CN118076922A

CN118076922A - Colored resin composition, color filter and image display device

Info

Publication number: CN118076922A
Application number: CN202280068115.7A
Authority: CN
Inventors: 石井宏明; 平冈紫阳; 福冈幸治; 大村直也
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2021-10-12
Filing date: 2022-10-12
Publication date: 2024-05-24
Also published as: TW202334326A; KR20240074783A; WO2023063336A1

Abstract

Provided is a colored resin composition which can give a cured film having excellent brightness and good contrast. The colored resin composition of the present invention comprises (A) a colorant comprising a specific phthalocyanine compound, (B) a solvent, (C) an alkali-soluble resin comprising an alkali-soluble resin (C-1) having a repeating unit containing an aromatic ring in a side chain, and (D) a photopolymerization initiator and (E) a photopolymerizable monomer, wherein the total content of the repeating units containing an aromatic ring in a side chain in the alkali-soluble resin (C-1) is 20 mol% or more.

Description

Colored resin composition, color filter and image display device

Technical Field

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

The present application claims priority from japanese patent application No. 2021-167165, 10-12 in 2021, and the contents thereof are incorporated herein by reference.

Background

Conventionally, pigment dispersion, dyeing, electrodeposition, and printing have been known as methods for manufacturing color filters used in liquid crystal display devices and the like. Among them, the pigment dispersion method having excellent characteristics in a balanced manner is most widely used from the viewpoints of spectroscopic 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 colorant for determining the color of a color filter, a pigment is generally used from the viewpoints of heat resistance, light resistance, and the like, but in particular, the market demands are not satisfied in terms of high brightness, and studies on using a dye instead of a pigment as a colorant are actively being conducted. With respect to green pixels, studies using a specific phthalocyanine compound as a dye are being conducted (for example, see patent documents 1 to 3).

Prior art literature

Patent literature

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

Patent document 2: international publication No. 2020/171060

Patent document 3: japanese patent laid-open No. 2020-046655

Disclosure of Invention

Problems to be solved by the invention

The inventors of the present invention found that, when studied: the colored resin compositions described in patent documents 1 to 3 have insufficient contrast in practical use.

Accordingly, an object of the present invention is to provide a colored resin composition capable of obtaining a cured film having a good contrast.

Solution for solving the problem

The present inventors have conducted intensive studies and as a result found that: the present invention has been completed by using a specific phthalocyanine compound as a colorant and further using an alkali-soluble resin having a specific structure, whereby the above-described problems can be solved.

That is, the present invention has the following configuration.

[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 aforementioned (C) alkali-soluble resin contains an alkali-soluble resin (C-1) having a repeating unit containing an aromatic ring in a side chain,

When the total mole number of the repeating units in the alkali-soluble resin (c-1) is 100 mole%, the total content of the repeating units having an aromatic ring in a side chain is 20 mole% or more.

( In the formula (1), a ¹～A¹⁶ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Wherein 1 or more of A ¹～A¹⁶ represents a fluorine atom, and 1 or more of A ¹～A¹⁶ represents a group represented by the following general formula (2). )

( In formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may optionally have an optional substituent. * Representing an atomic bond. )

[2] The colored resin composition according to [1], wherein the total content of the repeating units having an aromatic ring in a side chain in the alkali-soluble resin (c-1) is 30 mol% or more.

[3] The colored resin composition according to [1] or [2], wherein the alkali-soluble resin (c-1) has a repeating unit having an alicyclic structure in a side chain, and the alicyclic structure is a saturated alicyclic structure.

[4] The colored resin composition according to [3], wherein a distance from the main chain to the alicyclic structure in the repeating unit having an alicyclic structure in a side chain is 4 or less.

[5] The colored resin composition according to [3] or [4], wherein the total content of repeating units having an alicyclic structure in a side chain is 10 mol% or less, based on 100 mol% of the total number of repeating units in the alkali-soluble resin (c-1).

[6] The colored resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (c-1) has at least 1 kind of repeating unit selected from the group consisting of the repeating units represented by the following general formula (3) and the following general formula (4) as the repeating unit containing an aromatic ring in a side chain.

( In the formula (3) and the formula (4), R ¹ each independently represents a hydrogen atom or a methyl group. The benzene rings in the formula (3) and the formula (4) may optionally have any substituent. )

[7] The colored resin composition according to [6], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the general formula (3) as the repeating unit containing an aromatic ring in a side chain.

[8] The colored resin composition according to any one of [3] to [5], wherein the alkali-soluble resin (c-1) has at least 1 kind of repeating unit selected from the group consisting of the repeating units represented by the following general formula (5) and the following general formula (6) as the repeating unit containing an alicyclic structure in a side chain.

( In the formula (5) and the formula (6), R ¹ each independently represents a hydrogen atom or a methyl group. The saturated hydrocarbon ring in the formula (5) and the formula (6) may have any substituent. )

[9] The colored resin composition according to [8], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the general formula (5) as the repeating unit having an alicyclic structure in a side chain.

[10] The colored resin composition according to any one of [1] to [9], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the following general formula (I).

(In the formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.

R ² represents a trivalent hydrocarbon group optionally having a substituent.

R ⁴ represents a divalent hydrocarbon group optionally having a substituent. )

[11] The colored resin composition according to any one of [1] to [10], wherein the content of the colorant (A) is 10% by mass or more relative to the total solid component amount of the colored resin composition.

[12] The colored resin composition according to any one of [1] to [11], wherein the content of the alkali-soluble resin (c-1) is 10 mass% or more relative to the total solid component amount of the colored resin composition.

[13] A color filter comprising pixels produced using the colored resin composition according to any one of [1] to [12 ].

[14] An image display device is provided with a color filter of [13 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a colored resin composition capable of obtaining a cured film excellent in brightness and contrast can be provided.

Drawings

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

Detailed Description

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

In the present invention, unless otherwise specified, the term "amine value" means an amine value in terms of an effective solid content, and is a value expressed by mass of KOH corresponding to the amount of alkali per 1g of the solid content of the dispersant.

In the present invention, unless otherwise specified, the acid value means an acid value in terms of an effective solid content, and is calculated by neutralization titration.

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

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

In the present invention, "(meth) acrylic" means "either or both of acrylic and methacrylic".

In the present invention, the numerical range indicated by "to" means a range including the numerical values described before and after "to" as the lower limit value and the upper limit value.

[1] 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, other additives other than the above components may be blended as needed.

[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, sometimes referred to as "phthalocyanine compound (1)").

In the formula (1), a ¹～A¹⁶ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Wherein 1 or more of A ¹～A¹⁶ represents a fluorine atom, and 1 or more of A ¹～A¹⁶ represents a group represented by the following general formula (2).

In formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may optionally have an optional substituent. * Representing an atomic bond.

(A¹～A¹⁶)

In the above formula (1), a ¹～A¹⁶ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following formula (2). Wherein 1 or more of A ¹～A¹⁶ represents a fluorine atom, and 1 or more of A ¹～A¹⁶ represents a group represented by the following general formula (2).

Examples of the halogen atom in a ¹～A¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms are preferable from the viewpoints of adjusting the hue to a green pigment optimal for use in a color filter and improving the brightness.

1 Or more of a ¹～A¹⁶ represents a fluorine atom, preferably 6 or more, more preferably 7 or more, further preferably 8 or more, and further preferably 15 or less, more preferably 12 or less, further preferably 10 or less. When the content is not less than the above-mentioned lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and when the content is not more than the above-mentioned upper limit, the affinity with the dispersant and the solvent in the colored resin composition tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the number of substituents in A ¹～A¹⁶ representing fluorine atoms is 1 to 15, preferably 6 to 12, more preferably 7 to 10.

(X)

X in formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom and a-N (R ^a1) -group (R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). From the viewpoint of stability of the phthalocyanine compound (1) at the time of baking, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

(Substituent optionally provided on benzene ring)

The benzene ring in the formula (2) may optionally have an optional substituent. Examples of the substituent include, but are not limited to, a halogen atom, an alkyl group (—r ^A group), an alkoxy group (—or ^A group (wherein R ^A represents an alkyl group)), an alkoxycarbonyl group (—coor ^A group (wherein R ^A represents an alkyl group)), an aryl group (—r ^B group), an aryloxy group (—or ^B group (wherein R ^B represents an aryl group)), and an aryloxycarbonyl group (—coor ^B group (wherein R ^B represents an aryl group). From the viewpoints of affinity with a solvent 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 with a solvent.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more 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 and foreign matter tend to be suppressed. When the solvent affinity is lower than the upper limit, the solvent affinity tends to be improved and the stability with time tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 2 to 4.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl and hexyl, and from the viewpoint of suppressing aggregation, methyl and ethyl are preferable, and ethyl is more preferable.

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

The carbon number of the aryl group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, and further preferably 8 or less. When the lower limit value is not less than the above-mentioned lower limit value, aggregation due to steric repulsion tends to be suppressed. When the solvent affinity is lower than the upper limit, the solvent affinity 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 having 1 free valence (FREE VALENCE), a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single 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-quinolizine ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine 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 optional substituent, the number of substitution is not particularly limited, but from the viewpoints of pi-pi stacking of the phthalocyanine compound (1) molecules with each other, improvement in heat resistance, suppression of reduction in brightness due to decomposition of the phthalocyanine compound (1), convergence of the phthalocyanine compound (1) molecules with each other, and improvement in contrast, the number of substitution is preferably 1 with respect to 1 benzene ring.

When the benzene ring in the formula (2) has an optional substituent, the substitution position may be ortho-position, meta-position or para-position, and para-position is preferable from the viewpoints of promoting pi-pi stacking of the phthalocyanine compound (1) molecules to each other, improving heat resistance, suppressing the decrease in brightness caused by the decomposition of the phthalocyanine compound (1), and improving the contrast by the convergence of the phthalocyanine compound (1) molecules to each other. In particular, from the viewpoint of improvement of contrast, an alkoxycarbonyl group is preferable as a substituent at the para position.

In the formula (1), 1 or more of A ¹～A¹⁶ represent a group represented by the formula (2). From the viewpoints of solubility in a solvent, pi-pi stacking of the phthalocyanine compound (1) molecules with each other, and enhancement of brightness and contrast by the molecules coming together, it is preferable that: more than 1 of a ¹～A⁴ are groups represented by formula (2), more than 1 of a ⁵～A⁸ are groups represented by formula (2), more than 1 of a ⁹～A¹² are groups represented by formula (2), and more than 1 of a ¹³～A¹⁶ are groups represented by formula (2); more preferred are: more than 2 of a ¹～A⁴ are groups represented by formula (2), more than 2 of a ⁵～A⁸ are groups represented by formula (2), more than 2 of a ⁹～A¹² are groups represented by formula (2), and more than 2 of a ¹³～A¹⁶ are groups represented by formula (2).

In the formula (1), 1 or more of a ¹～A¹⁶ represent a fluorine atom, and from the viewpoint of stability of the phthalocyanine compound, it is preferable that: more than 1 of a ¹～A⁴ are fluorine atoms, more than 1 of a ⁵～A⁸ are fluorine atoms, more than 1 of a ⁹～A¹² are fluorine atoms, and more than 1 of a ¹³～A¹⁶ are fluorine atoms; more preferred are: more than 2 of a ¹～A⁴ are fluorine atoms, more than 2 of a ⁵～A⁸ are fluorine atoms, more than 2 of a ⁹～A¹² are fluorine atoms, and more than 2 of a ¹³～A¹⁶ are fluorine atoms.

From the viewpoints of the maximum transmission wavelength and transmittance of the phthalocyanine compound (1), affinity with a dispersant or a solvent in the colored resin composition, uniformity of crystallization of the phthalocyanine compound at the time of firing the color filter, brightness and contrast, it is particularly preferable that: a ²、A³、A⁶、A⁷、A¹⁰、A¹¹、A¹⁴ and a ¹⁵ are groups represented by formula (2), and a ¹、A⁴、A⁵、A⁸、A⁹、A¹²、A¹³ and a ¹⁶ are fluorine atoms.

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

In the above formula, et represents ethyl.

As a method for producing the phthalocyanine compound (1), a known method can be used, and for example, a method described in Japanese patent application laid-open No. 05-345861 can be used.

(A) The colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of the other coloring agent include pigments and dyes. In the case of use for green pixels, for example, a green pigment, a green dye, a yellow pigment, a yellow dye are preferably used.

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 the green dyes classified as dyes in the dye index, c.i. solvent dyes, for example, c.i. solvent green 1, 3,4,5, 7, 28, 29, 32, 33, 34, 35 are cited. 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. intermediate green 1, 3,4,5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. From the viewpoint of suppressing decomposition of the dye at the time of firing, c.i. solvents green 1, 3,4,5, 7, 28, 29, 32, 33, 34, 35 are 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、35：1、36、36：1、37、37：1、40、41、42、43、48、53、55、61、62、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、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、191：1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208 and a compound obtained by inserting another compound into a 1:1 complex of azobarbituric acid represented by the following formula (i) and nickel or a tautomer thereof (hereinafter, sometimes referred to as "nickel azo complex represented by the formula (i)").

Examples of the other compound to be incorporated into the nickel azo complex represented by the formula (i) include compounds represented by the following formula (ii).

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

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 specific compounds described in JP-A2010-168831.

Examples of the yellow dye include c.i. solvent dyes, among yellow dyes classified as dyes in the dye index, 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, and 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、243、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, 141. Examples of the c.i. mediator dyes include c.i. mediator dyes 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65. Preferred examples of the solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 and 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、243、251、23、25、29、34、40、42、72、76、99、111、112、114、116、163、243、 include derivatives thereof.

From the viewpoint of suppressing decomposition of the dye at the time of firing, c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 are preferable.

The average primary particle diameter of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and still more preferably 0.04 μm or less. In micronizing the pigment, it is preferable to use, for example, solvent milling.

The content of the colorant (a) in the colored resin composition of the present invention is not particularly limited, but is preferably 10 mass% or more, more preferably 15 mass% or more, still more preferably 20 mass% or more, still more preferably 25 mass% or more, particularly preferably 30 mass% or more, and further preferably 80 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, particularly preferably 40 mass% or less, of the total solid content of the colored resin composition. When the lower limit value is equal to or higher than the above-mentioned lower limit value, a wide hue tends to be reproduced, and when the upper limit value is equal to or lower than the above-mentioned upper limit value, stability with time tends to be ensured. The upper limit and the lower limit may be arbitrarily combined. The upper limit and the lower limit 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, still more preferably 20 to 60% by mass, still more preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass, based on 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, and further preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass or less, of the total solid content of the colored resin composition. When the luminance is equal to or higher than the lower limit, the luminance tends to be improved, and when the luminance is equal to or lower than the upper limit, the temporal stability tends to be ensured. The upper limit and the lower limit may be arbitrarily combined. The upper limit and the lower limit may be arbitrarily combined. 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, still more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, based on the total solid content of the colored resin composition.

The content ratio of the coloring resin composition of the present invention is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass or more, particularly preferably 10% by mass or more, and further preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, based on the total solid content of the coloring resin composition. When the lower limit value is equal to or higher than the above-mentioned lower limit value, a wide hue tends to be reproduced, and when the upper limit value is equal to or lower than the above-mentioned upper limit value, stability with time tends to be ensured. The upper limit and the lower limit may be arbitrarily combined. 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, still more preferably 5 to 25% by mass, still more preferably 7 to 25% by mass, and particularly preferably 10 to 20% by mass, based on the total solid content of the colored resin composition.

[1-2] (B) solvent

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

The solvent (B) may be any solvent capable of dissolving or dispersing the respective components.

Examples of such solvents include: 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 t-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, tripropylene glycol methyl ether and other glycol monoalkyl ethers;

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 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 monopropyl 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, 3-methyl-3-methoxybutyl acetate and the like;

Glycol diacetates 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, dipentyl ether, ethylisobutyl ether, dihexyl ether, and the like;

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, and methoxy methyl amyl ketone;

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, 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 gamma butyrolactone;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxy methyl pentanone;

nitriles such as acetonitrile and benzonitrile.

Examples of the commercially available solvents belonging to the above materials include mineral spirits, varsol #2, apco #18solvent, apco thinner, socal solvent No.1 and No.2, solvent #150, shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all trade names). These solvents may be used alone or in combination of 1 or more than 2.

When forming pixels of a color filter by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200 ℃ (pressure 1013.25[ hPa ]). More preferably a solvent having a boiling point of 120 to 170 ℃.

Among the solvents, glycol alkyl ether acetates are preferred in view of good balance of coatability, surface tension, etc., and high solubility of constituent components in the composition.

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

As another embodiment, 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 dry, but has an effect of less likely to cause destruction of the interrelationship of the constituent components in the pigment dispersion due to 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 solvent (B) 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, for example, foreign matter defects caused by precipitation and solidification of color material components and the like at the tip of the slit nozzle tend to be easily avoided, and when the upper limit value is set to the lower limit value, problems such as beat defects in the reduced pressure drying process and needle marks in the pre-baking, which are caused by the slow drying rate of the composition, tend to be easily avoided.

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

The solvent having a boiling point of 150℃or higher may be preferably 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 or triacetin.

When forming pixels of a color filter by an inkjet 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 upper limit value, uniformity of the obtained coating film tends to be improved, and when the upper limit value is not more than the upper limit value, residual solvent tends to be easily reduced at the time of firing.

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 case of manufacturing a color filter by the inkjet method, since the ink ejected from the nozzle is very fine and several to several tens of pL, the solvent tends to evaporate before falling around the nozzle opening or into the pixel array, and the ink tends to be concentrated and dried. 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. When the solvents having a boiling point of 180 ℃ or higher are used in combination, the content of the solvent having a boiling point of 180 ℃ or higher in the solvent (B) is preferably 50 mass% or higher, more preferably 70 mass% or higher, and most preferably 90 mass% or higher. When the lower limit value is not less than the above-mentioned lower limit value, the effect of preventing evaporation of the solvent from the droplets tends to be exhibited sufficiently.

Examples of the solvent having a boiling point of 180℃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 among the above solvents.

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

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

The content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit thereof is preferably 99 mass% or less, more preferably 90 mass% or less, and still more preferably 85 mass% or less. When the upper limit value is less than or equal to the above-described upper limit value, a coating film tends to be formed easily. On the other hand, the lower limit of the solvent content is preferably 70 mass% or more, more preferably 75 mass% or more, and still more preferably 78 mass% or more, in view of the viscosity and the like suitable for coating. The upper limit and the lower limit may be arbitrarily combined. 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 even more preferably 78 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 (C) alkali-soluble resin, both the film curability by photopolymerization and the solubility by a developer can be achieved.

The alkali-soluble resin (C) in the colored resin composition of the present invention contains an alkali-soluble resin (C-1) having a repeating unit containing an aromatic ring in a side chain, and the total content of repeating units containing an aromatic ring in a side chain is 20 mol% or more, assuming that the total mole number of repeating units in the alkali-soluble resin (C-1) is 100 mol%.

The alkali-soluble resin (c-1) preferably has a repeating unit having an alicyclic structure in a side chain, and the alicyclic structure is a saturated alicyclic structure.

It can be considered that: by containing the alkali-soluble resin (c-1), the aromatic ring contained in the alkali-soluble resin (c-1) and pi-pi accumulation of the phthalocyanine compound (1) bring the phthalocyanine compounds (1) close to each other, and as shown in patent document 2, molecules of a specific phthalocyanine compound come together in the firing step, thereby promoting ordered alignment (crystallization) and improving contrast. It can be further considered that: when the content of the alicyclic structure is small, the bulky alicyclic structure is prevented from blocking the association of molecules of the phthalocyanine compound, and the contrast is improved.

When the total mole number of the repeating units in the alkali-soluble resin (c-1) is 100 mole%, the total content of the repeating units having an aromatic ring in a side chain is 20 mole% or more, preferably 30 mole% or more, and more preferably 40 mole% or more from the viewpoint of contrast. From the viewpoint of developing patterning properties, it is preferably 70 mol% or less, more preferably 60 mol% or less.

When the total mole number of the repeating units in the alkali-soluble resin (c-1) is 100 mole%, the total content of the repeating units having an alicyclic structure in the side chain is preferably 10 mole% or less, more preferably 5 mole% or less, and even more preferably 2 mole% or less, from the viewpoint of contrast. The lower limit is not particularly limited, but is preferably 0.5 mol% or more from the viewpoint of improving adhesion and suppressing undercut.

The repeating units comprising an aromatic ring in the side chain include: among the repeating units formed in the copolymerization reaction of the synthetic alkali-soluble resin, repeating units derived from a monomer having an aromatic ring in a side chain; and a unit in which an aromatic ring is subsequently introduced into a side chain of a monomer having no aromatic ring in the side chain by an addition reaction with a compound containing an aromatic ring or an aromatic ring reaction after the copolymerization reaction. From the viewpoint of contrast, the repeating unit containing an aromatic ring in a side chain is preferably a repeating unit derived from a monomer containing an aromatic ring in a side chain.

The repeating unit derived from the monomer having an aromatic ring in a side chain may be further introduced into the aromatic ring by an addition reaction with a compound having an aromatic ring or an aromatic ring reaction.

Examples of the aromatic ring in the repeating unit having an aromatic ring in a side chain include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The carbon number is preferably 4 or more, more preferably 6 or more, and still more preferably 12 or less. For example, it is preferably 2 to 12, more preferably 6 to 12. When the lower limit value is not less than the above-mentioned lower limit value, heat resistance tends to be improved. When the solvent affinity is lower than the upper limit, the solvent affinity tends to be improved and the stability with time tends to be improved.

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 benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 1 free valence,A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring having 1 free valence. From the viewpoint of brightness, a benzene ring or naphthalene ring having 1 free valence is preferable, and a benzene ring having 1 free valence is more preferable.

These aromatic rings may have a substituent, and examples of the substituent include, but are not particularly limited to, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; alkyl of 1 to 8 carbon atoms; alkenyl of 2 to 8 carbon atoms; a hydroxyl group; alkoxy of 1 to 8 carbon atoms: aromatic hydrocarbon ring groups such as phenyl, trimethylphenyl, tolyl, naphthyl, and the like; cyano group; a carboxyl group; an acetoxy group; alkylcarbonyloxy having 2 to 9 carbon atoms; a sulfonic acid group; a sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; a carbonyl group; alkylcarbonyl of 2 to 9 carbon atoms; a hydroxyethyl group; acetyl amide groups; a dialkylaminoethyl group to which an alkyl group having 1 to 4 carbon atoms is bonded; trifluoromethyl; trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and alkyl group having 1 carbon atom or no substituent is desirable from the viewpoint of ease of synthesis.

The structure of the repeating unit having an aromatic ring in a side chain is preferably 1 or 2 selected from the following general formula (3) and the following general formula (4), and more preferably the following general formula (3) from the viewpoints of ease of synthesis and ease of pi-pi stacking with the phthalocyanine compound (1).

In the formula (3) and the formula (4), R ¹ each independently represents a hydrogen atom or a methyl group. The benzene rings in the formula (3) and the formula (4) may optionally have any substituent.

The repeating unit including an alicyclic structure in a side chain includes: among the repeating units formed in the copolymerization reaction of the synthetic alkali-soluble resin, repeating units derived from a monomer having an alicyclic structure in a side chain; and a unit in which an alicyclic structure is introduced into a side chain after the copolymerization reaction by an addition reaction with a compound having an alicyclic structure or a hydrocarbon ring reaction with respect to a monomer having no alicyclic structure in the side chain. From the viewpoint of contrast, the repeating unit having an alicyclic structure in the side chain is preferably a repeating unit derived from a monomer having an alicyclic structure in the side chain, and when the total mole number of the repeating units in the alkali-soluble resin (c-1) is 100 mole%, the total content of the repeating units derived from the monomer having an alicyclic structure in the side chain is preferably 10 mole% or less.

The repeating unit derived from a monomer having an alicyclic structure in a side chain may be further introduced into the alicyclic structure by an addition reaction with a compound having an alicyclic structure or a hydrocarbon ring formation reaction.

From the viewpoint of contrast, in the repeating unit having an alicyclic structure in the side chain, the distance from the main chain to the alicyclic structure is preferably 4 or less atoms, more preferably 2 or less atoms. It can be considered that: the total content of the repeating units having the above-mentioned range in the distance from the main chain to the alicyclic structure is set to the above-mentioned content range, thereby suppressing the occurrence of inhibition of the junction between molecules of the phthalocyanine compound (1) and improving the contrast.

Here, a distance from the main chain to the alicyclic structure of 4 or less means that: the number of atoms contained in the bonding chain from the bonding portion of the main chain and the side chain of the alkali-soluble resin (c-1) to the alicyclic structure is not included in the number of atoms as carbon atoms of the bonding portion of the main chain and the side chain and carbon atoms constituting the alicyclic structure. For example, the number average atomic count of the following general formulae (5) and (6) is 2.

The alicyclic structure in the repeating unit having an alicyclic structure in a side chain may be a single ring or a condensed ring. Examples of the alicyclic structure include cyclopropyl ring, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring, norbornyl ring, tricyclodecane ring, and adamantane ring. From the viewpoints of heat resistance and ease of synthesis, a cyclohexyl ring or a tricyclodecane ring is desirable.

The alicyclic structure is preferably a saturated alicyclic structure.

The alicyclic structure may have a substituent, and examples of the substituent include, but are not particularly limited to, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; alkyl of 1 to 8 carbon atoms; alkenyl of 2 to 8 carbon atoms; a hydroxyl group; alkoxy of 1 to 8 carbon atoms: aromatic hydrocarbon ring groups such as phenyl, trimethylphenyl, tolyl, naphthyl, and the like; cyano group; a carboxyl group; an acetoxy group; alkylcarbonyloxy having 2 to 9 carbon atoms; a sulfonic acid group; a sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; a carbonyl group; alkylcarbonyl of 2 to 9 carbon atoms; a hydroxyethyl group; acetyl amide groups; a dialkylaminoethyl group to which an alkyl group having 1 to 4 carbon atoms is bonded; trifluoromethyl; a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms are preferably methyl groups or are not substituted from the viewpoint of ease of synthesis.

The structure including the repeating unit having an alicyclic structure in a side chain is preferably 1 or 2 selected from the following general formula (5) and the following general formula (6), and more preferably the following general formula (5) from the viewpoints of ease of synthesis and heat resistance.

In the formula (5) and the formula (6), R ¹ each independently represents a hydrogen atom or a methyl group. The saturated hydrocarbon ring in the formula (5) and the formula (6) may have any substituent.

The alkali-soluble resin (c-1) may further contain a repeating unit represented by the following general formula (I) in addition to the repeating unit containing an aromatic ring in a side chain and the repeating unit containing an alicyclic structure in a side chain.

In formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.

R ² represents a trivalent hydrocarbon group optionally having a substituent.

R ⁴ represents a divalent hydrocarbon group optionally having a substituent.

The carboxyl group in the repeating unit represented by the formula (I) is sufficiently far from the main chain, and is highly flexible, and the carboxyl groups do not form strong hydrogen bonds with each other, and are easily disposed so as to be exposed to the outside of the resin molecule. It can be considered that: when the alkali-soluble resin (c-1) has a repeating unit represented by the formula (I), the resin covers the phthalocyanine compound (1) by forming a bond such as a hydrogen bond with a carboxyl group of the alkali-soluble resin (c-1) through a central metal site, an ether bond site or the like in the phthalocyanine compound (1), thereby inhibiting decomposition reaction of the phthalocyanine compound (1) at the time of firing, and as a result, high brightness is obtained.

(R²)

In the formula (I), R ² represents a trivalent hydrocarbon group optionally having a substituent. Examples of the trivalent hydrocarbon group include trivalent aliphatic hydrocarbon groups. Examples of the trivalent aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group in which these groups are combined.

The carbon number of the trivalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 5 or less. When the content is within the above range, hydrogen bond with the phthalocyanine compound (1) is likely to be formed, and the luminance tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 1 to 15, more preferably 1 to 10, still more preferably 2 to 8, and particularly preferably 3 to 5.

Specific examples of the trivalent aliphatic hydrocarbon group include the following. When the alicyclic structure is contained as in the following general formula (R-2), the alicyclic structure is not included in the repeating unit containing the alicyclic structure.

In the formula (R-1) and (R-2), the atom bond is represented.

Examples of the substituent optionally contained in the trivalent hydrocarbon group include an alkoxy group, an aryloxy group, an aryloxysulfide group, and a halogen atom. When the substituent contains an aromatic ring, the substituent is not included in the repeating unit containing an aromatic ring, and when the substituent contains an alicyclic structure, the substituent is not included in the repeating unit containing an alicyclic structure.

(R⁴)

In the formula (I), R ⁴ represents a divalent hydrocarbon group optionally having a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon ring group.

Examples of the divalent aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group in which these groups are combined.

The carbon number of the divalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 4 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 6 or less. When the lower limit is not less than the above-mentioned lower limit, the hydrogen bond between the phthalocyanine compound (1) and the carboxyl group of the alkali-soluble resin (c-1) tends to be formed firmly, and when the upper limit is not more than the above-mentioned upper limit, the hydrogen bond between the phthalocyanine compound (1) and the carboxyl group of the alkali-soluble resin (c-1) tends to be maintained. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 1 to 15, more preferably 2 to 10, still more preferably 3 to 8, and particularly preferably 4 to 6.

Specific examples of the divalent aliphatic hydrocarbon group include vinyl, propenyl, ethynylene (ethynylene), cyclohex-4-en-1, 2-diyl, and cyclohex-1, 2-diyl. Among these, vinyl, ethynylene, cyclohex-4-ene-1, 2-diyl are preferable from the viewpoint of promoting hydrogen bonding with the carboxyl group of the alkali-soluble resin (c-1).

The number of carbon atoms in the divalent aromatic hydrocarbon ring group is not particularly limited, but is preferably 6 or more, and more preferably 12 or less. For example, it is preferably 6 to 12. When the lower limit is not less than the above-mentioned lower limit, pi-pi interaction with the phthalocyanine compound (1) tends to be promoted, and when the upper limit is not more than the above-mentioned upper limit, the alkali-soluble resin (c-1) tends to suppress a decrease in brightness due to yellowing at the time of firing in the color filter production step.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, having 2 free valences,A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Examples of the substituent optionally contained in the divalent hydrocarbon group include an alkoxy group, a halogen atom, and a carboxyl group.

The alkali-soluble resin (c-1) may further contain other repeating units.

The other repeating unit is preferably a repeating unit represented by the following general formula (II) from the viewpoint of forming hydrogen bond with the phthalocyanine compound (1) and improving curability in the production of a color filter by using an olefinic double bond.

In the formula (II), R ⁵ represents a hydrogen atom or a methyl group.

R ⁶ represents a trivalent hydrocarbon group optionally having a substituent.

R ⁷ represents a hydrogen atom or a methyl group.

As the trivalent hydrocarbon group optionally having a substituent in R ⁶, the groups listed in R ² can be preferably used. When R ⁶ contains an aromatic ring, the repeating unit containing an aromatic ring is not included, and when R ⁶ contains an alicyclic structure, the repeating unit containing an alicyclic structure is not included.

In addition, the other repeating unit is preferably a repeating unit represented by the following general formula (III) from the viewpoint of suppressing yellowing at the time of firing in the color filter production process.

In the formula (III), R ⁸ represents a hydrogen atom or a methyl group.

R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group optionally having a substituent.

(R⁹)

In the formula (III), R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group optionally having a substituent. Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon ring group. When R ⁹ contains an aromatic ring, the repeating unit containing an aromatic ring is not included, and when R ⁹ contains an alicyclic structure, the repeating unit containing an alicyclic structure is not included.

Examples of the monovalent aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group in which these groups are combined.

The number of carbon atoms of the monovalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, more preferably 5 or more, particularly preferably 7 or more, and is preferably 20 or less, more preferably 18 or less, more preferably 15 or less, particularly preferably 12 or less. When the lower limit value is not less than the upper limit value, yellowing at the time of firing in the color filter manufacturing process can be suppressed, and when the upper limit value is not more than the upper limit value, alkali developability at the time of manufacturing a color filter tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 1 to 20, more preferably 2 to 20, still more preferably 3 to 18, still more preferably 5 to 15, and particularly preferably 7 to 12.

Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, tetrahydrodicyclopentadiene and cyclohexyl. Among these, methyl or tetrahydrodicyclopentadiene is preferable from the viewpoint of suppressing yellowing by heat.

The monovalent aromatic hydrocarbon ring group is not particularly limited, and the carbon number is preferably 6 or more, and more preferably 12 or less. For example, it is preferably 6 to 12. When the ratio is equal to or higher than the lower limit, pi-pi interaction with the phthalocyanine compound (1) tends to be promoted, and when the ratio is equal to or lower than the upper limit, reduction in brightness due to yellowing at the time of firing in the color filter production step tends to be suppressed.

The aromatic hydrocarbon ring in the monovalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 1 free valence,A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. /(I)

Examples of the substituent optionally contained in the monovalent hydrocarbon group include an alkoxy group, an aryloxy group, and a halogen atom.

When the alkali-soluble resin (c-1) contains the repeating unit represented by the formula (I), the content is not particularly limited, but is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 35 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, particularly preferably 50 mol% or less, based on 100 mol% of the total number of repeating units in the alkali-soluble resin (c-1). When the content is not less than the above-mentioned lower limit, alkali developability is improved and hydrogen bond with the phthalocyanine compound (1) is likely to be formed firmly, and when the content is not more than the above-mentioned upper limit, thermal decomposition of the resin itself is likely to be suppressed. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 15 to 80 mol%, more preferably 20 to 70 mol%, still more preferably 30 to 60 mol%, particularly preferably 35 to 50 mol%.

When the alkali-soluble resin (c-1) contains the repeating unit represented by the formula (II), the content is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 12 mol% or more, still more preferably 15 mol% or more, particularly preferably 18 mol% or more, and further preferably 45 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less, and particularly preferably 30 mol% or less, based on 100 mol% of the total number of repeating units in the alkali-soluble resin (c-1). When the content is not less than the above-mentioned lower limit, alkali developability is improved and hydrogen bond with the phthalocyanine compound (1) is likely to be formed firmly, and when the content is not more than the above-mentioned upper limit, thermal decomposition of the resin itself is likely to be suppressed. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 5 to 45 mol%, more preferably 10 to 45 mol%, still more preferably 12 to 40 mol%, still more preferably 15 to 35 mol%, particularly preferably 18 to 30 mol%.

When the alkali-soluble resin (c-1) contains the repeating unit represented by the formula (III), the content is not particularly limited, and the total mole number of the repeating unit in the alkali-soluble resin (c-1) is preferably 1 mole% or more, more preferably 5 mole% or more, still more preferably 10 mole% or more, still more preferably 15 mole% or more, still more preferably 20 mole% or more, particularly preferably 25 mole% or more, and further preferably 50 mole% or less, more preferably 45 mole% or less, still more preferably 40 mole% or less, particularly preferably 35 mole% or less, based on 100 mole% of the total mole number of the repeating unit. When the lower limit is not less than the above-mentioned lower limit, yellowing due to thermal decomposition of the resin at the time of producing a color filter tends to be suppressed, and when the upper limit is not more than the above-mentioned upper limit, deterioration of alkali developability tends to be suppressed. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 45 mol%, still more preferably 15 to 45 mol%, still more preferably 20 to 40 mol%, and particularly preferably 25 to 35 mol%.

The alkali-soluble resin (C) in the colored resin composition of the present invention contains an alkali-soluble resin (C-1), and may further contain other alkali-soluble resins (C-2).

As the other alkali-soluble resin (c-2), for example, known polymer compounds described in JP-A7-207211, JP-A8-259876, JP-A10-300922, JP-A11-140144, JP-A11-174224, JP-A2000-56118, JP-A2003-233753 and JP-A2009-053652 among resins which do not conform to the alkali-soluble resin (c-1) can be used. Among them, the following resins (c-2-1) to (c-2-5) are preferable.

(C-2-1): for a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, a resin obtained by adding an unsaturated monoacid 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-2-1)")

(C-2-2) a linear alkali-soluble resin having a carboxyl group in the main chain (hereinafter sometimes referred to as "resin (c-2-2)")

(C-2-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl portion of the aforementioned resin (c-2-2) (hereinafter sometimes referred to as "resin (c-2-3)")

(C-2-4) (meth) acrylic resin (hereinafter sometimes referred to as "resin (c-2-4)")

(C-2-5) epoxy (meth) acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (c-2-5)")

Among them, the resin (c-2-1) is particularly preferably exemplified.

The resins (c-2-2) to (c-2-5) may be those having solubility to the extent that they can be dissolved in an alkaline developer and perform the target development treatment, and those described as the item in japanese patent application laid-open No. 2009-025813 may be preferably used.

The resin (c-2-1) is a resin obtained by adding an unsaturated monoacid to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, at least a part of the epoxy groups contained in 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.

As a preferred embodiment of the resin (c-2-1), there may be mentioned "a resin obtained by adding an unsaturated monobasic acid to 5 to 90 mol% of a (meth) acrylate containing an epoxy group and 10 to 95 mol% of another radically polymerizable monomer, 10 to 100 mol% of an epoxy group contained in the copolymer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction".

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, methyl (3, 4-epoxycyclohexyl) 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 an amount of 1 kind or in an amount of 2 or more kinds.

As the other radically polymerizable monomer 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～R⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ are optionally linked to each other to form a ring.

In the formula (V), the ring formed by connecting R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, and may be saturated or unsaturated, and the carbon number is preferably 5 to 6.

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

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

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

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

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

When the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer contains a repeating unit derived from the mono (meth) acrylate represented by the formula (VI), 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 unit derived from the other radically polymerizable monomer.

The radically polymerizable monomer other than the mono (meth) acrylate represented by the formula (VI) is not particularly limited, and specific examples thereof include vinyl aromatic compounds such as styrene, α -, o-, m-, p-alkyl groups of styrene, nitro groups, cyano groups, amides, and ester derivatives; 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, isopentyl (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, anthracene (meth) acrylate, anthracenyl nonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furanyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic esters such as 1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-N-propyl (meth) acrylate, perfluoro-isopropyl (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, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-diisopropylamide (meth) acrylate, anthrylamide (meth) acrylate, and the like; vinyl compounds such as (meth) acrylamides, (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; mono-maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloylphthalimide.

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

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

In the copolymerization reaction of the epoxy group-containing (meth) acrylate with another radically polymerizable monomer, a known solution polymerization method can be used. The solvent to be 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 and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, etc.; propylene glycol monoalkyl ether acetates; acetic acid esters such as dipropylene glycol monoalkyl ether acetate; glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol, and the like; 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, decane, etc.; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide, N-methylpyrrolidone. These solvents may be used alone or in combination of 2 or more.

The amount of the solvent used in the solution polymerization method is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, based on 100 parts by mass of the copolymer 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 peroxide, peroxyketal, hydrogen peroxide, diallyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate.

Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, diisopropylbenzene peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy (2-ethylhexanoate), t-hexyl peroxy2-ethylhexanoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyl-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene peroxide, diisopropylbenzene hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3, 5-trimethylhexanoyl peroxide, lauryl peroxide (laurylperoxide), 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, and 1, 1-bis (t-hexylperoxy) -3, 5-trimethylcyclohexane.

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

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

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

In the copolymerization reaction, the monomer and the radical polymerization initiator used in the copolymerization reaction may be dissolved in a solvent, and the temperature may be raised while stirring, the monomer to which the radical polymerization initiator is added may be dropwise added to the solvent in which the temperature is raised and the stirring is performed, or the radical polymerization initiator may be added to the solvent, and the monomer may be dropwise added while the temperature is raised.

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

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

By setting the content of the repeating unit derived from the epoxy group-containing (meth) acrylate to the above lower limit or more, the amount of the unsaturated monoacid or polybasic acid anhydride to be described later added tends to be sufficient.

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

With respect to the resin (c-2-1), an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) are reacted with an epoxy group of a copolymer of an epoxy group-containing (meth) acrylate and other radically polymerizable monomer.

As the unsaturated monoacid to be 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 monoacid added to the epoxy group include (meth) acrylic acid; crotonic acid; ortho-, meta-, para-vinylbenzoic acid; mono carboxylic acids such as (meth) acrylic acid in which the α -position is substituted 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 singly or in combination of 1 or more than 2.

By adding an unsaturated monobasic acid to an epoxy group, polymerizability can be imparted to the resin (c-2-1).

When the total of the epoxy groups contained in the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer is 100 mol%, the unsaturated monoacid is usually added to 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. When the lower limit value is not less than the above, the stability of the colored resin composition tends to be good with time.

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

The acid anhydride may be a known acid anhydride which is added to a hydroxyl group formed when an unsaturated monoacid is added to an epoxy group of a copolymer.

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 chlorobridge anhydride; and anhydrides of ternary or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferable. These polybasic acid anhydrides may be used singly or in combination of 1 or more than 2 kinds.

The base solubility of the resin (c-2-1) can be imparted by adding a polybasic acid anhydride to a hydroxyl group formed when an unsaturated monobasic acid is added to the epoxy group of the copolymer.

When the total of hydroxyl groups generated by adding an unsaturated monoacid to the epoxy groups of the copolymer is 100 mol%, the polybasic acid anhydride is usually added to 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. When the content is equal to or less than the upper limit, the residual film rate at the time of development tends to be good, and when the content is equal to or more than the lower limit, 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.

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

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.

These may be added in 1 kind alone or in combination of 2 or more kinds.

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

Commercially available products include trade names manufactured by Nagase ChemteX Corporation "DENACOL EX-111"、"DENACOL EX-121"、"DENACOL EX-141"、"DENACOL EX-145"、"DENACOL EX-146"、"DENACOL EX-171"、"DENACOL EX-192".

The structure of the resin (c-2-1) is described in, for example, JP-A-8-297366 and JP-A-2001-89533.

The weight average molecular weight of the resin (c-2-1) in terms of polystyrene as measured by GPC is not particularly limited, but is preferably 3000 or more, and particularly preferably 5000 or more. Preferably 100000 or less, particularly preferably 50000 or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 3000 to 100000, particularly preferably 5000 to 50000. When the lower limit value is not less than the upper limit value, the heat resistance and the film strength tend to be improved, and when the upper limit value is not more than the upper limit value, the solubility with respect to the developer tends to be improved.

As a criterion for molecular weight distribution, the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the resin (c-2-1) is preferably 2.0 to 5.0.

From the viewpoint of the curability of the coating film upon ultraviolet exposure, among the resins (c-2-4), the (c 1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain (hereinafter, sometimes referred to as (c 1) acrylic copolymer resin) is preferable.

(C1) The partial structure of the acrylic copolymer resin containing a side chain having an ethylenically unsaturated group is not particularly limited, and is preferably a partial structure represented by the following general formula (I') from the viewpoint of both the coating film curability upon uv exposure and the alkali solubility upon alkali development.

In the formula (I'), R ^1' and R ^2' each independently represent a hydrogen atom or a methyl group. * Representing an atomic bond.

Among the partial structures represented by the formula (I '), the partial structure represented by the following formula (II') is preferable from the viewpoints of sensitivity and alkali developability.

In the formula (II'), R ^1' and R ^2' each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polyacid residue.

The polyacid residue refers to a 1-valent group obtained by removing 1 OH group from a polyacid 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, chlorobridge acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic 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 singly or in combination of 1 or more than 2 kinds.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (I '), the content of the partial structure represented by the formula (I') contained in the (c 1) acrylic copolymer resin is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and further preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, still more 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 upper limit value, the coating film curability upon ultraviolet exposure tends to be improved, and when the upper limit value is not more than the upper limit value, the alkali solubility upon alkali development tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the partial structure represented by the formula (I') contained in the acrylic copolymer resin (c 1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 85 mol%, still more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (II '), the content of the partial structure represented by the formula (II') contained in the (c 1) acrylic copolymer resin is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and further preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, still more 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 upper limit value, the coating film curability upon ultraviolet exposure tends to be improved, and when the upper limit value is not more than the upper limit value, the alkali solubility upon alkali development tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the partial structure represented by the formula (I') contained in the acrylic copolymer resin (c 1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 85 mol%, still more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

(C1) When the acrylic copolymer resin contains a partial structure represented by the formula (I '), the partial structure is not particularly limited, and from the viewpoint of alkali solubility at the time of alkali development, for example, the acrylic copolymer resin preferably has a partial structure represented by the following general formula (III').

In the formula (III'), R ^3' represents a hydrogen atom or a methyl group, and R ^4' represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

(R^4')

In the formula (III'), R ^4' represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

Examples of the alkyl group in R ^4' include linear, branched or cyclic alkyl groups. The carbon number 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, particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 5 to 14, particularly preferably 8 to 12.

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

Examples of the substituent optionally included in the alkyl group include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, and methacryl. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferable.

Examples of the aromatic ring group in R ^4' include a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group. The carbon number is preferably 6 or more, more preferably 24 or less, still more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, still more preferably 6 to 20, particularly preferably 6 to 18.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and combinations thereof,Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single 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 included in the aromatic ring group include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferable.

Examples of the alkenyl group in R ^4' include a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, particularly preferably 2 to 14.

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

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

R ^4' represents an optionally substituted alkyl group, an optionally substituted aromatic ring group or an optionally substituted alkenyl group, and from the viewpoints of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (III '), the content of the partial structure represented by the formula (III') in the (c 1) acrylic copolymer resin is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, and 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 content is not less than the lower limit, alkali solubility tends to be improved, and when the content is not more than the upper limit, storage stability of the colored resin composition tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the partial structure represented by the formula (III') in the acrylic copolymer resin (c 1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, particularly preferably 20 to 40 mol%.

(C1) When the acrylic copolymer resin contains a partial structure represented by the formula (I '), the partial structure represented by the following formula (IV') is preferably contained as the partial structure contained in the resin, from the viewpoint of improving the alkali solubility of the phthalocyanine compound (1) by improving the affinity between the phthalocyanine compound (1) and the (c 1) acrylic copolymer resin.

In the formula (IV'), R ^5' represents a hydrogen atom or a methyl group, and 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 alkyl sulfide group optionally having a substituent. t represents an integer of 0 to 5.

(R^6')

In the formula (IV'), 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 optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group.

Examples of the alkyl group in R ^6' include linear, branched or cyclic alkyl groups. The carbon number 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 content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 3 to 14, particularly preferably 5 to 12.

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

Examples of the alkenyl group in R ^6' include a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, particularly preferably 2 to 14.

Examples of the alkenyl group include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl. 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.

Examples of the alkynyl group in R ^6' include a linear, branched or cyclic alkynyl group. The carbon number is preferably 2 or more, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the number of carbon atoms of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, particularly preferably 2 to 14.

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

Examples of the substituent optionally included in the alkynyl group include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl and carboxyl. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferable.

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

Examples of the alkoxy group in R ^6' include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, particularly preferably 1 to 12.

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

Examples of the substituent optionally contained in the alkoxy group include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, and methacryl. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferable.

Examples of the alkyl sulfide group in R ^6' include linear, branched or cyclic alkyl sulfide groups. The carbon number is preferably 1 or more, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the hydrophilicity and the solubility in a solvent tend to be improved, and when the content is equal to or lower than the upper limit, the hydrophilicity and the alkali solubility tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, 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, a methyl sulfide group and an ethyl sulfide group are preferable.

Examples of the substituent optionally included in the alkyl group in the alkyl sulfide group include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, and methacryl. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferable from the viewpoint of image developing devices.

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 alkyl sulfide group, and from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

In the formula (IV'), t represents an integer of 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (IV '), the content of the partial structure represented by the formula (IV') in the (c 1) acrylic copolymer resin 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, and 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 not less than the above-mentioned lower limit, the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin (c 1) tends to be improved and the alkali solubility tends to be improved, and when the content is not more than the above-mentioned upper limit, the content ratio of other partial structures tends to be increased and the alkali solubility tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the partial structure represented by the formula (IV') in the acrylic copolymer resin (c 1) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, still more preferably 5 to 30 mol%, particularly preferably 8 to 20 mol%.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (I '), the partial structure contained in the resin is preferably a partial structure represented by the following general formula (V') from the viewpoint of developability.

In the formula (V'), R ^7' represents a hydrogen atom or a methyl group.

(C1) When the acrylic copolymer resin has a partial structure represented by the formula (V '), the content of the partial structure represented by the formula (III') in the acrylic copolymer resin (c 1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less. When the content is not less than the lower limit, alkali solubility tends to be improved, and when the content is not more than the upper limit, storage stability of the colored resin composition tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the partial structure represented by the formula (III') in the acrylic copolymer resin (c 1) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even 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, more preferably 40mgKOH/g or more, more preferably 50mgKOH/g or more, particularly preferably 60mgKOH/g or more, still more preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, more preferably 200mgKOH/g or less, and still more preferably 150mgKOH/g or less. When the content is not less than the lower limit, alkali solubility tends to be improved, and when the content is not more than the upper limit, storage stability of the colored resin composition tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the acid value of the alkali-soluble resin (C) is preferably 10 to 300mgKOH/g, more preferably 30 to 300mgKOH/g, still more preferably 40 to 250mgKOH/g, still more preferably 50 to 200mgKOH/g, particularly preferably 60 to 150mgKOH/g.

(C) The weight average molecular weight of the alkali-soluble resin is not particularly limited, and is preferably 1000 or more, more preferably 2000 or more, more preferably 4000 or more, more preferably 6000 or more, still more preferably 7000 or more, particularly preferably 8000 or more, and further preferably 30000 or less, more preferably 20000 or less, more preferably 15000 or less, particularly preferably 10000 or less. When the lower limit value is not less than the upper limit value, the heat resistance and the coating film curability tend to be improved, and when the upper limit value is not more than the upper limit value, the alkali solubility tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, further preferably 4000 to 20000, further preferably 6000 to 20000, further preferably 7000 to 15000, 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, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, particularly preferably 30% by mass or more, and further preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass, based on the total solid content of the colored resin composition. When the lower limit value is not less than the above-mentioned lower limit value, a firm film tends to be obtained, and adhesion to a substrate tends to be excellent. Further, when the upper limit value is equal to or less than the above, the permeability of the developer to the exposed portion is low, and the surface smoothness and sensitivity of the pixel tend to be deteriorated. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the alkali-soluble resin (C) in the colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 60% by mass, still more preferably 20 to 60% by mass, particularly preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass, based on 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 the photopolymerization initiator (D), film curability by photopolymerization can be obtained.

(D) The photopolymerization initiator may be used as a mixture (photopolymerization initiator system) with an accelerator (chain transfer agent) and optionally an additive such as a sensitizing dye. The photopolymerization initiator system is a component having a function of directly absorbing light or photosensitizing light 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 a titanocene compound as described in Japanese unexamined patent application publication Nos. 59-152396 and 61-151197, hexaarylbisimidazole derivatives, halomethyl s-triazine derivatives, N-aryl- α -amino acids such as N-phenylglycine, free radical activators such as N-aryl- α -amino acid salts and N-aryl- α -amino acid esters as described in Japanese unexamined patent application publication No. 10-39503, α -aminoalkylbenzophenone compounds and oxime ester initiators as described in Japanese unexamined patent application publication No. 2000-80068.

Specific examples of photopolymerization initiators that can be used in the present invention are listed 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, 2-trichloromethyl-5-furanyl-1, 3, 4-oxadiazole and the like;

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, and (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer;

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

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-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-hydroxycyclohexyl phenyl ketone, α -hydroxy-2-methylphenyl acetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-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-dimethylbenzophenazine;

anthrone derivatives such as benzanthrone;

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) phenyl titanium and the like;

α -aminoalkyl phenones such as 2-methyl-1- [4- (methylsulfanyl) 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-dimethylaminopropiophenone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone;

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

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

Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in the structure, it has high sensitivity even in a small amount and is stable to thermal reaction, and a colored resin composition having high sensitivity even in a small amount can be designed. In particular, from the viewpoint of light absorptivity 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 optionally substituted alkyl group or an optionally substituted aromatic ring group.

R ^21b represents an optional substituent containing 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.

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

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

Examples of the substituent optionally included in the alkyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 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 preferred.

Examples of the aromatic ring group in R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, still more preferably 5 to 12, particularly preferably 5 to 8.

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

Examples of the substituent optionally included in the aromatic ring group include a hydroxyl group, an alkyl group optionally included in the aromatic ring group, an alkoxy group optionally included 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, hydroxyl groups and carboxyl groups are preferable, and carboxyl groups are more preferable. Examples of the substituent in the alkyl group optionally having a substituent or the alkoxy group optionally having a substituent include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. From the viewpoint of developability, R ^21a is preferably an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.

R ^21b is an optional substituent containing an aromatic or heteroaromatic ring. From the viewpoints of solubility in a solvent and sensitivity to exposure, a carbazolyl group optionally having a substituent, a thioxanthonyl group optionally having a substituent, a diphenyl sulfide group optionally having a substituent, a fluorenyl group optionally having a substituent, and a group in which these groups are bonded to a carbonyl group are preferable. From the viewpoint of light absorbability to i-rays (365 nm) of an exposure light source, a carbazolyl group optionally having a substituent or a group in which a carbazolyl group optionally having a substituent is linked to a carbonyl group is preferable.

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

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 5 or less, from the viewpoints of solubility in a solvent and sensitivity. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, still more preferably 2 to 5, particularly preferably 3 to 5.

Examples of the alkanoyl group include Acetyl (Acetyl), acetyl (Ethyloyl), propionyl and butyryl.

Examples of the substituent optionally included in the alkanoyl group include an aromatic ring 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 alkanoyl group is preferably unsubstituted.

The number of carbons of the aroyl group in R ^22a is not particularly limited, but is preferably 7 or more, more preferably 8 or more, still more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less from the viewpoints of solubility in a solvent and sensitivity. The upper limit and the lower limit may be arbitrarily combined. For example, the number of carbons of the aroyl group is preferably 7 to 20, more preferably 7 to 15, still more preferably 7 to 10, particularly preferably 8 to 10.

Examples of the aroyl group include benzoyl and naphthoyl.

Examples of the substituent optionally included 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 aroyl group is preferably unsubstituted.

The compound represented by the following general formula (I-2) or (I-3) is exemplified as the compound represented by the formula (I-1) from the viewpoint of light absorption of I-rays (365 nm) from an exposure light source.

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

R ^23a represents an optionally substituted alkyl group.

R ^24a represents an optionally substituted alkyl group, an optionally substituted aroyl group, an optionally substituted heteroaroyl group or a nitro group.

The benzene ring constituting the carbazole ring is optionally further condensed by an aromatic ring to form a polycyclic aromatic ring.

The carbon number of the alkyl group in R ^23a is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of solubility in a solvent. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 2 to 5.

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

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

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

The carbon number of the alkyl group in R ^24a is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of solubility in a solvent. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 2 to 5.

The number of carbons of the aroyl group in R ^24a is not particularly limited, but is preferably 7 or more, more preferably 8 or more, further preferably 9 or more, and is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 9 or less, from the viewpoint of solubility in a solvent. The upper limit and the lower limit may be arbitrarily combined. For example, the number of carbons 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 benzoyl and naphthoyl.

Examples of the substituent optionally included in the aroyl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. Ethyl is preferred from the viewpoint of ease of synthesis.

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

Examples of heteroaryl groups include fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl and bromonaphthoyl.

Examples of the substituent optionally included in the heteroaroyl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. From the viewpoint of ease of synthesis, non-substitution is preferred.

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 the commercial products of the oxime ester compound include OXE-02, OXE-03, TR-PBG-304, TR-PBG-314, and N-1919, NCI-930, and NCI-831, both manufactured by BASF corporation, and manufactured by Hezhou powerful electronic New materials, inc.

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

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These photopolymerization initiators may be used alone or in combination of at least 2.

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

The chain transfer agent may be any compound having the above-mentioned function, and various chain transfer agents may be used, and examples thereof include mercapto group-containing compounds and carbon tetrachloride, and mercapto group-containing compounds are more preferably used in view of the tendency of high chain transfer effect. The reason is considered to be that the S-H bond energy is small, and thus bond cleavage, hydrogen abstraction reaction, and chain transfer reaction are liable to occur. Is effective in improving sensitivity and surface curability.

Examples of the mercapto-containing compound include mercapto-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-containing compounds such as hexanedithiol, decanedithiol, butanediyl bis (3-mercaptopropionate), butanediyl dimercaptoacetate, ethyleneglycol bis (3-mercaptopropionate), ethyleneglycol dimercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trimercaptate, trishydroxyethyl trimercaptate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediyl bis (3-mercaptobutyrate), ethyleneglycol bis (3-mercaptobutyrate), trimethylol propane 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 surface smoothness, a compound having a plurality of mercapto groups is preferable.

As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable, and as the aliphatic mercapto group-containing compound, 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 are preferable.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, trimethylol propane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylol propane 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, more preferable are pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

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

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, further preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 6% by mass or less, of the total solid content of the colored resin composition. When the ratio is equal to or higher than the lower limit, patterning characteristics after development tend to be ensured, and when the ratio is equal to or lower than the upper limit, transmittance degradation due to excessive addition of a photopolymerization initiator tends to be suppressed. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the photopolymerization initiator (D) in the colored resin composition is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, still more preferably 3 to 8% by mass, and particularly preferably 4 to 6% by mass, based on the total solid content of the colored resin composition.

The content ratio of the chain transfer agent in the colored resin composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, still more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less, based on the total solid content of the colored resin composition. When the solvent resistance is set to the above lower limit or more, the solvent resistance tends to be improved, and when the solvent resistance is set to the above upper limit or less, the storage stability tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, when the colored resin composition contains the chain transfer agent, the content thereof is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, still more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1% by mass, based on the total solid content of the colored resin composition.

[1-5] (E) photopolymerizable monomer

(E) The photopolymerizable monomer is not particularly limited as long as it is a low molecular compound capable of polymerization, 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 undergoes addition polymerization and curing by the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with active light. The monomer in the present invention is a concept of a polymer, and includes a concept of a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.

In the present invention, it is particularly desirable to use a polyfunctional olefinic monomer having 2 or more olefinic double bonds in 1 molecule. The number of olefinic double bonds in the polyfunctional olefinic monomer is not particularly limited, but is preferably 2 or more, more preferably 4 or more, further preferably 5 or more, further preferably 8 or less, and further preferably 7 or less. When the lower limit value is equal to or higher than the above-mentioned lower limit value, the sensitivity tends to be high, and when the upper limit value is equal to or lower than the above-mentioned upper limit value, the solubility in a solvent tends to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the number of olefinic double bonds of the polyfunctional olefinic monomer is preferably 2 to 8, more preferably 2 to 7, still more preferably 4 to 7, and particularly preferably 5 to 7.

Examples of the olefinic compound 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 esterification of an unsaturated carboxylic acid and a polycarboxylic acid with a polyhydroxy compound such as the aliphatic polyhydroxy compound and the aromatic polyhydroxy compound, and an olefinic compound having a urethane skeleton obtained by reaction of a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic esters such as ethylene glycol diacrylate, triethylene 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 in which the acrylic acid moiety of the acrylic acid ester is replaced with a methacrylic acid moiety, itaconic acid esters in which the acrylic acid moiety is replaced with an itaconic acid moiety, crotonates in which the acrylic acid moiety is replaced with a crotonic acid moiety, and maleates in which the acrylic acid moiety is replaced with a maleic acid moiety.

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

The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polycarboxylic acid and the polyhydroxy compound is not necessarily a single substance, but may be a mixture. Examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensation products of methacrylic acid, terephthalic acid and pentaerythritol; condensation products 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 reactants of an aliphatic diisocyanate such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, an alicyclic diisocyanate such as cyclohexane diisocyanate and isophorone diisocyanate, an aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, and a (meth) acryloyl group-containing hydroxyl compound such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1, 1-triacrylate oxymethyl) propane and 3-hydroxy (1, 1-trimethacryloyloxymethyl) propane.

Examples of the olefinic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate.

The olefinic compound 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 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.

Although 1 kind of these monomers may be used alone, 2 or more kinds of these monomers may be used in combination because it is difficult to use a single compound in production. In addition, a polyfunctional monomer having no acid group may be used as a monomer in combination with a polyfunctional monomer having an acid group as required.

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

In the present invention, the more preferable polyfunctional monomer having an acid group is a mixture of succinic acid esters of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate, which are sold as TO1382, manufactured by Toyo Kagaku Co. The multifunctional monomer may also be used in combination with other multifunctional monomers. Further, the polyfunctional monomers described in paragraphs [0056] and [0057] of Japanese patent application laid-open No. 2013-140346 may be used.

In the present invention, the polymerizable monomer described in japanese patent application laid-open No. 2013-195971 is preferable from the viewpoints of improving chemical resistance of the pixel and linearity of the pixel edge.

From the viewpoint of both the coating film sensitivity and the reduction of the development time, the polymerizable monomer described in JP-A2013-195974 is preferable.

In the colored resin composition of the present invention, the content ratio of the (E) photopolymerizable monomer is not particularly limited, but is preferably more than 0 mass%, more preferably 5 mass% or more, still more preferably 10 mass% or more, still more preferably 15 mass% or more, particularly preferably 20 mass% or more, and further preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, still more preferably 40 mass% or less, particularly preferably 30 mass% or less, of the total solid content of the colored resin composition. When the lower limit value is not less than the upper limit value, the coating film tends to be cured more, and when the upper limit value is not more than the upper limit value, the alkali developability tends to be suppressed. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the photopolymerizable monomer (E) is preferably more than 0 mass% and 70 mass% or less, more preferably 5 to 60 mass%, still more preferably 10 to 50 mass%, still more preferably 15 to 40 mass%, and particularly preferably 20 to 30 mass% of the total solid content of the colored resin composition.

[1-6] Other solid Components

The colored resin composition of the present invention may further contain solid components other than the above components, if necessary. Examples of such components include dispersants, dispersion aids, surfactants, and antioxidants.

[1-6-1] Dispersant, dispersing aid

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

Examples of the polymer 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 such dispersants include dispersants described by the trade names EFKA (registered trademark, manufactured by BASF corporation), disperbyk (registered trademark, manufactured by BYK-Chemie corporation), DISPARON (registered trademark, manufactured by Mach-Zehnder corporation), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by Xinyue chemical industry Co., ltd.), polyflow (manufactured by co-Rong chemical Co., ltd.), and Japanese patent application laid-open No. 2013-119568.

Among the polymer dispersants, a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer is more preferable from the viewpoints of dispersibility and storage stability.

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

Examples of the functional group containing a nitrogen atom include a primary to tertiary amino group and a quaternary ammonium salt group, and from the viewpoints of dispersibility and storage stability, a primary to tertiary amino group is preferable, and a tertiary amino group is more preferable.

The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, and the repeating unit represented by the following general formula (F1) is preferable from the viewpoints of dispersibility and storage stability.

In the above formula (F1), R ¹ and R ² are each independently 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, and R ¹ and R ² are optionally bonded to each other to form a cyclic structure. R ³ is a hydrogen atom or a methyl group. X is a divalent linking group.

The carbon number of the alkyl group optionally having a substituent in R ¹ and R ² of the above formula (F1) is not particularly limited, but is preferably 1 or more, and further 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 methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, and methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferable, and methyl, ethyl, propyl, and butyl are more preferable. The alkyl group in the above formula (F1) may be either a straight chain or a branched chain. The alkyl group in the above formula (F1) optionally contains a cyclic structure such as a cyclohexyl group or methylcyclohexyl group.

The carbon number of the aryl group optionally having a substituent in R ¹ and R ² of the above formula (F1) is not particularly limited, but is preferably 6 or more, and is 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 phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl and anthracenyl groups, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl and diethylphenyl groups, more preferably phenyl, methylphenyl and ethylphenyl groups.

The carbon number of the aralkyl group optionally having a substituent in R ¹ and R ² of the above formula (F1) is not particularly limited, but is preferably 7 or more, and is 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 phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and preferably a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group, and more preferably a phenylmethyl group and a phenylethyl group.

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

The substituent optionally contained in the alkyl group, aralkyl group or aryl group in R ¹ and R ² of the above formula (F1) may be, for example, a halogen atom, an alkoxy group, a benzoyl group or a hydroxyl group, and is preferably unsubstituted from the viewpoint of ease of synthesis.

In the above formula (F1), examples of the cyclic structure formed by bonding R ¹ and R ² to each other include a nitrogen-containing heterocyclic monocyclic ring having five to seven membered rings, or a condensed ring formed by condensing 2 of these rings. The nitrogen-containing heterocycle is preferably not aromatic, and is more preferably saturated. Specifically, nitrogen-containing heterocycles of the following formula (F4) are exemplified.

The cyclic structure of the above formula (F4) may optionally further have a substituent.

In the above formula (F1), examples of the divalent linking group X include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ¹³ -group, -COOR ¹⁴ -group (wherein R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms), and are preferably-COO-R ¹⁴ -group.

The content of the repeating unit represented by the formula (F1) in the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, still more preferably 15 mol% or more, particularly preferably 20 mol% or more, most preferably 25 mol% or more, and further preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, and particularly preferably 40 mol% or less based on the total repeating units. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the repeating unit represented by the formula (F1) in the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, still more preferably 10 to 70 mol%, still more preferably 15 to 70 mol%, particularly preferably 20 to 50 mol%, and most preferably 25 to 40 mol% based on the total repeating units. In the case of the above range, both dispersion stability and high brightness tend to be achieved.

The block copolymer preferably has a repeating unit represented by the following formula (F2) from the viewpoints of improving compatibility with a binder component such as a solvent and improving dispersion stability.

In the above formula (F2), R ¹⁰ is ethylene or propylene, R ¹¹ is alkyl optionally having a substituent, and R ¹² is a hydrogen atom or methyl.

N is an integer of 1 to 20.

The carbon number of the alkyl group optionally having a substituent in R ¹¹ of the above formula (F2) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. The upper limit and the lower limit may be arbitrarily combined. For example, the carbon number of the alkyl group in R ¹¹ of the above formula (F2) is preferably 1 to 10, more preferably 1 to 6, still more preferably 2 to 4.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, and methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferable, and methyl, ethyl, propyl, and butyl are more preferable.

The alkyl group in R ¹¹ of the above formula (F2) may be either a straight chain or a branched chain.

The alkyl group in R ¹¹ of the above formula (F2) optionally contains a cyclic structure such as cyclohexyl and methylcyclohexyl.

Examples of the substituent optionally included in the alkyl group in R ¹¹ of the above formula (F2) include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

From the viewpoints of compatibility with and dispersibility in a binder component such as a solvent, n in the above formula (F2) is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.

The content of the repeating unit represented by the formula (F2) in 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 based on the total repeating units. The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the repeating unit represented by the formula (F2) in the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol% based on the total repeating units. In the case of the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be compatible.

In addition, from the viewpoint of improving compatibility with a binder component such as a solvent and improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (F3).

In the above formula (F3), R ⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. R ⁹ is a hydrogen atom or a methyl group.

The carbon number of the alkyl group optionally having a substituent in R ⁸ of the above formula (F3) is not particularly limited, but is preferably 1 or more, and is preferably 10 or less, more preferably 6 or less. For example, it is preferably 1 to 10, more preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, and methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferable, and methyl, ethyl, propyl, and butyl are more preferable.

The alkyl group in R ⁸ of the above formula (F3) may be either a straight chain or a branched chain.

The alkyl group in R ⁸ of the above formula (F3) optionally contains a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The carbon number of the aryl group optionally having a substituent in R ⁸ of the above formula (F3) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, more preferably 12 or less. For example, it is preferably 6 to 16, more preferably 6 to 12. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl and anthracenyl groups, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl and diethylphenyl groups, more preferably phenyl, methylphenyl and ethylphenyl groups.

The carbon number of the aralkyl group optionally having a substituent in R ⁸ of the above formula (F3) is not particularly limited, but is preferably 7 or more, and is preferably 16 or less, more preferably 12 or less. For example, it is preferably 7 to 16, more preferably 7 to 12. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and preferably a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group, and more preferably a phenylmethyl group and a phenylethyl group.

From the viewpoints of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl group.

Examples of the substituent optionally contained in the alkyl group in R ⁸ include a halogen atom and an alkoxy group. Examples of the substituent optionally included in the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, and an alkoxy group. The chain alkyl group represented by R ⁸ includes a straight chain and a branched chain.

The content of the repeating unit represented by the formula (F3) in the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less based on the total repeating units. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the repeating unit represented by the formula (F3) in the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol% based on the total repeating units. In the case of the above range, both dispersion stability and high brightness tend to be achieved.

The block copolymer may have a repeating unit other than the repeating unit represented by the general formula (F1), the repeating unit represented by the general formula (F2), and the repeating unit represented by the general formula (F3). Examples of such a repeating unit include repeating units derived from: styrene monomers such as styrene and α -methylstyrene; (meth) acrylic acid salt-based 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; n-methacryloyl morpholine.

From the viewpoint of further improving dispersibility, the block copolymer is preferably ase:Sub>A block copolymer comprising an ase:Sub>A block having ase:Sub>A repeating unit represented by the above general formulase:Sub>A (F1) and ase:Sub>A B block having no repeating unit represented by the above general formulase:Sub>A (F1), and more preferably an ase:Sub>A-B block copolymer or ase:Sub>A B-ase:Sub>A-B block copolymer. The B block preferably has a repeating unit represented by the aforementioned general formula (F2) and a repeating unit represented by the aforementioned general formula (F3).

The A block may contain a repeating unit other than the repeating unit represented by the general formula (F1). Examples of such a repeating unit include repeating units derived from the (meth) acrylate monomer. The content of the repeating units other than the repeating units represented by the general formula (F1) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, the A block does not contain a repeating unit other than the repeating unit represented by the general formula (F1).

The B block may contain a repeating unit other than the repeating unit represented by the above general formula (F2) and the repeating unit represented by the above general formula (F3). Examples of such a repeating unit include repeating units derived from: styrene monomers such as styrene and α -methylstyrene; (meth) acrylic acid salt-based 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; n-methacryloyl morpholine. The content of the repeating unit other than the repeating unit represented by the above general formula (F2) and the repeating unit represented by the above general formula (F3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, the B block does not contain a repeating unit other than the repeating unit represented by the above general formula (F2) and the repeating unit represented by the above general formula (F3).

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

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

The amine value represents an amine value converted from an effective solid content, and is a value expressed by the mass of KOH corresponding to the amount of alkali per 1g of solid content.

The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of weight average molecular weight (Mw). In the above range, the following tends to occur: the dispersion stability is improved, and dry foreign matter is less likely to be generated when coating is performed by a 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 having each of the above-mentioned repeating units introduced therein. As the living polymerization method, for example, known methods described in JP-A9-62002, JP-A2002-31713, 、P.Lutz,P.Masson et al,Polym.Bull.12,79(1984)、B.C.Anderson,G.D.Andrews et al,Macromolecules,14,1601(1981)、K.Hatada,K.Ute,et al,Polym.J.17,977(1985),K.Hatada,K.Ute,et al,Polym.J.18,1037(1986)、, ji-Tian, polymer processing, 36,366 (1987), dongcunmin-Ming-Can, zehnguang-Man, polymer theory, 46,189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Soc,109,4737 (1987), xiang Tianzhuo, ji-Ping-Pong, organic Synthesis chemistry, 43,300 (1985), D.Y.Sogoh, W.R.Hertler et al, macromolecules,20,1473 (1987) can be used.

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 mass% or more, more preferably 0.01 mass% or more, further preferably 0.1 mass% or more, particularly preferably 1 mass% or more, and further preferably 25 mass% or less, more preferably 20 mass% or less, further preferably 15 mass% or less, particularly preferably 10 mass% or less, of the total solid content of the colored resin composition. When the content is not less than the lower limit, dispersibility and storage stability tend to be improved. When the upper limit value is less than or equal to the above-described upper limit value, the electric reliability and the developing property tend to be improved. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the dispersant in the total solid content of the colored resin composition is preferably 0.001 to 25% by mass, more preferably 0.01 to 20% by mass, still more preferably 0.1 to 15% by mass, and particularly preferably 1 to 10% by mass.

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

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

Examples of the pigment derivative include derivatives of azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoline-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, pyrenone-based, diketopyrrolopyrrole-based, and dioxazine-based pigments.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group, a quaternary salt of a sulfonamide group, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group, and examples of the substituent include a group obtained by bonding or directly bonding the substituent to a pigment skeleton via an alkyl group, an aryl group, and a heterocyclic group. The substituent is preferably a sulfonamide group, a quaternary salt of a sulfonamide group, or a sulfonic acid group, and more preferably a sulfonic acid group.

The pigment may have a plurality of substituents substituted on one pigment skeleton, or may be a mixture of compounds having different numbers of substituents.

Specific 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

The colored resin composition of the present invention may contain a surfactant, and as the surfactant, various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants may be used, and from the viewpoint of low possibility of adversely affecting the respective characteristics, nonionic surfactants are preferable. When the colored resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, still more preferably 0.05 mass% or more, particularly preferably 0.1 mass% or more, and further preferably 10 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.3 mass% or less, based on the total solid content of the colored resin composition. The upper limit and the lower limit may be arbitrarily combined. For example, the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, still more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass, based on the total solid content of the colored resin composition.

[2] Preparation of colored resin composition

In the case of preparing a colored resin composition containing a pigment as the colorant of (a), for example, a pigment dispersion is prepared by weighing a prescribed amount of the pigment, a solvent and a dispersant, respectively, and dispersing the colorant containing the pigment in a dispersion treatment step. As described above, in the dispersion treatment step, for example, a dispersion aid and/or a dispersion resin are preferably used in combination.

In the dispersion treatment step, for example, a paint shaker, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, and a homogenizer can be used. By performing the dispersion treatment, the colorant is micronized, and therefore, the coating property of the colored resin composition is improved, and the transmittance of pixels in the color filter substrate as a product is improved. When the dispersion treatment is carried out by using a sand mill, glass beads or zirconia beads having a diameter of 0.1 to several mm are preferably used.

The temperature during the dispersion treatment is preferably set to 0℃or higher, more preferably set to room temperature (e.g., 25 ℃) or higher, and is preferably set to 100℃or lower, more preferably set to 80℃or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature may be set to 0 to 100 ℃,0 to 80 ℃, or room temperature to 80 ℃. The proper time for the dispersion time varies depending on the composition of the pigment dispersion and the size of the apparatus of the sand mill, and therefore, the dispersion time may be properly adjusted.

A uniform dispersion solution is prepared by mixing a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, and if necessary, other components than those described above, with the pigment dispersion obtained in the dispersion treatment step. In the dispersion treatment step and the mixing step, fine dirt may be mixed, and therefore, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.

In the preparation of the colored resin composition containing no pigment in the colorant (a), the solvent (B), the alkali-soluble resin (C), the photopolymerization initiator (D), and the photopolymerizable monomer (E), as required, other components than the above, and the like can be mixed and obtained as a homogeneous solution. The resulting solution is preferably subjected to filtration treatment using a filter or the like.

(C) The alkali-soluble resin (c-1) having a repeating unit containing an aromatic ring in a side chain contained in the alkali-soluble resin is preferably a resin obtained by polymerizing a monomer mixture containing a monomer containing an aromatic ring. Further, the monomer mixture more preferably contains a monomer having an alicyclic structure. The alicyclic structure is more preferably a saturated alicyclic structure. Particularly preferred is a resin obtained by polymerizing a monomer mixture containing a (meth) acrylic monomer having an aromatic ring and a (meth) acrylic monomer having an alicyclic structure.

[3] Manufacture of color filter substrate

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

[3-1] Transparent substrate (support)

The transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate 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, epoxy resins, thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, various glasses, and the like. Among them, glass or heat-resistant resin is preferable from the viewpoint of heat resistance.

In order to improve the surface physical properties such as adhesion, the transparent substrate and the substrate provided with a black matrix described later may be subjected to a corona discharge treatment, an ozone treatment, a 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 preferably 0.05mm or more, more preferably 0.1mm or more, and is preferably 10mm or less, more preferably 7mm or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 0.05 to 10mm, more preferably 0.1 to 7mm.

In addition, when the film forming treatment of various resins is performed, the film thickness is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 10 μm or less, more preferably 5 μm or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 0.01 to 10. Mu.m, more preferably 0.05 to 5. Mu.m.

[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 preferably forming a pixel image of red, green, and blue. The colored resin composition of the present invention is preferably used as a coating liquid for forming green pixels (resist patterns) among red, green and blue pixels. The pixel image is formed by performing various treatments such as coating, heat drying, image exposure, development, and firing 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 green pixel (resist pattern) formation.

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

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

In this case, first, a thin film of the metal or metal/metal oxide is formed on a transparent substrate by vapor deposition, sputtering, or the like. 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 of stripes, mosaics, triangles, and the like, thereby forming 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 colored resin composition containing a black colorant is used to form a black matrix. For example, a Black matrix can be formed by using a colored resin composition containing one or more of Black materials such as carbon Black, graphite, iron Black, aniline Black, cyanine Black (Cyanine Black), titanium Black, or the like, or a Black material obtained by mixing red, green, blue, or the like appropriately selected from inorganic or organic pigments and dyes, in the same manner as the method for forming a red, green, or blue pixel image described later.

[3-3] Formation of pixels

A colored resin composition of one of red, green, and blue is applied to a transparent substrate provided with a black matrix, and after drying, a photomask is superimposed on the coating film, and an image is exposed, developed, and thermally cured or photo-cured as necessary through the photomask, thereby forming a pixel image. This operation is performed on the colored resin compositions of three colors of red, green, and blue, respectively, whereby a color filter image can be formed.

The colored resin composition for color filters can be applied by spin coating, bar coating, flow coating, die coating, roll coating, spray coating, or the like. Among them, the use of the die coating method is preferable from the standpoint of the overall point of view that the amount of the coating liquid can be greatly reduced, the influence of mist or the like adhering when coating by the spin coating method is completely avoided, and the generation of foreign matters or the like can be suppressed.

When the thickness of the coating film is too large, development of the pattern becomes difficult, and in the liquid crystal cell formation step, it may be difficult to adjust the gap, while when too small, it may be difficult to increase the pigment concentration, and a desired color may not be exhibited. The thickness of the coating film is preferably 0.2 μm or more, more preferably 0.5 μm or more, still more preferably 0.8 μm or more, and further preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, in terms of the film thickness after drying. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 0.2 to 20. Mu.m, more preferably 0.5 to 10. Mu.m, still more preferably 0.8 to 5. Mu.m.

[3-4] Drying of coating film

The drying of the coating film after the colored resin composition is coated on the substrate is preferably based on a drying method using a hot plate, an IR oven, or a convection oven. Generally, after the pre-drying, the coating film is dried by heating again. The conditions for the preliminary drying may be appropriately selected depending on the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is preferably 40 ℃ or higher, more preferably 50 ℃ or higher, and further preferably 80 ℃ or lower, more preferably 70 ℃ or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature is preferably 40 to 80℃and more preferably 50 to 70 ℃. The drying time is preferably 15 seconds or more, more preferably 30 seconds or more, and is preferably 5 minutes or less, more preferably 3 minutes or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 15 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.

The temperature condition for the reheating drying is preferably a temperature higher than the pre-drying temperature, specifically, preferably 50 ℃ or higher, more preferably 70 ℃ or higher, further preferably 200 ℃ or lower, more preferably 160 ℃ or lower, further preferably 130 ℃ or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature is preferably 50 to 200 ℃, more preferably 50 to 160 ℃, and still more preferably 70 to 130 ℃. The drying time varies depending on the heating temperature, and is preferably 10 seconds or more, more preferably 15 seconds or more, and is preferably 10 minutes or less, more preferably 5 minutes or less. The upper limit and the lower limit may be arbitrarily combined. For example, it is preferably 10 seconds to 10 minutes, more preferably 15 seconds to 5 minutes. When the drying temperature is too high, the alkali-soluble resin may decompose, and thermal polymerization may be induced, resulting in development failure. As the drying step of the coating film, a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be used.

[3-5] Exposure procedure

The image exposure is performed by superimposing a negative matrix pattern on a coating film of the colored resin composition and irradiating the coating film with ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, an oxygen blocking 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: light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and the like; and laser 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] Development procedure

After image exposure of a coating film using the colored resin composition of the present invention with the above light source, development is performed using an aqueous solution containing a surfactant and an alkaline compound, whereby an image can be formed on a substrate to produce a color filter of the present invention. The aqueous solution may further contain 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 hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogenphosphate, potassium hydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, 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 may be used alone or in combination of 1 or more than 2.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoalkyl glycerides (Monoglyceride ALKYL ESTER), anionic surfactants such as alkylbenzenesulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates, 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. The organic solvent may be used in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited, and the development temperature is preferably 10 ℃ or higher, more preferably 15 ℃ or higher, further preferably 20 ℃ or higher, and further preferably 50 ℃ or lower, more preferably 45 ℃ or lower, further preferably 40 ℃ or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature is preferably 10 to 50 ℃, more preferably 15 to 45 ℃, and still more preferably 20 to 40 ℃.

The developing method may be based on any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method, and the like.

Firing [3-7]

Firing is performed on the color filter after development. The firing conditions in this case are preferably selected so that the temperature is in the range of 100℃or higher, more preferably 150℃or higher, and preferably 280℃or lower, more preferably 250℃or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature is preferably 100 to 280℃and more preferably 150 to 250 ℃. The time is selected in the range of 5 minutes to 60 minutes. Through this series of processes, the patterned image formation of one color is completed. This process is repeated in order, and black, red, green, and blue are patterned to form a color filter. The order of patterning the 4 colors is not limited to the above.

[3-8] Formation of transparent electrode

The color filter of the present invention can be used as a part of a member such as a color display or a liquid crystal display device by forming a transparent electrode such as ITO on an image in such a state, but may be provided with a surface coating such as polyamide or polyimide on the image as required in order to improve surface smoothness and durability. In some in-plane-oriented drive systems (IPS mode) and other applications, a transparent electrode may not be formed.

[4] Image display device (Panel)

The image display device of the present invention is provided with the color filter of the present invention.

A liquid crystal display device and an organic EL display device as an image display device will be described in detail below.

[4-1] Liquid crystal display device

A method for manufacturing a liquid crystal display device according to 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 a color filter of the present invention, and a spacer is arranged 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. When forming an alignment film, a gravure printing method and/or a flexographic printing method are generally used, and the thickness of the alignment film is set to be 10nm. After the curing treatment of the alignment film by firing, the surface treatment is performed by ultraviolet irradiation or treatment with rubbing cloth, so that the tilt of the liquid crystal can be adjusted.

The spacer may have a thickness corresponding to the gap (gap) between the counter substrates, and the thickness is preferably 2 to 8 μm. Photo Spacers (PS) of a transparent resin film may be formed on the color filter substrate by photolithography, and may be used instead of the spacers. 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 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 inlet is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating and the liquid crystal cell is sealed around.

The liquid crystal cell sealed around is cut into panel units, then the vacuum chamber is depressurized, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal leaks into the chamber, whereby the liquid crystal is injected into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is preferably 1×10 ^-2 Pa or less, more preferably 1×10 ^-3 Pa or less, and further preferably 1×10 ^-7 Pa or more, more preferably 1×10 ^-6 Pa or more. The upper limit and the lower limit may be arbitrarily combined. Preferably 1X 10 ^-7～1×10^-2 Pa, more preferably 1X 10 ^-6～1×10^-3 Pa. The liquid crystal cell is preferably heated at a reduced pressure, and the heating temperature is preferably 30 ℃ or higher, more preferably 50 ℃ or higher, and further preferably 100 ℃ or lower, more preferably 90 ℃ or lower. The upper limit and the lower limit may be arbitrarily combined. For example, the temperature is preferably 30 to 100℃and more preferably 50 to 90 ℃.

The temperature rise during the depressurization is maintained in the range of 10 minutes to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell injected with the liquid crystal is cured with the UV curable resin to seal the liquid crystal injection port, thereby completing the liquid crystal display device (panel).

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

[4-2] Organic EL display device

In the case of manufacturing an organic EL display device having the color filter of the present invention, for example, as shown in fig. 1, a pixel 20 is formed on a transparent support substrate 10 using the colored resin composition of the present invention, and an organic light-emitting element 500 is laminated on a blue color filter on which the pixel 20 is formed via an organic protective layer 30 and an inorganic oxide film 40, thereby manufacturing a multicolor organic EL element 100.

As a lamination method of the organic light-emitting body 500, there can be mentioned: 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; and a method of bonding the organic light-emitting body 500 formed on the other 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 driving system or an organic EL display device of an active driving 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 unless the gist thereof is exceeded.

< Phthalocyanine Compound A >

A phthalocyanine compound A having the following chemical structure, which was synthesized based on example 30 of Japanese patent application laid-open No. 05-345861, was used.

< Dispersant A >

A methacrylic AB block copolymer comprising an A block having a functional group containing a nitrogen atom and a B block having a solvophilic group. Comprises 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 formulas (1 a), (2 a), (3 a), (4 a) and (5 a) in the total repeating units was 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 replaced with nitrogen, and the temperature was raised to 120 ℃. To this were added dropwise a mixture of 38.5 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi chemical Co., ltd.) over 3 hours, and further 8.47 parts by mass of 2.2' -azobis-2-methylbutyronitrile, followed by stirring at 90℃for 2 hours. Then, the reaction vessel was replaced with air, and 0.3 parts by mass of tris (dimethylaminomethyl) phenol and 0.06 parts by mass of hydroquinone were charged into 11.8 parts by mass of acrylic acid, and the reaction was continued at 120℃for 6 hours. Thereafter, 43.6 parts by mass of Succinic Anhydride (SA) and 1.4 parts by mass of triethylamine were added, and the mixture was reacted at 120℃for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin A thus obtained was about 9000 in terms of polystyrene as measured by GPC, the acid value was 100mgKOH/g, and the double bond equivalent was 410g/mol. When the total mole number of the repeating units in the alkali-soluble resin a is 100 mole%, the repeating unit having an aromatic ring in the side chain is 37 mole%, and the repeating unit having a saturated alicyclic structure in the side chain is 3 mole%, and the alkali-soluble resin a corresponds to the alkali-soluble resin (c-1).

Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content became 40 mass%, and the resin solution was used as an alkali-soluble resin A to prepare a colored resin composition.

< Alkali-soluble resin B >

145 Parts by mass of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. To this were added dropwise a mixture of 38.5 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi chemical Co., ltd.) over 3 hours, and further 8.47 parts by mass of 2.2' -azobis-2-methylbutyronitrile, followed by stirring at 90℃for 2 hours. Then, the reaction vessel was replaced with air, and 0.3 parts by mass of tris (dimethylaminomethyl) phenol and 0.06 parts by mass of hydroquinone were charged into 11.8 parts by mass of acrylic acid, and the reaction was continued at 120℃for 6 hours. Thereafter, 66.3 parts by mass of tetrahydrophthalic anhydride (THPA) and 1.4 parts by mass of triethylamine were added, and the mixture was reacted at 120℃for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene as measured by GPC of the alkali-soluble resin B thus obtained was about 14000, the acid value was 100mgKOH/g, and the double bond equivalent was 440g/mol. When the total mole number of the repeating units in the alkali-soluble resin B is 100 mole%, the repeating unit having an aromatic ring in the side chain is 37 mole% and the repeating unit having a saturated alicyclic structure in the side chain is 3 mole%, and the alkali-soluble resin B corresponds to the alkali-soluble resin (c-1).

Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content became 40 mass%, and the resin solution was used as an alkali-soluble resin B to prepare a colored resin composition.

< Alkali-soluble resin C >

145 Parts by mass of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. To this was added dropwise 10.4 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi chemical Co., ltd.) in 3 hours, and a mixture of 8.47 parts by mass of 2.2' -azobis-2-methylbutyronitrile was further added dropwise, and stirring was continued at 90℃for 2 hours. Then, the reaction vessel was replaced with air, and 0.3 parts by mass of tris (dimethylaminomethyl) phenol and 0.06 parts by mass of hydroquinone were charged into 15.1 parts by mass of acrylic acid, and the reaction was continued at 120℃for 6 hours. Thereafter, 59.3 parts by mass of tetrahydrophthalic anhydride (THPA) and 1.4 parts by mass of triethylamine were added, and the mixture was reacted at 120℃for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene as measured by GPC of the alkali-soluble resin C thus obtained was about 9000, the acid value was 80mgKOH/g, and the double bond equivalent was 480g/mol. When the total mole number of the repeating units in the alkali-soluble resin C is 100 mole%, the repeating unit having an aromatic ring in the side chain is 10 mole% and the repeating unit having a saturated alicyclic structure in the side chain is 30 mole%, and the alkali-soluble resin C does not satisfy the alkali-soluble resin (C-1).

Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content became 40 mass%, and the resin solution was used as an alkali-soluble resin C to prepare a colored resin composition.

< Alkali-soluble resin D >

145 Parts by mass of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. To this was added dropwise 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate and 4.4 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi chemical Co., ltd.) in 3 hours, and a mixed solution of 8.47 parts by mass of 2.2' -azobis-2-methylbutyronitrile was further added dropwise, and stirring was continued at 90℃for 2 hours. Then, the reaction vessel was replaced with air, and 0.7 part by mass of tris (dimethylaminomethyl) phenol and 0.12 part by mass of hydroquinone were charged into 59.8 parts by mass of acrylic acid, and the reaction was continued at 120℃for 6 hours. Thereafter, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added, and the mixture was reacted at 120℃for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin D thus obtained was about 9000 in terms of polystyrene as measured by GPC, the acid value was 25mgKOH/g, and the double bond equivalent was 260g/mol. When the total mole number of the repeating units in the alkali-soluble resin D is 100 mole%, the repeating unit having an aromatic ring in the side chain is 5 mole% and the repeating unit having a saturated alicyclic structure in the side chain is 2 mole%, and the alkali-soluble resin D does not satisfy the alkali-soluble resin (c-1).

Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content became 40 mass%, and the resin solution was used as an alkali-soluble resin D to prepare a colored resin composition.

< Alkali-soluble resin E >

As a reaction tank, a separable flask equipped with a condenser was prepared, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the reaction tank was heated with an oil bath while stirring, and the temperature of the reaction tank was raised to 90 ℃.

On the other hand, 30 parts by mass of dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-propionate, 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 the monomer tank, 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank, and after the temperature of the reaction tank had stabilized to 90 ℃, the polymerization was initiated by dropping from the monomer tank and the chain transfer agent tank. The reaction vessel was set to 110℃by dropping the solution for 135 minutes while maintaining the temperature at 90℃and starting the temperature rise after 60 minutes from the end of the dropping.

After maintaining 110℃for 3 hours, a gas introduction 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 parts by mass of 2,2' -methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the reaction was directly carried out at 110℃for 9 hours.

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

When the total mole number of the repeating units in the alkali-soluble resin E is 100 mole%, the repeating unit having an aromatic ring in the side chain is 0 mole% and the repeating unit having a saturated alicyclic structure in the side chain is 44 mole%, and the alkali-soluble resin E does not satisfy the alkali-soluble resin (c-1).

< Preparation of Green dye Dispersion A >

As shown in table 1, 9.9 parts by mass of the phthalocyanine compound a, 0.1 part 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 a 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 were filled into 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 a filter to prepare a green dye dispersion a.

< Preparation of Green pigment Dispersion A >

As shown in table 1, 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 E in terms of solid content, 80.0 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 E), and 225 parts by mass of zirconia beads having a diameter of 0.5mm were filled into a stainless steel vessel, 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 a filter to prepare a green pigment dispersion a.

< Preparation of yellow pigment Dispersion A >

As shown in table 1, a stainless steel vessel was filled with 11.4 parts by mass of c.i. pigment yellow, 2.9 parts by mass of dispersant a in terms of solid content, 5.7 parts by mass of alkali-soluble resin E 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 E), 4.0 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 by a paint shaker. After the end of the dispersion, the beads were separated from the dispersion by a filter to prepare a yellow pigment dispersion a.

TABLE 1

< Photopolymerizable monomer A >

Pentaerythritol tetraacrylate (PE-4A, manufactured by co-Rong chemical Co., ltd.)

< Photopolymerization initiator A >

Oxime ester compound (4-acetoxyimino-5- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -5-oxopentanoic acid methyl ester) having the following chemical structure

< Surfactant A >

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

< Preparation of colored resin composition >

The components shown in table 2 were mixed at the solid content ratios shown in the above, to prepare a colored resin composition. Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Propylene Glycol Monomethyl Ether (PGME) were used so that the content of the total solid content of the colored resin composition became 15.2 mass%. The mixing ratio (mass ratio) of PGMEA/PGME in the resulting colored resin composition was 90/10.

TABLE 2

< Evaluation of color Property >

The colored resin composition was applied to a glass substrate (manufactured by AGC Co., ltd., AN 100) having a thickness of 0.5mm at a square of 50mm by spin coating, dried under reduced pressure, and then prebaked on a hot plate at 90℃for 90 seconds. Next, the entire surface was exposed to light with an exposure of 40mJ/cm ² and an illuminance of 30mW/cm ² by using a 2kW high-pressure mercury lamp. Thereafter, firing was performed in a clean oven at 230 ℃ for 20 minutes to prepare a colored substrate. Using the obtained colored substrate, a transmission spectrum was measured under a C light source using a spectrophotometer U-3310 manufactured by hitachi, and chromaticity (sx, sy) and luminance LY were calculated.

Further, the contrast at chromaticity of sy=0.607 under the C light source was measured by a contrast meter (CT-1) manufactured by kusakusakun motor company using the obtained colored substrate. The measured contrast is shown in table 2.

From table 2, it can be seen that: examples 1 to 2 containing the alkali-soluble resin a or B conforming to the alkali-soluble resin (c-1) have significantly higher contrast than comparative examples 1 to 3 containing no alkali-soluble resin (c-1). This is considered to be because: since the alkali-soluble resin (c-1) contains a large amount of repeating units having aromatic rings in the side chains, the aromatic rings and the phthalocyanine compound a are pi-piled up, whereby the phthalocyanine compounds a are brought close to each other, molecules meet each other in the firing step, alignment (crystallization) is regularly promoted, and contrast is improved. In addition, it can be considered that: since the amount of the repeating unit having an alicyclic structure in the side chain is small, the bulky alicyclic structure is prevented from blocking the junction of molecules of the phthalocyanine compound, and the contrast is improved.

In addition, as shown in reference examples 1 to 2, when the c.i. pigment green 58 which does not conform to the phthalocyanine compound (1) is used, the contrast change due to the presence or absence of the alkali-soluble resin (c-1) is not observed. This also verifies the above mechanism that the alkali-soluble resin (c-1) specifically acts on the phthalocyanine compound (1) to improve the contrast.

The present invention has been described in detail with reference to specific embodiments, but it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Industrial applicability

Description of the reference numerals

10. Transparent support substrate

20. Pixel arrangement

30. Organic protective layer

40. Inorganic oxide film

50. Transparent anode

51. Hole injection layer

52. Hole transport layer

53. Light-emitting 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 (C) alkali-soluble resin contains an alkali-soluble resin C-1, the alkali-soluble resin C-1 having a repeating unit containing an aromatic ring in a side chain,

When the total molar amount of the repeating units in the alkali-soluble resin c-1 is 100 mol%, the total content of the repeating units having an aromatic ring in a side chain is 20 mol% or more,

In the formula (1), A ¹～A¹⁶ each independently represents a hydrogen atom, a halogen atom, or a group represented by the following formula (2), wherein 1 or more of A ¹～A¹⁶ represent a fluorine atom, and 1 or more of A ¹～A¹⁶ represent a group represented by the following formula (2),

In the formula (2), X represents a divalent linking group, and the benzene ring in the formula (2) may have any substituent, and represents an atomic bond.

2. The colored resin composition according to claim 1, wherein the total content of the repeating units containing an aromatic ring in a side chain in the alkali-soluble resin c-1 is 30 mol% or more.

3. The colored resin composition according to claim 1 or 2, wherein the alkali-soluble resin c-1 has a repeating unit containing an alicyclic structure in a side chain, the alicyclic structure being a saturated alicyclic structure.

4. The colored resin composition according to claim 3, wherein the distance from the main chain to the alicyclic structure in the repeating unit having an alicyclic structure in the side chain is 4 or less atoms.

5. The colored resin composition according to claim 3 or 4, wherein the total content of the repeating units having an alicyclic structure in a side chain is 10 mol% or less, assuming that the total mole number of the repeating units in the alkali-soluble resin c-1 is 100 mol%.

6. The colored resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin c-1 has at least 1 selected from the repeating units represented by the following general formula (3) and the following general formula (4) as the repeating unit containing an aromatic ring in a side chain,

In the formula (3) and the formula (4), R ¹ each independently represents a hydrogen atom or a methyl group, and the benzene rings in the formula (3) and the formula (4) may have any substituent.

7. The colored resin composition according to claim 6, wherein the alkali-soluble resin c-1 has the repeating unit represented by the general formula (3) as the repeating unit containing an aromatic ring in a side chain.

8. The colored resin composition according to any one of claims 3 to 5, wherein the alkali-soluble resin c-1 has at least 1 kind of repeating units selected from the group consisting of the repeating units represented by the following general formula (5) and the following general formula (6) as the repeating units containing an alicyclic structure in a side chain,

In the formula (5) and the formula (6), R ¹ each independently represents a hydrogen atom or a methyl group, and the saturated hydrocarbon ring in the formula (5) and the formula (6) may have any substituent.

9. The colored resin composition according to claim 8, wherein the alkali-soluble resin c-1 has the repeating unit represented by the general formula (5) as the repeating unit containing an alicyclic structure in a side chain.

10. The colored resin composition according to any one of claims 1 to 9, wherein the alkali-soluble resin c-1 has a repeating unit represented by the following general formula (I),

In the formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group,

R ² represents a trivalent hydrocarbon group optionally having a substituent,

R ⁴ represents a divalent hydrocarbon group optionally having a substituent.

11. The colored resin composition according to any one of claims 1 to 10, wherein the content ratio of the (a) colorant is 10 mass% or more with respect to the total solid component amount of the colored resin composition.

12. The colored resin composition according to any one of claims 1 to 11, wherein the content ratio of the alkali-soluble resin c-1 is 10 mass% or more with respect to the total solid component amount of the colored resin composition.

13. A color filter comprising pixels produced using the colored resin composition according to any one of claims 1 to 12.

14. An image display device provided with the color filter according to claim 13.