposure, vinyl groups and allyl groups are preferable, and vinyl groups are more preferable.

As R ⁶ Examples of the alkynyl group in (3) include a linear, branched or cyclic alkynyl group. The carbon number thereof is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkynyl group include a 1-propyn-3-yl group, a 1-butyn-4-yl group, a 1-pentyn-5-yl group, a 2-methyl-3-butyn-2-yl group, a 1, 4-pentadiyn-3-yl group, a 1, 3-pentadiyn-5-yl group and a 1-hexyn-6-yl group.

Examples of the substituent optionally contained in the alkynyl group include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

As R ⁶ Examples of the halogen atom in (1) include a fluorine atom, a chlorine atom, a bromine atom,An iodine atom. From the viewpoint of storage stability of the acrylic copolymer resin, a fluorine atom is preferable.

As R ⁶ Examples of the alkoxy group in (1) include linear, branched or cyclic alkoxy groups. The carbon number thereof is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the alkoxy group has preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, yet more preferably 1 to 14, and particularly preferably 1 to 12 carbon atoms.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group.

Examples of the substituent optionally contained in the alkoxy group include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

As R ⁶ Examples of the alkyl sulfide group in (b) include linear, branched or cyclic alkyl sulfide groups. The carbon number thereof is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, yet more preferably 1 to 14, and particularly preferably 1 to 12.

Examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. From the viewpoint of developability, methyl sulfide group and ethyl sulfide group are preferable.

Examples of the substituent optionally contained in the alkyl group of the alkyl sulfide group include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group or an oligoethylene glycol group is preferable.

R ⁶ Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylsulfide group, and from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

In the formula (CIII), t represents an integer of 0 to 5. From the viewpoint of ease of production, t is preferably 0.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the formula (CIII), (c 1) the content ratio of the partial structure represented by the formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, particularly preferably 8 mol% or more, further preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. When the content is equal to or higher than the lower limit, the heat resistance tends to be improved and the luminance is suppressed from being lowered, and when the content is equal to or lower than the upper limit, the content ratio of the other partial structure tends to be increased and the alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, still more preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the formula (CI), it is also preferable that the acrylic copolymer resin further contains a partial structure represented by the following general formula (CIV) from the viewpoint of developability.

In the formula (CIV), R ⁷ Represents a hydrogen atom or a methyl group.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the formula (CIV), the content ratio of the partial structure represented by the formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, further preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. When the lower limit is not less than the above-mentioned lower limit, the alkali solubility tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the storage stability of the colored resin composition tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in a side chain (c 1) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%.

(C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 40mgKOH/g or more, further preferably 50mgKOH/g or more, particularly preferably 60mgKOH/g or more, further preferably 300mgKOH/g or less, further preferably 250mgKOH/g or less, further preferably 200mgKOH/g or less, and further preferably 150mgKOH/g or less. When the lower limit is not less than the above-mentioned lower limit, the alkali solubility tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the storage stability of the colored resin composition tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the acid value of the alkali-soluble resin (C) is preferably from 10 to 300mgKOH/g, more preferably from 30 to 300mgKOH/g, still more preferably from 40 to 250mgKOH/g, yet more preferably from 50 to 200mgKOH/g, and particularly preferably from 60 to 150mgKOH/g.

(C) The weight average molecular weight of the alkali-soluble resin is not particularly limited, and is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, further preferably 7000 or more, particularly preferably 8000 or more, and further usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less. When the lower limit value is not less than the above-mentioned lower limit value, heat resistance and coating film curability tend to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, alkali solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, still more preferably 4000 to 20000, yet more preferably 6000 to 20000, particularly preferably 7000 to 15000, and particularly preferably 8000 to 10000.

The content ratio of the alkali-soluble resin (C) in the colored resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, further preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less in the entire solid content of the colored resin composition. When the lower limit value is not less than the lower limit value, the coating film curability during ultraviolet ray exposure tends to be improved, and when the upper limit value is not more than the upper limit value, the developer solubility tends to be improved and the residue tends to be suppressed. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the alkali-soluble resin (C) in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass, of the total solid content of the colored resin composition.

[1-4] (D) photopolymerization initiator

The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing (D) a photopolymerization initiator, curability can be imparted to the film by photopolymerization.

(D) The photopolymerization initiator may be used in the form of a mixture (photopolymerization initiator system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the photopolymerization initiator include metallocene compounds containing titanocene compounds described in Japanese patent application laid-open Nos. 59-152396 and 61-151197, hexaarylbisimidazole derivatives, halomethyl s-triazine derivatives described in Japanese patent application laid-open No. 10-39503, N-aryl-alpha-amino acids such as N-phenylglycine, radical activators such as N-aryl-alpha-amino acid salts and N-aryl-alpha-amino acid esters, alpha-aminoalkylbenzophenone compounds, and oxime ester initiators described in Japanese patent application laid-open No. 2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are shown below.

Halomethylated triazine derivatives such as 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, and 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine;

halomethylated oxadiazole derivatives such as 2-trichloromethyl-5- (2 ' -benzofuranyl) -1,3, 4-oxadiazole, 2-trichloromethyl-5- [ beta- (2 ' -benzofuranyl) vinyl ] -1,3, 4-oxadiazole, 2-trichloromethyl-5- [ beta- (2 ' - (6 "-benzofuranyl) vinyl) ] -1,3, 4-oxadiazole, and 2-trichloromethyl-5-furanyl-1, 3, 4-oxadiazole;

imidazole derivatives such as 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer, and the like;

benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and the like;

anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone;

benzophenone derivatives such as benzophenone, michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone;

acetophenone derivatives such as 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α -hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and 1, 1-trichloromethyl- (p-butylphenyl) ketone;

thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone;

benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;

phenazine derivatives such as 9, 10-dimethylbenzphenazine;

anthrone derivatives such as benzanthrone;

titanocene derivatives such as bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 3,5, 6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 4, 6-trifluorophenyl) titanium, bis (cyclopentadienyl) -2, 6-difluorophenyl titanium, bis (cyclopentadienyl) -2, 4-difluorophenyl titanium, bis (methylcyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) -2, 6-difluoro-3- (pyrrol-1-yl) phenyltitanium and the like;

α -aminoalkylphenone-based compounds such as 2-methyl-1, [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropyl ketone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like;

oxime ester compounds such as 1, 2-octanedione-1- [4- (phenylsulfanyl) phenyl ] -2- (O-benzoyloxime) ethanone and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime).

From the viewpoint of sensitivity and surface properties, an oxime ester compound (oxime ester photopolymerization initiator) is preferred.

Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, it is possible to design a colored resin composition that has high sensitivity even in a small amount, is stable against thermal reaction, and has high sensitivity even in a small amount. Particularly, from the viewpoint of light absorption to i-rays (365 nm) of an exposure light source, an oxime ester compound having a carbazole ring optionally having a substituent is preferable.

Examples of the oxime ester compound include compounds represented by the following general formula (I-1).

In the formula (I-1), R ^21a Represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.

R ^21b Represents an optional substituent comprising an aromatic ring or a heteroaromatic ring.

R ^22a Represents an alkanoyl group optionally having a substituent or an aroyl group optionally having a substituent.

R ^21a The carbon number of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity to exposure. The above upper and lower limits may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group and a propyl group.

Examples of the substituent optionally contained in the alkyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, non-substitution is preferable.

As R ^21a The aromatic ring group in (1) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, and is preferably 5 or more from the viewpoint of solubility in the colored resin composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, still more preferably 12 or less, and particularly preferably 8 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.

Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group, and a fluorenyl group are preferable, and a phenyl group and a fluorenyl group are more preferable.

Examples of the substituent optionally contained in the aromatic ring group include a hydroxyl group, an alkyl group optionally contained in the aromatic ring group, an alkoxy group optionally contained in the aromatic ring group, a carboxyl group, a halogen atom, an amino group, an amide group and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Examples of the substituent of the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group.

From the viewpoint of developability, R is ^21a An alkyl group optionally having a substituent is preferable, an unsubstituted alkyl group is more preferable, and a methyl group is further preferable.

R ^21b Is an optional substituent comprising an aromatic or heteroaromatic ring. From the viewpoint of solubility in a solvent and sensitivity to exposure, preferred are carbazolyl groups optionally having a substituent, thioxanthone groups optionally having a substituent, diphenylsulfide groups optionally having a substituent, or fluorenyl groups optionally having a substituent, and groups in which these groups are bonded to a carbonyl group. From the viewpoint of light absorption with respect to i-rays (365 nm) of an exposure light source, preferred is a carbazolyl group optionally having a substituent or a group in which a carbazolyl group optionally having a substituent is bonded to a carbonyl group.

Examples of the substituent optionally having the carbazolyl group include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; F. halogen atoms such as Cl, br, I, etc.; an acyl group having 1 to 10 carbon atoms; alkyl ester group having 1 to 10 carbon atoms; alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; an aromatic ring group having 4 to 10 carbon atoms; an amino group; aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; an aroyl group optionally having a substituent; a heteroaroyl group optionally having a substituent; a thenoyl group optionally having a substituent.

R ^22a The number of carbon atoms of the alkanoyl group in (b) is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 10, further preferably 2 to 5, and particularly preferably 3 to 5.

Examples of the alkanoyl group include an Acetyl group (ethyl), a propionyl group, and a butyryl group.

Examples of the substituent optionally contained in the alkanoyl group include an aromatic cyclic group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group and an amide group, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

R ^22a The number of carbon atoms of the aroyl group in (b) is not particularly limited, but is usually 7 or more, preferably 8 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the aroyl group is preferably 7 to 20, more preferably 7 to 15, still more preferably 7 to 10, and particularly preferably 8 to 10.

Examples of the aroyl group include a benzoyl group and a naphthoyl group.

Examples of the substituent optionally contained in the aroyl group include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

The compound represented by the formula (I-1) includes compounds represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption with respect to I-ray (365 nm) of an exposure light source.

In the formulae (I-2) and (I-3), R ^21a And R ^22a The same as in the formula (I-1).

R ^23a Represents an alkyl group optionally having a substituent.

R ^24a Represents an alkyl group optionally having a substituent, an aroyl group optionally having a substituent, a heteroaroyl group optionally having a substituent, or a nitro group.

The benzene rings constituting the carbazole ring are optionally condensed with an aromatic ring to form a polycyclic aromatic ring.

R ^23a The carbon number of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 10 or less, from the viewpoint of solubility in a solventIs 5 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.

Examples of the substituent optionally contained in the alkyl group include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, non-substitution is preferable.

As R ^23a From the viewpoint of solubility in a solvent and ease of synthesis, ethyl is more preferable.

R ^24a The number of carbon atoms of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

R ^24a The number of carbon atoms of the aroyl group in (b) is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less, from the viewpoint of solubility in a solvent. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the aroyl group is preferably 7 to 20, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.

Examples of the aroyl group include a benzoyl group and a naphthoyl group.

Examples of the substituent optionally contained in the aroyl group include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, ethyl is preferred.

R ^24a The number of carbon atoms of the heteroaroyl group in (b) is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less, from the viewpoint of solubility in a solvent. The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms of the heteroaroyl group is preferably 7 to 20, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.

Examples of the heteroaroyl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group and a bromonaphthoyl group.

Examples of the substituent optionally contained in the heteroarylacyl group include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, non-substitution is preferable.

As R ^24a From the viewpoint of sensitivity, an aroyl group optionally having a substituent is preferable, and a benzoyl group is more preferable.

Examples of commercially available oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou super electronic materials, N-1919, NCI-930 and NCI-831 manufactured by ADEKA.

Specific examples of the oxime ester compound include the following compounds.

These photopolymerization initiators may be used alone in 1 kind, or 2 or more kinds may be used in combination.

In addition to the photopolymerization initiator (D), a chain transfer agent may be used. The chain transfer agent refers to a compound having a function of accepting a generated radical and transferring the accepted radical to other compounds.

The chain transfer agent may be any compound having the above-mentioned function, and various chain transfer agents can be used, and examples thereof include a mercapto group-containing compound and carbon tetrachloride, and a mercapto group-containing compound is more preferably used because the chain transfer effect tends to be high. The reason is considered to be that since the S-H bond energy is small, bond cleavage easily occurs, and hydrogen abstraction reaction and chain transfer reaction easily occur. It is effective for improving sensitivity and surface curability.

Examples of the mercapto group-containing compound include mercapto group-containing compounds having an aromatic ring, such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercaptonaphthalene, and 1, 4-dimethylmercaptobenzene; aliphatic mercapto group-containing compounds such as hexanedithiol, decanedithiol, butanediolbis (3-mercaptopropionate), butanedioldimethylacetate, ethanedioldis (3-mercaptopropionate), ethanedioldithioacetate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyltrimercaptopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediolbis (3-mercaptobutyrate), ethanedioldis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, and the like. From the viewpoint of surface smoothness, a compound having a plurality of mercapto groups is preferable.

The mercapto group-containing compound having an aromatic ring is preferably 2-mercaptobenzothiazole or 2-mercaptobenzimidazole, and the aliphatic mercapto group-containing compound is preferably trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, and trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate) are preferable.

These chain transfer agents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In the colored resin composition of the present invention, the content of the (D) photopolymerization initiator is not particularly limited, and is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, further preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less, of the total solid content of the colored resin composition. When the lower limit value is not less than the lower limit value, the curability of the coating film tends to be improved, and when the upper limit value is not more than the upper limit value, the luminance tends to be improved by reducing the visible light absorption. The above upper and lower limits may be arbitrarily combined. For example, the content of the photopolymerization initiator (D) in the colored resin composition is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, even more preferably 1.0 to 6% by mass, and particularly preferably 1.2 to 4% by mass, based on the total solid content of the colored resin composition.

When the colored resin composition of the present invention contains a chain transfer agent, the content thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, further preferably 3% by mass or less, more preferably 2.5% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, of the total solid content of the colored resin composition. When the amount is equal to or more than the lower limit, solvent resistance tends to be improved, and when the amount is equal to or less than the upper limit, storage stability tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, the content thereof is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, even more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1.5% by mass, based on the total solid content of the colored resin composition.

[1-5] (E) photopolymerizable monomer

The colored resin composition of the present invention contains (E) a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, and is preferably an addition polymerizable compound having at least one olefinic double bond (hereinafter referred to as "olefinic compound"). The olefinic compound is a compound having an olefinic double bond which is addition-polymerized and cured by the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with active light. The term "monomer" as used herein refers to a concept of a polymer substance and includes a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.

The photopolymerizable monomer (E) in the colored resin composition of the invention includes a photopolymerizable monomer (E1) having a partial structure represented by the following general formula (I) (hereinafter, sometimes referred to as "photopolymerizable monomer (E1)").

(in the formula (I), R ¹ Represents the number of carbonsAn alkylene group of 2 or more.

R ² Represents a hydrogen atom or a methyl group.

n represents an integer of 1 or more.

It represents a bond. )

It is considered that the photopolymerizable monomer (e 1) has an oxyalkylene chain, and thus can maintain favorable developer permeability even in a coating film state with a small amount of residual solvent such as 100 ℃, and thus can suppress a decrease in the pre-baking temperature dependence of the pore diameter even in a colored resin composition containing the phthalocyanine compound (1).

(R ¹ )

In the formula (I), R ¹ Represents an alkylene group having 2 or more carbon atoms. The alkylene group has no substituent.

The alkylene group may be linear, branched, cyclic, or a combination thereof. From the viewpoint of solvent solubility and solvent resistance, a linear alkylene group is preferable.

The number of carbon atoms of the alkylene group is not particularly limited as long as it is 2 or more, and is preferably 4 or less, more preferably 3 or less, and still more preferably 2. When the upper limit value is less than the above-mentioned upper limit value, the coating film sensitivity and solvent resistance tend to be improved. For example, the number of carbon atoms of the alkylene group is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.

Examples of the alkylene group include an ethylene group, an n-propylene group, an n-butylene group, and an isopropylene group. From the viewpoint of curability of the coating film, n-propylene and ethylene groups are preferred, and ethylene groups are more preferred.

(n)

In the formula (I), n represents an integer of 1 or more, preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. When the content is not more than the above upper limit, the curability of the coating film tends to be improved. For example, n is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

The photopolymerizable monomer (e 1) is preferably a compound represented by the following general formula (II) from the viewpoint of curability of the coating film.

(in the formula (II), R ¹ 、R ² And n is as defined for formula (I).

p represents an integer of 2 to 6.

The plural structures represented by the following general formula (II') contained in one molecule are optionally the same or different. )

(in the formula (III), R represents a bond.)

(Z)

In formula (II), X represents a direct bond, an oxygen atom, a sulfur atom, a 2-to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2-to 4-valent non-aromatic heterocyclic group, a 2-to 4-valent aromatic ring group, or a partial structure represented by formula (III).

The aliphatic hydrocarbon group having a valence of 2 to 4 may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms of the aliphatic hydrocarbon group having a valence of 2 to 4 is not particularly limited, but is preferably 10 or less, more preferably 9 or less, further preferably 8 or less, and usually 1 or more. When the amount is not more than the above upper limit, the curability of the coating film tends to be improved and the solvent resistance tends to be improved. For example, the aliphatic hydrocarbon group having a valence of 2 to 4 has preferably 1 to 10 carbon atoms, more preferably 1 to 9 carbon atoms, and still more preferably 1 to 8 carbon atoms.

Examples of the aliphatic hydrocarbon group having a valence of 2 to 4 include methane, ethane, propane and butane having a valence of 2 to 4.

The non-aromatic heterocyclic ring in the 2 to 4-valent non-aromatic heterocyclic group may be a monocyclic ring or a condensed ring. The non-aromatic heterocyclic ring is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. When the non-aromatic heterocyclic ring contains a plurality of hetero atoms, these may be the same or different.

The number of carbon atoms of the 2 to 4-valent non-aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and further preferably 8 or less, more preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, heat resistance tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, solvent solubility tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the non-aromatic heterocyclic group having a valence of 2 to 4 is preferably 3 to 8, more preferably 3 to 6, and further preferably 4 to 6.

Examples of the non-aromatic heterocyclic group having a valence of 2 to 4 include a piperidine ring and a pyrrolidine ring having 2 to 4 free valences.

Examples of the aromatic ring group having 2 to 4 valences include an aromatic ring group having 2 to 4 valences and an aromatic heterocyclic group having 2 to 4 valences.

The aromatic hydrocarbon ring in the 2 to 4-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. The number of carbons in the aromatic hydrocarbon ring group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and further preferably 15 or less, more preferably 12 or less, and further preferably 9 or less. When the lower limit value is not less than the lower limit value, heat resistance tends to be improved, and when the upper limit value is not more than the upper limit value, luminance tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the aromatic hydrocarbon ring group having a valence of 2 to 4 is preferably 3 to 15, more preferably 4 to 12, and further preferably 5 to 9.

As the aromatic hydrocarbon ring group having a valence of 2 to 4, examples thereof include benzene rings, naphthalene rings, anthracene rings, etc., having 2 to 4 free valences phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

The aromatic heterocyclic group in the 2 to 4-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms of the aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and further preferably 15 or less, more preferably 12 or less, and further preferably 9 or less. When the lower limit value is not less than the above-described lower limit value, heat resistance tends to be improved, and when the upper limit value is not more than the above-described upper limit value, luminance tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms of the aromatic heterocyclic group having a valence of 2 to 4 is preferably 3 to 15, more preferably 4 to 12, and further preferably 5 to 9.

Examples of the aromatic heterocyclic group having a valence of 2 to 4 include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring having a valence of 2 to 4.

From the viewpoint of curability and patterning characteristics, Z is preferably an oxygen atom, a sulfur atom, or a carbon atom having a valence of 4, and more preferably a carbon atom having a valence of 4.

(p)

In the formula (II), p represents an integer of 2 to 6. Preferably 3 or more, more preferably 5 or less, and still more preferably 4 or less. When the lower limit value is not less than the lower limit value, electrical reliability tends to be improved, and when the upper limit value is not more than the upper limit value, curability of the coating film tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, p is preferably 3 to 5, more preferably 3 to 4.

Examples of the photopolymerizable monomer (e 1) include the following monomers.

The photopolymerizable monomer (E) in the colored resin composition of the invention optionally contains a photopolymerizable monomer other than the photopolymerizable monomer (E1) (hereinafter sometimes referred to as "other photopolymerizable monomer (E2)"). As the other photopolymerizable monomer (e 2), it is particularly desirable to use a polyfunctional olefinic monomer having 2 or more olefinic double bonds in 1 molecule. The number of the ethylenic double bonds of the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and further preferably 8 or less, more preferably 7 or less. When the lower limit value is not less than the above-mentioned lower limit value, the sensitivity tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the solubility in a solvent tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of the ethylenic double bonds of the polyfunctional ethylenic monomer is preferably 2 to 8, more preferably 4 to 8, and still more preferably 5 to 7.

Examples of the other photopolymerizable monomer (e 2) include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, an ester obtained by an esterification reaction of an unsaturated carboxylic acid and a polycarboxylic acid with the above-mentioned aliphatic polyhydroxy compound, aromatic polyhydroxy compound and other polyhydroxy compounds, and an olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound.

Examples of the ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid include acrylic esters such as ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Examples of the acrylic acid ester include methacrylic acid esters obtained by replacing the acrylic acid moiety with a methacrylic acid moiety, itaconic acid esters obtained by replacing the acrylic acid moiety with an itaconic acid moiety, crotonic acid esters obtained by replacing the crotonic acid moiety, and maleic acid esters obtained by replacing the maleic acid moiety.

Examples of the ester of an aromatic polyol and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.

The esters obtained by esterification of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds need not be a single substance but may be mixtures. Examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; a condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol and glycerol.

Examples of the olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxyl compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; a reaction product of an aromatic diisocyanate such as tolylene diisocyanate or diphenylmethane diisocyanate and a (meth) acryloyl group-containing hydroxyl compound such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1, 1-triacryloxymethyl) propane or 3-hydroxy (1, 1-trimethylacryloyloxymethyl) propane.

In addition, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

The other photopolymerizable monomer (e 2) may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional monomer having an acid group obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound, and particularly preferably a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol in the ester.

These monomers may be used alone in 1 kind, but since it is difficult to use a single compound in production, 2 or more kinds may be used in combination. In addition, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used as the monomer in combination as needed.

The acid value of the polyfunctional monomer having an acid group is preferably from 0.1 to 40mgKOH/g, and particularly preferably from 5 to 30mgKOH/g. When the lower limit value is not less than the above-described lower limit value, the developing dissolution property tends to be good, and when the upper limit value is not more than the above-described upper limit value, the production and the operation tend to be good, and the photopolymerization performance and the curability such as the surface smoothness of the pixel tend to be good. Therefore, in the case of using a combination of 2 or more kinds of different polyfunctional monomers having different acid groups or in the case of using a combination of polyfunctional monomers having no acid group, it is preferable to adjust the acid groups as the whole polyfunctional monomers to be in the above range.

In the present invention, a more preferable polyfunctional monomer having an acid group is a mixture containing a dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate as the main component, which is manufactured by east asia synthesis corporation and sold as TO 1382. The polyfunctional monomer may also be used in combination with other polyfunctional monomers. Further, polyfunctional monomers described in paragraphs [0056] and [0057] of Japanese patent application laid-open No. 2013-140346 may also be used.

In the present invention, the polymerizable monomer described in jp 2013-195971 a is preferable from the viewpoint of improving the chemical resistance of the pixel and the linearity of the pixel edge.

From the viewpoint of achieving both the sensitivity of the coating film and the reduction of the development time, the polymerizable monomer described in jp 2013-195974 a is preferable.

The content ratio of the photopolymerizable monomer (E) in the colored resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more, and further preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less, of the total solid content of the colored resin composition. When the lower limit value is not less than the lower limit value, the coating film curability tends to be improved, and when the upper limit value is not more than the upper limit value, the storage stability tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the photopolymerizable monomer (E) in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass, of the total solid content of the colored resin composition.

The content of the photopolymerizable monomer (e 1) in the colored resin composition of the invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and further preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less of the total solid content of the colored resin composition. When the lower limit value is not less than the above lower limit value, the developer solubility tends to be improved, and the pattern shape tends to be good when the temperature of the hot plate is raised. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the photopolymerizable monomer (e 1) in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass of the total solid content of the colored resin composition.

In the colored resin composition of the present invention, the content of the photopolymerizable monomer (E1) to the photopolymerizable monomer (E) is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, particularly preferably 55% by mass or more, and further preferably 98% by mass or less, more preferably 96% by mass or less, further preferably 94% by mass or less, and particularly preferably 92% by mass or less. When the lower limit value is not less than the lower limit value, the developer solubility tends to be improved, and when the upper limit value is not more than the upper limit value, the patterning property tends to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the photopolymerizable monomer (E1) relative to the photopolymerizable monomer (E) is preferably 40 to 98% by mass, more preferably 45 to 96% by mass, still more preferably 50 to 94% by mass, and particularly preferably 55 to 92% by mass.

[1-6] other solid ingredients

The colored resin composition of the present invention may further contain a solid component other than the above components, if necessary. Examples of such components include a dispersant, a dispersing aid, a surfactant, and an adhesion improver.

[1-6-1] dispersing agent and dispersing aid

When the colored resin composition of the present invention contains a pigment as the colorant (a), it preferably contains a dispersant for stably dispersing the pigment. Among the dispersants, a polymer dispersant is preferable because it is excellent in dispersion stability with time.

Examples of the polymeric dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Examples of the polymer dispersant include those described in EFKA (registered trademark, manufactured by BASF), disperBYK (registered trademark, manufactured by byk chemical), disparlon (registered trademark, manufactured by nanko chemical industries), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by shin-Etsu chemical industries), polyflow (manufactured by Kyoho chemical Co., ltd.), and jp 2013-119568A.

The polymer dispersant is preferably a block copolymer having a functional group containing a nitrogen atom, and more preferably an acrylic block copolymer having a functional group containing a nitrogen atom, from the viewpoint of dispersibility and storage stability.

As the block copolymer having ase:Sub>A functional group containing ase:Sub>A nitrogen atom, an ase:Sub>A-B block copolymer or ase:Sub>A B-ase:Sub>A-B block copolymer, which is composed of an ase:Sub>A block having ase:Sub>A quaternary ammonium salt group and/or an amino group in ase:Sub>A side chain and ase:Sub>A B block having no quaternary ammonium salt group and no amino group, is preferable.

Examples of the functional group containing a nitrogen atom include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium salt group. From the viewpoint of dispersibility and storage stability, primary amino groups, secondary amino groups, and tertiary amino groups are preferred, and tertiary amino groups are more preferred.

The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, and a repeating unit represented by the following general formula (d 1) is preferable from the viewpoint of dispersibility and storage stability.

In the formula (d 1), R ¹ And R ² Each independently being a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R ¹ And R ² Optionally bonded to each other to form a ring structure. R ³ Is a hydrogen atom or a methyl group. X is a linking group having a valence of 2.

The number of carbon atoms of the alkyl group optionally having a substituent in the formula (d 1) is not particularly limited, and is usually 1 or more, preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. For example, it is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, more preferably methyl, ethyl, propyl, butyl. The alkyl group may be linear or branched. The alkyl group may have a cyclic structure such as cyclohexyl and cyclohexylmethyl.

The number of carbon atoms of the aryl group optionally having a substituent in the formula (d 1) is not particularly limited, and is usually 6 or more, preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. For example, it is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 8.

Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, and more preferably phenyl, methylphenyl, or ethylphenyl.

The number of carbons of the aralkyl group optionally having a substituent in the formula (d 1) is not particularly limited, and is usually 7 or more, preferably 16 or less, more preferably 12 or less, and further preferably 9 or less. For example, it is preferably 7 to 16, more preferably 7 to 12, and still more preferably 7 to 9.

Examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Preferred are phenylmethylene, phenylethylene, phenylpropylene and phenylbutylene, and more preferred are phenylmethylene and phenylethylene.

From the viewpoints of dispersibility, storage stability, electrical reliability and developability, R is ¹ And R ² Each independently is preferably an alkyl group optionally having a substituent, more preferably a methyl group or an ethyl group.

Examples of the substituent which the alkyl group, aralkyl group and aryl group in the formula (d 1) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group. From the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

In the formula (d 1), as R ¹ And R ² Examples of the cyclic structure formed by bonding to each other include a monocyclic ring of a 5 to 7-membered nitrogen-containing heterocycle or a condensed ring in which 2 of these rings are condensed. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and more preferably is a saturated ring. Specifically, for example, the cyclic structure of the following (IV) can be mentioned.

These cyclic structures optionally further have a substituent.

In the formula (d 1), examples of the linking group X having a valence of 2 include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ¹³ -radical, -COOR ¹⁴ -radical (wherein, R ¹³ And R ¹⁴ A single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms), preferably-COOR ¹⁴ -a radical.

The content ratio of the repeating unit represented by the formula (d 1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, particularly preferably 25 mol% or more, further preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. When the content is within the above range, dispersion stability and high luminance tend to be compatible. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the repeating unit represented by the formula (d 1) in the total repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, particularly preferably 20 to 50%, and particularly preferably 25 to 40 mol%.

From the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (d 2).

In the formula (d 2), R ¹⁰ Is ethylene or propylene, R ¹¹ Is an alkyl group optionally having a substituent, R ¹² Is a hydrogen atom or a methyl group. n is an integer of 1 to 20.

R of the formula (d 2) ¹¹ The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((b) is not particularly limited, and is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 11 to 4, particularly preferably 2 to 4.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, more preferably methyl, ethyl, propyl, butyl. The alkyl group may be linear or branched. The alkyl group may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.

Examples of the substituent optionally contained in the alkyl group include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

From the viewpoint of compatibility and dispersibility with a binder component such as a solvent, n in the formula (d 2) is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, n is preferably 1 to 10, more preferably 2 to 5.

The content ratio of the repeating unit represented by the formula (d 2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 4 mol% or more, and further preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be compatible with each other. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the repeating unit represented by the formula (d 2) in the total repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%.

From the viewpoint of improving compatibility with a binder component such as a solvent of the dispersant and improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (d 3).

In the formula (d 3), R ⁸ Is optionally substitutedAn alkyl group of the group, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. R ⁹ Is a hydrogen atom or a methyl group.

R of the formula (d 3) ⁸ The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. For example, it is preferably 1 to 10, more preferably 1 to 6.

R of the formula (d 3) ⁸ The number of carbons of the aryl group optionally having a substituent(s) in ((b) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. For example, it is preferably 6 to 16, and more preferably 6 to 12.

Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. The phenyl group, the methylphenyl group, the ethylphenyl group, the dimethylphenyl group, and the diethylphenyl group are preferred, and the phenyl group, the methylphenyl group, and the ethylphenyl group are more preferred.

R of the formula (d 3) ⁸ The number of carbons of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. For example, it is preferably 7 to 16, and more preferably 7 to 12.

Examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Preferable examples thereof include phenylmethylene, phenylethylene, phenylpropylene and phenylbutylene, and more preferable examples thereof include phenylmethylene and phenylethylene.

From the viewpoint of solvent compatibility and dispersion stability, R is ⁸ The alkyl group and the aralkyl group are preferable, and the methyl group, the ethyl group, and the phenylmethylene group are more preferable.

As R ⁸ The alkyl group in (1) optionally hasExamples of the substituent include a halogen atom and an alkoxy group.

Examples of the substituent optionally contained in the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, and an alkoxy group.

As R ⁸ The chain alkyl group includes both straight-chain and branched-chain alkyl groups.

The content ratio of the repeating unit represented by the formula (d 3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, further preferably 80 mol% or less, more preferably 70 mol% or less. When the content is within the above range, dispersion stability and high luminance tend to be compatible. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the repeating unit represented by the formula (d 3) in the total repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol%.

The block copolymer may have a repeating unit other than the repeating unit represented by the formula (d 1), the repeating unit represented by the formula (d 2), and the repeating unit represented by the formula (d 3). Examples of such repeating units include styrene-based monomers such as styrene and α -methylstyrene; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units of N-methacryloylmorpholine.

From the viewpoint of further improving the dispersibility, a block copolymer comprising an a block having a repeating unit represented by the formula (d 1) and a B block having no repeating unit represented by the formula (d 1) is preferable. The block copolymer is preferably an A-B block copolymer or ase:Sub>A B-A-B block copolymer. The B block more preferably has a repeating unit represented by the formula (d 2) and/or a repeating unit represented by the formula (d 3).

The repeating unit other than the repeating unit represented by the formula (d 1) may be contained in the a block. Examples of such a repeating unit include repeating units derived from the above-mentioned (meth) acrylic esters. The content of the repeating unit other than the repeating unit represented by the formula (d 1) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and still more preferably 0 mol%.

Repeating units other than the repeating unit represented by the formula (d 2) and the repeating unit represented by the formula (d 3) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and α -methylstyrene; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units of N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit represented by the formula (d 2) and the repeating unit represented by the formula (d 3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and further preferably 0 mol%.

From the viewpoint of dispersibility, the acid value of the block copolymer is preferably low, and particularly preferably 0mgKOH/g.

Here, the acid value represents the mg number of KOH required to neutralize 1g of the dispersant solid content.

From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 70mgKOH/g or more, yet more preferably 90mgKOH/g or more, particularly preferably 100mgKOH/g or more, particularly preferably 105mgKOH/g or more, further preferably 150mgKOH/g or less, and more preferably 130mgKOH/g or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably from 30 to 150mgKOH/g, more preferably from 50 to 150mgKOH/g, still more preferably from 70 to 150mgKOH/g, yet more preferably from 90 to 130mgKOH/g, particularly preferably from 100 to 130mgKOH/g, and particularly preferably from 105 to 130mgKOH/g.

Here, the amine number represents an amine number in terms of an effective solid content, and is a value represented by the mass of KOH corresponding to the amount of base per 1g of the solid content of the dispersant.

The weight average molecular weight of the block copolymer is preferably 1000 to 30000. When the amount is within the above range, dispersion stability is improved, and dry foreign matter is less likely to be generated when the coating is performed by the slit nozzle method.

The block copolymer can be produced by a known method. For example, the polymer can be produced by living polymerization of a monomer for introducing each repeating unit.

As the living polymerization method, known methods described below can be used: for example, japanese patent laid-open No. 9-62002; japanese patent laid-open publication No. 2002-31713; lutz, p masson et al, polym. Bull.12, 79 (1984); anderson, g.d. andrews et al, macromolecules,14, 1601 (1981); hatada, k.ute, et al, polym.j.17, 977 (1985), 18, 1037 (1986); right-handed Haoyi, or Hazu field-cultivated, polymer processing, 36, 366 (1987); tomayan Min Yan, zebenguan Men, high molecular discourse, 46, 189 (1989); m.kuroki, t.aida, j.am.chem.soc,109, 4737 (1987); zhangzhuosan, shangxiangping, organic synthetic chemistry, 43, 300 (1985); sogoh, W.R.Hertler et al, macromolecules,20, 1473 (1987).

When the colored resin composition of the present invention contains a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, further preferably 1% by mass or more, particularly preferably 2% by mass or more, further preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less, of the total solid content of the colored resin composition. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility and storage stability tend to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, electrical reliability and developability tend to be improved. The above upper and lower limits may be arbitrarily combined. For example, when the colored resin composition contains a dispersant, the content of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass, even more preferably 0.1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass, of the total solid content of the colored resin composition.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, further preferably 70 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the pigment. By setting the content within the above range, a colored resin composition having excellent dispersion stability and high brightness tends to be obtained. The upper and lower limits mentioned above may be combined arbitrarily. For example, when the colored resin composition contains a pigment and a dispersant, the content of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, still more preferably 10 to 50 parts by mass, yet more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, based on 100 parts by mass of the pigment.

When the colored resin composition of the present invention contains a pigment, a pigment derivative may be contained as a dispersion aid, for example, in order to improve the dispersibility of the pigment and to improve the dispersion stability.

Examples of the pigment derivative include derivatives of azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, quinophthalone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, anthraquinone pigments, indanthrone pigments, perylene pigments, pyreneone pigments, diketopyrrolopyrrole pigments, and dioxazine pigments. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, and the like, and preferable examples thereof include a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, and more preferable examples thereof are a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions may be used. Examples of the pigment derivative include a sulfonic acid derivative of an azo pigment, a sulfonic acid derivative of a phthalocyanine pigment, a sulfonic acid derivative of a quinophthalone pigment, a sulfonic acid derivative of an isoindoline pigment, a sulfonic acid derivative of an anthraquinone pigment, a sulfonic acid derivative of a quinacridone pigment, a sulfonic acid derivative of a diketopyrrolopyrrole pigment, and a sulfonic acid derivative of a dioxazine pigment.

[1-6-2] surfactant

As the surfactant, various surfactants such as anionic, cationic, nonionic, amphoteric surfactants and the like can be used, and nonionic surfactants are preferable in that the possibility of adversely affecting various properties is low. When the colored resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited, and is usually used in a range of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and further usually 10% by mass or less, preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, of the total solid content of the colored resin composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, even more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass, of the total solid content of the colored resin composition.

[1-6-3] adhesion improver

The colored resin composition of the present invention may contain an adhesion improver for improving adhesion to a substrate. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent. Silane coupling agents are preferred.

Examples of the silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by shin-Etsu Silicone Co., ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., ltd.). The silane coupling agent may be used alone in 1 kind, or 2 or more kinds may be used in combination in an arbitrary combination and ratio.

The photosensitive resin composition of the present invention may contain an adhesion improving agent other than the silane coupling agent. Examples thereof include phosphoric acid-based adhesion improvers and other adhesion improvers.

The phosphoric acid-based adhesion improver is preferably a phosphoric ester containing a (meth) acryloyloxy group. The phosphoric acid-based adhesion improver represented by the following general formulae (g 1), (g 2) and (g 3) is preferred.

In the formulae (g 1), (g 2) and (g 3), R ⁵¹ Each independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer of 1 to 10, and m each independently represents 1,2 or 3.

Examples of the other adhesion improver include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid-based adhesion promoters and other adhesion agents may be used alone in 1 kind, or 2 or more kinds may be used in combination.

When the colored resin composition of the present invention contains an adhesion improver, the content thereof is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, further preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, and particularly preferably 1% by mass or less of the total solid content. When the lower limit value is not less than the lower limit value, the patterning property tends to be improved and the pattern adhesion under high humidity tends to be improved, and when the upper limit value is not more than the upper limit value, the generation of residue tends to be suppressed. The above upper and lower limits may be arbitrarily combined. For example, when the colored resin composition contains an adhesion improver, the content thereof is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, still more preferably 0.3 to 1.5% by mass, and particularly preferably 0.4 to 1% by mass, of the total solid content.

[2] Preparation of colored resin composition

Next, a method for producing the colored resin composition (hereinafter, may be referred to as a resist) of the present invention will be described.

In the preparation of a colored resin composition containing a pigment as a colorant, first, predetermined amounts of the pigment, a solvent and a dispersant are weighed, and the colorant containing the pigment is dispersed in a dispersion treatment step to prepare a pigment dispersion liquid. In the dispersion treatment step, a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing the dispersion treatment to make the colorant fine, the coating properties of the colored resin composition are improved, and the transmittance of the pixels on the finished color filter substrate is improved.

When the pigment is subjected to dispersion treatment, it is preferable to use a dispersion aid, a dispersion resin, or the like in combination as appropriate, as described above.

When the dispersion treatment is carried out using a sand mill, glass beads or zirconia beads having a diameter of 0.1 to several mm are preferably used. The temperature at the time of dispersion treatment is usually 0 ℃ or higher, preferably room temperature or higher, and usually 100 ℃ or lower, preferably 80 ℃ or lower. The appropriate time varies depending on the composition of the pigment dispersion, the size of the sand mill, and the like, and therefore the dispersion time may be appropriately adjusted.

The pigment dispersion obtained by the dispersion treatment is mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, other components than those described above to prepare a uniform dispersion solution. In the dispersion treatment step and the mixing step, fine dust may be mixed, and therefore, it is preferable to perform a filtration treatment of the obtained pigment dispersion liquid with a filter or the like.

When the colorant does not contain a pigment, it can be obtained in the form of a uniform solution by mixing a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and components other than those described above, if necessary. The obtained solution is preferably subjected to filtration treatment using a filter or the like.

[3] Manufacture of color filter substrate

The color filter of the present invention has pixels produced using the colored resin composition of the present invention.

[3-1] transparent substrate (support)

The material of the transparent substrate for the color filter is not particularly limited as long as it is transparent and has suitable strength. Examples of the material include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among them, glass or a heat-resistant resin is preferable from the viewpoint of heat resistance.

In order to improve surface properties such as adhesiveness, the transparent substrate and the black matrix-forming substrate may be subjected to corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent and a urethane resin, and the like, as necessary. The thickness of the transparent substrate is usually 0.05mm or more, preferably 0.1mm or more, and usually 10mm or less, preferably 7mm or less. In addition, when a thin film forming process of various resins is performed, the film thickness is in the range of usually 0.01 μm or more, preferably 0.05 μm or more, further usually 10 μm or less, preferably 5 μm or less. For example, 0.01 to 10 μm and 0.05 to 5 μm.

[3-2] Black matrix

The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming pixel images of red, green, and blue colors in general. The colored resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist patterns) among red, green and blue pixels. A pixel image is formed by performing various processes such as coating, heat drying, image exposure, development, and heat curing on a resin black matrix formation surface formed on a transparent substrate or a metal black matrix formation surface formed using a light-shielding metal material such as a chromium compound using a coating liquid for forming green or blue pixels (resist pattern).

A black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, nickel, a tungsten alloy, or the like can be used, and these can be laminated in a multilayer form.

These metal light-shielding films are generally formed by a sputtering method, and after a desired pattern is formed in a film shape using a positive photoresist, chromium is etched using an etching solution of a mixture of ammonium ceric nitrate and perchloric acid and/or nitric acid, and the other materials are etched using an etching solution corresponding to the material, and finally the positive photoresist is peeled off with a special-purpose peeling agent, whereby a black matrix can be formed.

In this case, a thin film of these metals or metal/metal oxides is first formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, after a coating film of the colored resin composition is formed on the film, the coating film is exposed and developed using a photomask having a repeating pattern such as a stripe, mosaic, or triangle, to form a resist image. Then, the coating film may be subjected to etching treatment to form a black matrix.

In the case of using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, a Black matrix can be formed by using a colored resin composition containing one or more Black colored materials such as carbon Black, graphite, iron Black, aniline Black, cyanine Black (Cyanine Black), and titanium Black, or a Black colored material obtained by mixing red, green, and blue colors selected as appropriate from inorganic or organic pigments and dyes, in the same manner as the method for forming red, green, and blue pixel images described later.

[3-3] formation of pixels

A transparent substrate provided with a black matrix is coated with a colored resin composition of one of red, green and blue colors, dried, and then a photomask is placed on the coating film, and image exposure, development, and thermal curing or photo curing are performed as necessary through the photomask, thereby forming a pixel image. This operation is performed for the colored resin compositions of the three colors of red, green, and blue, respectively, whereby a color filter image can be formed.

The color resin composition for color filters can be applied by spin coating, wire bar coating, flow coating, die coating, roll coating, spray coating, or the like. Among these, the use of the die coating method is preferable from the overall viewpoint of being able to greatly reduce the amount of the coating liquid used, being able to prevent the occurrence of mist and the like adhering to the coating film by the spin coating method, and being able to suppress the generation of foreign matter.

When the thickness of the coating film is too large, pattern development becomes difficult, and it is sometimes difficult to adjust the gap in the liquid crystal cell process, while when it is too small, it is difficult to increase the pigment concentration, and it may not be possible to develop a desired color. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less in terms of the film thickness after drying. For example, 0.2 to 20 μm, 0.5 to 10 μm, and 0.8 to 5 μm.

[3-4] drying of coating film

The drying (prebaking) of the coating film after coating the colored resin composition on the substrate is preferably based on a drying method using a hot plate, an IR oven, a convection oven. Usually, after the preliminary drying, the coating film is dried by heating again. The conditions for the preliminary drying may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected depending on the kind of solvent component, the performance of the dryer used, and the like, and specifically, the drying temperature is usually 40 ℃ or more, preferably 50 ℃ or more, and usually 80 ℃ or less, and preferably 70 ℃ or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, and preferably 3 minutes or less.

The temperature condition for the reheating drying is preferably a temperature higher than the preliminary drying temperature, and specifically, is usually 50 ℃ or higher, preferably 70 ℃ or higher, and further usually 200 ℃ or lower, preferably 160 ℃ or lower, and particularly preferably 130 ℃ or lower. The drying time depends on the heating temperature, but is usually 10 seconds or more, particularly preferably 15 seconds or more, and further usually 10 minutes or less, particularly preferably 5 minutes or less. The higher the drying temperature, the more the adhesiveness to the transparent substrate is improved, but if the drying temperature is too high, the binder resin may decompose to cause thermal polymerization and cause development failure. As the drying step of the coating film, a reduced pressure drying method of drying in a reduced pressure chamber without raising the temperature may be used.

[3-5] Exposure Process

The image exposure is performed by superimposing a negative matrix pattern on a coating film of the colored resin composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent the decrease in sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer and then exposed to light as necessary. The light source used for the image exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.

[3-6] developing step

The color filter of the present invention can be produced by image-forming an image on a substrate by exposing a coating film using the colored resin composition of the present invention to light with the light source and then developing the resulting film with an aqueous solution containing a surfactant and a basic compound.

The aqueous solution may further comprise an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the basic compound include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine (tetramethylammonium hydroxide (TMAH), and choline. These basic compounds can be used alone in 1, also can be used in 2 or more combinations.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoalkyl glycerides (monoalkyl glyceride esters), anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents may be used in combination with the aqueous solution.

The conditions of the developing treatment are not particularly limited, and the developing temperature is preferably in the range of usually 10 ℃ or more, particularly 15 ℃ or more, further 20 ℃ or more, and further usually 50 ℃ or less, particularly 45 ℃ or less, further 40 ℃ or less. The developing method may be any of a dip developing method, a spray developing method, a brush developing method, an ultrasonic developing method, and the like.

[3-7] Heat curing treatment

The developed color filter is subjected to a heat curing treatment. As the conditions for the heat curing treatment at this time, the temperature is selected within the following range: is usually 100 ℃ or higher, preferably 150 ℃ or higher, and is usually 280 ℃ or lower, preferably 250 ℃ or lower; the time is selected from the range of 5 minutes to 60 minutes. Through the series of steps, the formation of a patterned image of one color is completed. This process is sequentially repeated to pattern black, red, green, and blue colors, thereby forming a color filter. The order of patterning the 4 colors is not limited to the above order.

[3-8] formation of transparent electrode

The color filter of the present invention can be used as a part of a member of a color display, a liquid crystal display device, or the like, by forming a transparent electrode such as ITO on an image as it is, but may be provided with a surface coating layer such as polyamide or polyimide on the image as necessary for the purpose of improving surface smoothness and durability. In some applications such as an in-plane alignment driving method (IPS mode), a transparent electrode may not be formed.

[4] Image display device (Panel)

The image display device of the present invention has the color filter of the present invention.

Hereinafter, a liquid crystal display device and an organic EL display device, which are image display devices, will be described in detail.

[4-1] liquid crystal display device

A method for manufacturing a liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is generally completed as follows: an alignment film is formed on the color filter of the present invention, spacers are scattered on the alignment film, and then the alignment film is bonded to a counter substrate to form a liquid crystal cell. The alignment film is preferably a resin film such as polyimide. In forming the alignment film, a gravure printing method and/or a flexographic printing method is generally used, and the thickness of the alignment film is set to several 10nm. After the alignment film is cured by heat baking, the alignment film is subjected to surface treatment by ultraviolet irradiation or treatment with a rubbing cloth, and is processed into a surface state in which the tilt of the liquid crystal can be adjusted.

The spacer may have a size corresponding to the gap (gap) between the substrates, and a spacer of 2 to 8 μm is generally preferable. Alternatively, a Photo Spacer (PS) of a transparent resin film may be formed on the color filter substrate by photolithography, instead of the spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferably used.

The gap between the counter substrate and the counter substrate is selected in a range of 2 μm to 8 μm, depending on the application of the liquid crystal display device. After the liquid crystal is bonded to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.

Cutting the sealed liquid crystal cell into panel units, reducing pressure in a vacuum chamber, and injecting the liquid crystalThe inlet is immersed in the liquid crystal and then leaks in the chamber, thereby injecting the liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1X 10 ^-2 Pa or more, preferably 1X 10 ^-3 Above, additionally usually 1X 10 ^-7 Pa or less, preferably 1X 10 ^-6 Pa or less. The temperature of the liquid crystal cell is preferably raised at the time of decompression, and the temperature rise temperature is usually in the range of 30 ℃ or more, preferably 50 ℃ or more, and usually 100 ℃ or less, preferably 90 ℃ or less.

The temperature rise at the time of pressure reduction is usually maintained in the range of 10 minutes to 60 minutes, and then the liquid crystal is immersed. The liquid crystal cell into which the liquid crystal is injected is sealed at the liquid crystal injection port by curing the UV curable resin, thereby completing a liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, lyotropic liquid crystals, thermotropic liquid crystals, and the like.

As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, and any of them is possible.

[4-2] organic EL display device

In the case of producing an organic EL display device having the color filter of the present invention, for example, as shown in fig. 1, pixels 20 are formed on a transparent support substrate 10 using the colored resin composition of the present invention, and an organic light emitting body 500 is laminated on a blue color filter on which the pixels 20 are formed, with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween, thereby producing a multicolor organic EL element.

Examples of the method for stacking the organic light-emitting body 500 include: a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter; a method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40. The organic EL element 100 thus manufactured can be applied to an organic EL display device of a passive drive system, and can also be applied to an organic EL display device of an active drive system.

Examples

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

< Phthalocyanine Compound A >

A phthalocyanine compound A having the following chemical structure synthesized based on example 30 of Japanese patent application laid-open No. H05-345861 was used.

Et in the formula represents an ethyl group.

< dispersant A >

Is a methacrylic AB block copolymer composed of an A block having a functional group containing a nitrogen atom and a B block having a solventropic group. Has a repeating unit represented by the following formula (1 a), a repeating unit represented by the following formula (2 a), a repeating unit represented by the following formula (3 a), a repeating unit represented by the following formula (4 a), and a repeating unit represented by the following formula (5 a). The amine value is 120mgKOH/g, and the acid value is less than 1mgKOH/g.

The content of the repeating units represented by the following formulae (1 a), (2 a), (3 a), (4 a) and (5 a) in the total repeating units is less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol% and 6.9 mol%, respectively.

< alkali-soluble resin A >

145 parts by mass of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 ℃. 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate, and 10 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi chemical Co., ltd.) were added dropwise thereto, and further stirring was continued at 120 ℃ for 2 hours. Then, the inside of the reaction vessel was changed to air-substituted, and 0.7 parts by mass of tris (dimethylaminomethyl) phenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued at 120 ℃ for 6 hours. Then, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added thereto, and the mixture was reacted at 120 ℃ for 3.5 hours. The alkali-soluble resin A thus obtained had a weight-average molecular weight Mw in terms of polystyrene measured by GPC of about 9000, an acid value of 25mgKOH/g, and a double bond equivalent of 260g/mol.

< alkali soluble resin B >

A separable flask equipped with a condenser tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was added thereto, nitrogen gas was replaced, and the mixture was heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ℃.

On the other hand, 30 parts by mass of dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butyl peroxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were charged into a monomer tank, 5.2 parts by mass of n-dodecylmercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into a chain transfer agent tank, and after the temperature in the reaction tank was stabilized at 90 ℃, dropwise addition was carried out from the monomer tank and the chain transfer agent tank to initiate polymerization. The temperature was maintained at 90 ℃ and the dropwise addition was carried out for 135 minutes, and after 60 minutes, the temperature was raised to 110 ℃.

After maintaining at 110 ℃ for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen =5/95 (v/v) was started. Then, 39.6 parts by mass of glycidyl methacrylate, 0.4 part by mass of 2,2' -methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part by mass of triethylamine were added to the reaction vessel, and the mixture was reacted at 110 ℃ for 9 hours.

After cooling to room temperature, an alkali-soluble resin B having a weight average molecular weight Mw of 9000 in terms of polystyrene, an acid value of 101mgKOH/g and a double bond equivalent of 550g/mol as measured by GPC was obtained.

< preparation of Green dye Dispersion A >

As shown in table 1, a stainless steel container was filled with 9.9 parts by mass of the phthalocyanine compound a, 0.1 parts by mass of the dispersant a in terms of solid content, 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from the dispersant a), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5mm, and dispersion treatment was performed for 6 hours using a paint shaker. After the end of the dispersion, the beads were separated from the dispersion by using a filter, thereby preparing a green dye dispersion a.

Preparation of Green pigment Dispersion A

As described in table 1, a stainless steel container was filled with 58.9 parts by mass of c.i. pigment green, 1.9 parts by mass of dispersant a in terms of solid content, 4.2 parts by mass of alkali-soluble resin B in terms of solid content, 80.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant a and the solvent derived from alkali-soluble resin B as well), and 225 parts by mass of zirconia beads having a diameter of 0.5mm, and dispersion treatment was performed for 6 hours using a paint shaker. After the end of dispersion, the beads were separated from the dispersion by using a filter, thereby preparing a green pigment dispersion a.

Preparation of yellow pigment Dispersion A

As shown in table 1, 11.4 parts by mass of c.i. pigment yellow 138, 2.9 parts by mass of dispersant a in terms of solid content, 5.7 parts by mass of alkali-soluble resin B in terms of solid content, 76.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including a solvent derived from dispersant a and a solvent derived from alkali-soluble resin B), 4.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5mm were filled in a stainless steel container, and dispersion treatment was performed for 6 hours by a paint shaker. After the end of the dispersion, the beads were separated from the dispersion by means of a filter, thereby preparing a yellow pigment dispersion a.

[ Table 1]

< photopolymerizable monomer A >

Polyethoxylated tetramethylolmethane tetraacrylate (NK ESTER ATM-4E, manufactured by Newzhongcun chemical industries, ltd.) is ethoxylated pentaerythritol tetraacrylate in which an average of 4 moles of ethylene oxide was added per 1 mole. Belonging to the photopolymerizable monomer (e 1).

< photopolymerizable monomer B >

A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Newzhongcun chemical industries, ltd.). Not belonging to the photopolymerizable monomer (e 1).

< photopolymerizable monomer C >)

Ethylene oxide-modified (12) dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by NIPPON CHEMICAL Co., ltd.). Belongs to the photopolymerizable monomer (e 1).

< photopolymerization initiator A >

An oxime ester compound having the following chemical structure.

(4-Acetoxyimino-5- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -5-oxopentanoic acid methyl ester)

In the formula, me represents a methyl group.

< chain transfer agent A >)

Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Takara chemical Co., ltd.)

< surfactant A >

MEGAFAC F-554 (DIC Co., ltd.)

< Adhesivity-improving agent A >

A compound having the following chemical structure.

In the formula, C ₂ H ₄ Represents a dimethylene group, C ₃ H ₆ Represents a trimethylene group.

< preparation of colored resin composition >

The components shown in table 2 were mixed in the solid content ratios shown, to prepare colored resin compositions. Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Propylene Glycol Monomethyl Ether (PGME) were used so that the content of the entire solid content of the colored resin composition was 17.3 mass%. The mixing ratio (mass ratio) of PGMEA/PGME in the obtained colored resin composition was 90/10.

[ Table 2]

< determination of color characteristics >

The resulting colored resin composition was applied to a 50mm square glass substrate (manufactured by AGC Co., ltd., AN 100) having a thickness of 0.7mm by a spin coating method, dried under reduced pressure, and then prebaked at 90 ℃ for 90 seconds on a hot plate. Then, a 2kW high-pressure mercury lamp was used at 40mJ/cm ² Exposure and illumination of 30mW/cm ² And carrying out whole surface exposure treatment. Then, a development treatment was performed for 60 seconds at a developer temperature of 23 ℃ using a 0.04 mass% aqueous solution of potassium hydroxide. Then, at 1kg/cm ² The water pressure of (2) was subjected to spray washing treatment for 10 seconds. Then, a heat curing treatment was performed at 230 ℃ for 20 minutes in a clean oven, thereby producing a colored substrate.

The obtained colored substrate was measured for its transmission spectrum by a spectrophotometer U-3310 manufactured by hitachi corporation, and the luminance was calculated for the chromaticity sy =0.576 under the C light source. The results are shown in Table 2.

< evaluation of Pattern formability >

The obtained colored resin composition was applied to a 50mm square glass substrate (AN 100 manufactured by AGC corporation) having a thickness of 0.7mm by a spin coating method so that the chromaticity after the heat curing treatment was sy =0.576 under a C light source, and prebaked at 80 ℃ for 90 seconds. Then, a 2kW high-pressure mercury lamp was used at 40mJ/cm ² Exposure and illumination of 30mW/cm ² The exposure treatment was performed through an exposure mask having a circular covering portion with a diameter of 30 μm. Then, 0.04 mass% of potassium hydroxide water was usedThe solution was subjected to a development treatment at a developer temperature of 23 ℃ for 60 seconds. Then, at 1kg/cm ² The water pressure of (2) was subjected to spray washing treatment for 10 seconds. Then, a heat curing treatment was performed at 230 ℃ for 20 minutes, thereby producing a pattern substrate. The diameter (μm) of the hole of the pattern (aperture a) of the obtained pattern substrate a was measured using an optical microscope.

Then, the pattern substrate B was produced under the same conditions except that the temperature of the prebaking in the above step of the pattern substrate a was changed from 80 ℃ to 100 ℃. The diameter (μm) of the hole of the pattern (aperture B) was measured using an optical microscope for the obtained pattern substrate B.

The influence of the pre-baking temperature on the pore diameter was calculated from the pore diameter a and the pore diameter B as an index of temperature dependence. The results of temperature dependence (= (pore diameter A-pore diameter B) [ μm ]/(100-80) [. Degree. C. ]) are shown in Table 2.

As is clear from table 2, the luminance was improved when the phthalocyanine compound a was used as in comparative example 1, as compared with the colored resin composition containing c.i. pigment green 58 of comparative example 2. However, the use of the phthalocyanine compound a greatly deteriorates the pre-baking temperature dependence of the pore diameter.

In general, unlike pigments, dyes present as single molecules in the system can provide high brightness and high tinting strength, but the molecules are isolated and therefore have poor heat resistance, and sublimation and oxidation occur in a heat curing process for obtaining a pattern, so that the brightness of the pattern after the heat curing process tends to be reduced.

In contrast, the phthalocyanine compound (1) has a structure in which 1 or more of the hydrogen atoms constituting the phthalocyanine skeleton are substituted with fluorine atoms having a small atomic radius, and the association of the phthalocyanine compounds (1) is not easily inhibited, and therefore, when the intermolecular distance is decreased by heating or the like, the formation of an associated body suppresses the decrease in luminance due to heating. In addition, since the particle diameter thereof becomes smaller than c.i. pigment green 58 after the association, it is considered that the luminance of the pattern becomes high after the heat curing treatment as a whole.

On the other hand, in comparison between comparative example 1 and comparative example 2, the use of the phthalocyanine compound (1) deteriorates the pre-baking temperature dependence of the pore diameter.

In comparative example 1, the phthalocyanine compound (1) is an associated body having a small particle diameter and is present densely in the coating film, and it is considered that the state in which the penetration and dissolution of the developer into the coating film are easily suppressed is formed. It is considered that when the prebaking temperature is 80 ℃, the residual solvent is present in the coating film in a certain amount, and thereby the penetration of the developer into the coating film can be promoted. On the other hand, in a high temperature region where the prebaking temperature is 100 ℃, the residual solvent is small, the penetration of the developer into the inside of the coating film is insufficient, and the solubility of the coating film in the developer is also insufficient in the unexposed portion, which results in poor patterning and a reduction in the pore diameter, thereby deteriorating the prebaking temperature dependence of the pore diameter.

On the other hand, examples 1,2 and 3 containing the phthalocyanine compound (1) maintained high luminance and had good pre-baking temperature dependence of the pore diameter. In examples 1,2 and 3, since part or all of the photopolymerizable monomer B of comparative example 1 was replaced with the photopolymerizable monomer (e 1) and the photopolymerizable monomer (e 1) had an oxyalkylene chain, it was considered that the developing solution permeability could be maintained good even in a coating film state with a small residual solvent such as 100 ℃, and pores having a diameter comparable to that in a coating film state with a large residual solvent such as 80 ℃ could be formed, and thus deterioration of the pre-baking temperature dependency of the pore diameter could be suppressed.

In the colored resin composition containing c.i. pigment green 58 of comparative example 2, the particle size of c.i. pigment green 58 is larger than the particle size of the associated body of phthalocyanine compound (1) of examples 1,2, 3 and 1, and a sufficient gap for allowing the developer to penetrate into the coating film is ensured, and therefore, sufficient developer permeability is obtained regardless of the amount of the residual solvent, that is, regardless of the prebaking temperature, and it is considered that the prebaking temperature dependency of the pore size is good.

The present invention has been described in detail using specific embodiments, but it is a matter of course that various changes and modifications can be made by those skilled in the art without departing from the intention and scope of the present invention.

Description of the reference numerals

10. Transparent support substrate

20. Pixel

30. Organic protective layer

40. Inorganic oxide film

50. Transparent anode

51. Hole injection layer

52. Hole transport layer

53. Luminescent layer

54. Electron injection layer

55. Cathode electrode

100. Organic EL element

500. Organic light-emitting body

Claims

1. A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer,

the colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1),

the photopolymerizable monomer (E) comprises a photopolymerizable monomer (E1) having a partial structure represented by the following general formula (I),

in the formula (1), A ¹ ～A ¹⁶ Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2) wherein A ¹ ～A ¹⁶ Represents a fluorine atom, and A ¹ ～A ¹⁶ Wherein 1 or more of the above-mentioned groups represent a group represented by the following general formula (2),

in the formula (2), X represents a linking group having a valence of 2, the benzene ring in the formula (2) may have an optional substituent, and represents a linking bond,

in the formula (I), R ¹ Represents an alkylene group having 2 or more carbon atoms,

R ² represents a hydrogen atom or a methyl group,

n represents an integer of 1 or more,

it represents a connecting bond.

2. The colored resin composition according to claim 1, wherein the photopolymerizable monomer (e 1) is a compound represented by the following general formula (II),

in the formula (II), R ¹ 、R ² And n is as defined for formula (I),

z represents a direct bond, an oxygen atom, a sulfur atom, a 2-to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2-to 4-valent non-aromatic heterocyclic group, a 2-to 4-valent aromatic ring group, or a partial structure represented by the following general formula (III),

p represents an integer of 2 to 6,

further, a plurality of structures represented by the following general formula (II') contained in one molecule are optionally the same or different,

in the formula (III), the bond is represented by the formula (III).

3. The colored resin composition according to claim 1 or 2, wherein the content ratio of the (a) colorant is 10% by mass or more in the entire solid content.

4. The colored resin composition according to any one of claims 1 to 3, wherein the content of the photopolymerizable monomer (e 1) is 1% by mass or more of the total solid content.

5. A color filter having a pixel manufactured using the colored resin composition according to any one of claims 1 to 4.

6. An image display device having the color filter according to claim 5.