TWI812845B - Colored resin composition, color filter and image display device - Google Patents

Abstract

The present invention provides a colored resin composition with high brightness and suppressed generation of residues. The colored resin composition of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and the above-mentioned (A) colorant contains the following general properties: For a phthalocyanine compound with a chemical structure represented by formula (1), the above-mentioned solvent (B) contains a high-boiling point solvent having a boiling point of 160°C or higher at 1013.25 hPa. (In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2); wherein, at least one of A ¹ to A ¹⁶ represents a fluorine atom, and One or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2)) (In formula (2), X represents a divalent linking group; the benzene ring in formula (2) can have any substituent; * represents a bond)

Description

Colored resin composition, color filter and image display device

The present invention relates to a colored resin composition, a color filter and an image display device. The entire contents of the specification, patent scope, drawings and abstract of the Japanese Patent Application No. 2019-030548 filed with the Japan Patent Office on February 22, 2019, and the Japanese Patent Application No. 2019-030548 filed with the Japan Patent Office on June 27, 2019. Part or all of the disclosure content of the specification, patent application scope, drawings and abstract of No. 2019-119240, as well as the documents cited in this specification, are hereby cited and incorporated as the disclosure content of this specification.

Conventionally, as methods for manufacturing color filters used in liquid crystal display devices and the like, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods have been known. Among them, the pigment dispersion method, which has average excellent characteristics in terms of spectral characteristics, durability, pattern shape, and accuracy, is most widely used.

In recent years, color filters have been required to have higher brightness, higher contrast, and higher color gamut. As a colorant that determines the color of color filters, pigments are usually used in terms of heat resistance, light resistance, etc. However, pigments, especially in terms of high brightness, are gradually unable to meet market requirements. The industry is now using dyes instead of pigments as colorants. Research on agents. Regarding green pixels, use of specific phthalocyanine compounds as dyes is being studied (see, for example, Patent Documents 1 to 3). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2009-051896 [Patent Document 2] International Publication No. 2014/157387 [Patent Document 3] Japanese Patent Application Publication No. 2014-43556

[Problem to be solved by the invention]

As a result of research conducted by the present inventors, it was found that the colored resin composition described in Patent Document 1 or Patent Document 2 has insufficient brightness for practical use. Furthermore, it was found that the colored resin composition described in Patent Document 3 has insufficient alkaline developability in the alkaline development step when manufacturing a color filter, and residues derived from the colored resin composition are generated on the glass substrate. Therefore, an object of the present invention is to provide a colored resin composition with high brightness and suppressed generation of residues. [Technical means to solve problems]

The present inventors conducted intensive research and found that the above-mentioned problems can be solved by using a specific phthalocyanine compound as a colorant and a solvent having a specific boiling point or higher as a solvent, and thus completed the present invention. That is, the present invention has the following configuration.

[1] A colored resin composition characterized by containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and The coloring agent (A) above contains a phthalocyanine compound having a chemical structure represented by the following general formula (1), The above (B) solvent contains a high boiling point solvent with a boiling point of 160°C or higher at 1013.25 hPa.

[Chemical 1]

(In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2); wherein, at least one of A ¹ to A ¹⁶ represents a fluorine atom, and One or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2))

[Chemicalization 2]

(In formula (2), X represents a divalent linking group; the benzene ring in formula (2) can have any substituent; * represents a bond)

[2] The colored resin composition according to [1], wherein the content of the solvent (B) in the colored resin composition is 50% by mass or more. [3] The colored resin composition according to [1] or [2], wherein the content ratio of the high-boiling-point solvent in the solvent (B) is 0.5% by mass or more. [4] The colored resin composition according to any one of [1] to [3], wherein the content ratio of the phthalocyanine compound is 5 mass % or more based on the total solid content. [5] The colored resin composition according to any one of [1] to [4], wherein the (D) photopolymerization initiator contains an oxime ester-based photopolymerization initiator.

[6] A color filter having pixels produced using the colored resin composition according to any one of [1] to [5]. [7] An image display device having the color filter according to [6]. [Effects of the invention]

According to the present invention, it is possible to provide a colored resin composition with high brightness and suppressed generation of residues.

The structural elements and the like of the present invention will be described in detail below. These are examples of embodiments of the present invention and are not limited to these contents. In the present invention, "weight average molecular weight" means the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In addition, in the present invention, the "amine value" means the amine value in terms of the effective solid content unless otherwise specified, and is determined by the mass of KOH equivalent to the alkali content per 1 g of the solid content of the dispersant. The value represented. In addition, in the present invention, "C.I." means dye index. Moreover, in the present invention, "(meth)acrylic~", "(meth)acrylate", etc. mean "acrylic~ and/or methacrylic~", "acrylate and/or methacrylate" etc., for example, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid". Moreover, in this invention, "total solid content" means all components except the solvent component contained in a pigment dispersion liquid or a colored resin composition. In addition, in the present invention, the numerical range represented by "～" means a range including the numerical values described before and after "～".

[1] Components of colored resin composition Hereinafter, each component of the colored resin composition of the present invention will be described. The colored resin composition of the present invention contains (A) colorant, (B) solvent, (C) alkali-soluble resin, and (D) photopolymerization initiator as essential components. Furthermore, components other than the above-mentioned components may be blended as necessary. Other additives, etc. Each component is explained below.

[1-1](A) Colorant The (A) coloring agent contained in the colored resin composition of the present invention contains a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter may be referred to as "phthalocyanine compound (1)").

[Chemical 3]

In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). Among them, one or more of A ¹ to A ¹⁶ represents a fluorine atom, and one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Chemical 4]

In formula (2), X represents a bivalent linking group. The benzene ring in formula (2) may have any substituent. *Indicates bonding key.

The coloring agent (A) contained in the colored resin composition of the present invention contains a phthalocyanine compound (1). Since the phthalocyanine compound (1) has a group represented by the above-mentioned general formula (2), it has high solubility in a solvent, thereby eliminating the need for a dispersion treatment step or making it possible to reduce the amount of a dispersant necessary in the dispersion treatment step to a very small amount. Therefore, it is considered that in the colored resin composition, there is no or only a very small amount of dispersant or alkali-soluble resin around the phthalocyanine compound (1), and that in the colored resin composition, the phthalocyanine compound (1) and the alkali-soluble resin The affinity becomes weaker. In particular, it is thought that the molecules of the phthalocyanine compound (1) are easily associated with each other due to the π-π interaction between the phthalocyanine rings and the π-π interaction between the groups represented by the general formula (2), and furthermore, by having For fluorine atoms with smaller atomic radius, the molecules become denser, the brightness becomes higher, and the affinity with alkali-soluble resin becomes weaker.

It is thought that the brightness becomes higher due to the higher solubility in the solvent. On the other hand, in the alkaline development step, the interaction between the alkaline developer and the phthalocyanine compound (1) becomes smaller, and the phthalocyanine compound (1) ) will not be fully dissolved in the alkaline developer and will tend to remain on the glass substrate.

Therefore, by containing a high-boiling solvent with a boiling point of 160°C or higher at 1013.25 hPa, the colored resin composition of the present invention is considered to be able to suppress the drying of the coating film during the alkaline development step and achieve a fully moist state. It fully penetrates into the coating film to promote the neutralization reaction, and residues derived from the colored resin composition are less likely to be generated on the glass substrate.

(A ¹ to A ¹⁶ ) In the above formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). Among them, one or more of A ¹ to A ¹⁶ represents a fluorine atom, and one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Chemistry 5]

In formula (2), X represents a bivalent linking group. The benzene ring in formula (2) may have any substituent. *Indicates bonding key.

(X) X in the above general formula (2) represents a bivalent linking group. The bivalent linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, or a -N(R ^a1 )- group (R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Among these, from the viewpoint of stability during baking of the phthalocyanine compound (1), an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

(Substituents that the benzene ring may have) In addition, the benzene ring in formula (2) may have any substituents. The substituent is not particularly limited, and examples thereof include: halogen atom, alkyl group ( ^-RA group (where R ^A represents an alkyl group)), alkoxy group (-OR ^A group (where R ^A represents an alkyl group) ), alkoxycarbonyl group (-COOR ^A group (where R ^A represents an alkyl group)), aryl group (-RB group (where R ^B represents an aryl group)), aryloxy group (-OR ^B group (where R ^B represents an aryl group) , R ^B represents an aryl group)), aryloxycarbonyl group (-COOR ^B group (where R ^B represents an aryl group)), the alkyl group (-R ^A group) or aryl group (-R ^B group contained in these groups group) may be further substituted by such substituents. Among these, an alkoxycarbonyl group is preferred from the viewpoint of solubility in a solvent or brightness.

Furthermore, the alkyl groups contained in these groups may be linear, branched, or cyclic. From the viewpoint of solubility in solvents, linear groups are preferred. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less. By setting the value above the lower limit, the lipophilicity tends to increase, and the solubility of the phthalocyanine compound (1) in the solvent tends to increase. Also, by setting the value below the above upper limit, the hydrophilicity increases, and the phthalocyanine compound (1) contains phthalocyanine. The colored resin composition of the cyanine compound (1) tends to have improved solubility in an alkaline developer. Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., so as to achieve both lipophilicity and hydrophilicity, that is, the solubility of the phthalocyanine compound (1) in the solvent. From the viewpoint of the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, a methyl group or an ethyl group is preferred, and an ethyl group is more preferred.

In addition, the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. By setting it as above the said lower limit value, the solubility of a phthalocyanine compound (1) in a solvent tends to improve, and by setting it as below the said upper limit value, the hue change by an aryl group tends to be suppressed.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of aromatic hydrocarbon ring groups include groups such as benzene ring, naphthalene ring, pentacene ring, indene ring, azulene ring, and β ring having one free atom valence. In addition, 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, and a 1,3-ethazole ring having one free atom valence. Isothiazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furoxin ring, pyridine ring, pyrimidine ring, pyrimidine ring, 1,3,5-tristriazole ring, benzo Furan ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indole 𠯤 ring, 2H-1-benzopyran Ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinoline, benzimidazole ring, 1H-indazole ring, quinoline ring, quinazoline ring, azoline Ring, phthalate ring, 1,8-naphthyridine ring, purine ring, pteridine ring and other bases.

When the benzene ring in the formula (2) has any substituent, the number of substitutions is not particularly limited, taking into account the polarity of the phthalocyanine compound (1), that is, taking into account the influence of the phthalocyanine compound (1) in the solvent. From the viewpoint of the lipophilicity of the solubility and the hydrophilicity affecting the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, it is preferable that the number of substitutions per one benzene ring is is 1. In addition, when the benzene ring in formula (2) has any substituent, the substitution position may be ortho, meta, or para, taking into account the polarity of the phthalocyanine compound (1). , that is, from the viewpoint of balancing the lipophilicity that affects the solubility of the phthalocyanine compound (1) in the solvent and the hydrophilicity that affects the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer. In other words, counterpoint is better.

At least one of A ¹ to A ¹⁶ represents a fluorine atom, but the brightness or lipophilicity affecting the solubility of the phthalocyanine compound (1) in the solvent and the lipophilicity affecting the colored resin composition containing the phthalocyanine compound (1) are both considered. From the viewpoint of hydrophilicity of alkaline development solubility, it is preferable that there are 2 or more fluorine atoms, more preferably 4 or more, still more preferably 6 or more, and more preferably 14 or less, still more preferably 12 or less, more preferably 10 or less. For example, in A ¹ to A ¹⁶ , the number of fluorine atoms is preferably 1 to 14, more preferably 2 to 14, further preferably 4 to 12, and particularly preferably 6 to 10.

At least one of A ¹ to A ¹⁶ represents a fluorine atom, but in terms of brightness or the polarity of the phthalocyanine compound (1), that is, the lipophilicity that affects the solubility of the phthalocyanine compound (1) in the solvent and the influence of the phthalocyanine compound containing the phthalocyanine compound (1). From the hydrophilic point of view of the alkaline development solubility of the colored resin composition of the cyanine compound (1), it is preferred that at least one of A ¹ to A ⁴ be a fluorine atom, and that at least one of A ⁵ to A ⁸ be a fluorine atom. , one or more of A ⁹ to A ¹² is a fluorine atom, and one or more of A ¹³ to A ¹⁶ is a fluorine atom, more preferably two or more of A ¹ to A ⁴ are fluorine atoms, and two of A ⁵ to A ⁸ are The above are fluorine atoms, two or more of A ⁹ to A ¹² are fluorine atoms, and two or more of A ¹³ to A ¹⁶ are fluorine atoms.

At least one of A ¹ to A ¹⁶ represents the group represented by the above-mentioned general formula (2), but from the viewpoint of solubility in a solvent, it is preferably 2 or more, more preferably 4 or more, and still more preferably The number is 6 or more, and preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less. For example, in A ¹ to A ¹⁶ , the number of groups represented by the general formula (2) is preferably 1 to 14, more preferably 2 to 14, further preferably 4 to 12, and particularly preferably 6 to 10 Piece.

In addition, at least one of A ¹ to A ¹⁶ represents a group represented by the above-mentioned general formula (2). However, from the viewpoint of solubility in a solvent, it is preferable that at least one of A ¹ to A ⁴ represents the above-mentioned general formula. (2) As for the group represented by (2), at least one of A ⁵ to A ⁸ is a group represented by the above general formula (2), and at least one of A ⁹ to A ¹² is a group represented by the above general formula (2), and A More than one of ¹³ to A ¹⁶ is a group represented by the above general formula (2), more preferably two or more of A ¹ to A ⁴ are groups represented by the above general formula (2), and 2 of A ⁵ to A ⁸ are More than two are groups represented by the above general formula (2), two or more of A ⁹ to A ¹² are groups represented by the above general formula (2), and two or more of A ¹³ to A ¹⁶ are groups represented by the above general formula ( 2) The basis represented. Especially from the viewpoint of hue, brightness, and solubility in solvents required for color filters, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ is a group represented by the above general formula (2), and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are fluorine atoms.

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

[Chemical 6]

Et in the formula represents ethyl group.

[Chemical 7]

[Chemical 8]

[Chemical 9]

As a method for producing the phthalocyanine compound (1), a known method can be used. For example, the method described in Japanese Patent Application Laid-Open No. 5-345861 can be used.

(A) Colorant In addition to the phthalocyanine compound (1), other colorants may be included. Examples of other colorants include pigments and dyes. Among them, when the colored resin composition of the present invention is used for green pixels, it is preferable to use green pigments, green dyes, yellow pigments, yellow dyes, etc. Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, and 63. From the viewpoint of brightness, C.I. Pigment Green 58 is preferred. Examples of the green dye include C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 which are C.I. Solvent dyes among those classified as dyes in the Dye Index, and further examples include: C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 as C.I. acid dye; C.I. mordant green 1 as C.I. mordant dye. 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. Among these, from the viewpoint of suppressing dye decomposition during thermal baking, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 are preferred.

Examples of yellow pigments 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 the 1:1 mixture of azobarbituric acid and nickel represented by the following formula (i) The compound or its interchange isomer is a compound in which other compounds are inserted (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)"), etc.

[Chemical 10]

In addition, as other compounds to be inserted into the 1:1 complex of azobarbituric acid and nickel represented by the above formula (i) or its interchange isomer, those represented by the following formula (ii) can be cited Compounds etc.

[Chemical 11]

Among them, from the viewpoint of high brightness and high color gamut, C.I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and nickel azozine represented by formula (i) are preferred. The compound is more preferably a nickel azo complex represented by C.I. Pigment Yellow 83, 138, 139, 180, 185 and formula (i).

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, cyanine dyes, and the like. Specific examples thereof include specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531. Among those classified as dyes in the dye index, C.I. solvent dyes include: C.I. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 , 163 etc. Moreover, examples of C.I. acid dyes include: 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 or their derivatives. Also, examples of C.I. direct dyes 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 and other dyes. Furthermore, examples of C.I. mordant dyes include: C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and other dyes, preferably Listed: C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 or their derivatives. Among these, from the viewpoint of suppressing dye decomposition during thermal baking, it is preferable to be selected from C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98 At least one of the group consisting of , 99, 162 and 163.

The average primary particle diameter of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less. When micronizing the pigment, a method such as solvent salt milling can be suitably used.

The content ratio of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but it is preferably 5 mass % or more, more preferably 10 mass % or more, in the total solid content of the colored resin composition. It is more preferably 20 mass% or more, still more preferably 30 mass% or more, particularly preferably 35 mass% or more, and further preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass%. % or less, preferably 45 mass% or less. By setting the value above the lower limit, color characteristics such as brightness and color gamut tend to be improved, and by setting the value below the upper limit, pattern formability tends to be improved. For example, the content ratio of the colorant (A) is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, further preferably 20 to 50 mass%, still more preferably 30 to 45 mass%, and particularly preferably It is 35~45% by mass.

The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited. In the total solid content of the colored resin composition, it is preferably 5 mass % or more, and more preferably 10 mass % or more. , more preferably 20 mass% or more, still more preferably 30 mass% or more, particularly preferably 35 mass% or more, and more preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% % or less, preferably 45 mass% or less. By setting the value above the lower limit, color characteristics such as brightness and color gamut tend to be improved, and by setting the value below the upper limit, pattern formability tends to be improved.

When other colorants are contained, the content ratio is not particularly limited, but in the total solid content of the colored resin composition, it is preferably 0.1 mass % or more, more preferably 1 mass % or more, and still more preferably 3 Mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, and preferably 60 mass% or less, more preferably 50 mass% or less, further preferably 40 mass% or less, particularly preferably 30% by mass or less. By setting the value above the lower limit, color characteristics such as brightness and color gamut tend to be improved, and by setting the value below the upper limit, pattern formability tends to be improved.

[1-2](B)Solvent (B) The solvent has the function of dissolving or dispersing the colorant, alkali-soluble resin, photopolymerization initiator, and other components in the colored resin composition of the present invention and adjusting the viscosity. The solvent (B) may be any solvent that can dissolve or disperse each component.

In the colored resin composition of the present invention, the solvent (B) contains a high-boiling-point solvent having a boiling point of 160° C. or higher at 1013.25 hPa (hereinafter, may be referred to as a “high-boiling-point solvent”). It is thought that by containing a high-boiling point solvent as described above, the drying of the coating film during the alkaline development step can be suppressed and the coating film can be brought into a fully moist state. The alkaline developer can fully penetrate into the coating film and promote the neutralization reaction. Even if it contains The coating film of the phthalocyanine compound (1) does not easily produce residues on the glass substrate.

The boiling point of the above-mentioned high-boiling point solvent at 1013.25 hPa (hereinafter simply referred to as "boiling point" unless otherwise specified) is usually 160°C or higher, preferably 165°C or higher, more preferably 170°C or higher, and further preferably 180°C. ℃ or higher, more preferably 190°C or higher, particularly preferably 200°C or higher, most preferably 220°C or higher, and preferably 340°C or lower, more preferably 300°C or lower, still more preferably 280°C or lower. By setting it above the lower limit value, the alkali solubility is improved, and the occurrence of bumping during VCD (vacuum drying) (reduced pressure drying) in the color filter manufacturing step tends to be suppressed. Also, by By setting it below the above upper limit, the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing step tends to be improved. For example, the boiling point of the above-mentioned high-boiling point solvent is preferably 160-340°C, more preferably 165-340°C, further preferably 170-300°C, further preferably 180-300°C, particularly preferably 190-300°C, especially The preferred temperature range is 200-280°C, and the optimum temperature range is 220-280°C. The high boiling point solvent may be used alone or in combination of two or more types.

In addition, the vapor pressure of the above-mentioned high boiling point solvent at 20°C is not particularly limited, but is preferably 1 Pa or more, more preferably 5 Pa or more, further preferably 10 Pa or more, and more preferably 2000 Pa or less, and more It is preferably 1,500 Pa or less, more preferably 1,000 Pa or less, and particularly preferably 500 Pa or less. By setting the value above the above lower limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing step tends to be improved, and by setting the value below the above upper limit, the alkali solubility is improved, and the color filter The tendency of bumping during VCD (vacuum pressure drying) in the filter manufacturing process is suppressed. For example, the vapor pressure of the above-mentioned high boiling point solvent at 20°C is preferably 1 to 2000 Pa, more preferably 1 to 1500 Pa, further preferably 5 to 1000 Pa, and particularly preferably 10 to 500 Pa.

Specific examples of the high boiling point solvent include: ethylene glycol mono-n-butyl ether (boiling point: 171°C), propylene glycol mono-n-butyl ether (boiling point: 170°C), and diethylene glycol diethyl ether (boiling point: 188°C) , Diethylene glycol monoethyl ether (boiling point: 202°C), ethyl 3-ethoxypropionate (boiling point: 170°C), 3-methoxybutyl acetate (boiling point: 171°C), 3-methoxy acetate Glycol ethers such as methyl-3-methylbutyl ester (boiling point: 187°C); Ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C), diethylene glycol monoethyl ether acetate (boiling point: 217°C), diethylene glycol monobutyl ether acetate (boiling point: 245°C), etc. Glycol ether acetates; Glycol diacetate esters such as ethylene glycol diacetate (boiling point: 191°C), 1,3-butanediol diacetate (boiling point: 232°C); Amines such as N-methylpyrrolidone (boiling point: 202°C), and glycol ethers or glycol ethers are preferred from the viewpoint of the solubility of the phthalocyanine compound (1) in the colored resin composition. Acetate esters, more preferably glycol ethers.

Among these high boiling point solvents, from the viewpoint of moderate residue suppression and improvement of the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process, it is preferable to use one with a boiling point of 160°C or more and less than 200°C. High boiling point solvent (hereinafter sometimes referred to as "high boiling point solvent A"). The boiling point of the high-boiling point solvent A is not particularly limited as long as it is 160°C or higher and less than 200°C. It is preferably 165°C or higher, more preferably 170°C or higher, further preferably 175°C or higher, and more preferably 195°C. °C or lower, more preferably 190°C or lower, further preferably 185°C or lower. By setting it to the above-mentioned lower limit value or more, alkali solubility is improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned upper limit value, In the following, there is a tendency for the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process to be improved. For example, the boiling point of the high-boiling point solvent A is preferably 165°C to 195°C, more preferably 170°C to 190°C, and further preferably 175°C to 185°C. The high boiling point solvent A may be used alone or in combination of two or more types.

Specific examples of the high boiling point solvent A include: ethylene glycol mono-n-butyl ether (boiling point: 171°C), propylene glycol mono-n-butyl ether (boiling point: 170°C), and diethylene glycol diethyl ether (boiling point: 188°C) , ethyl 3-ethoxypropionate (boiling point: 170°C), 3-methoxybutyl acetate (boiling point: 171°C), 3-methoxy-3-methylbutyl acetate (boiling point: 187°C) ) and other glycol ethers; Glycol ether acetates such as ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C); From the viewpoint of the solubility of the phthalocyanine compound (1) in the colored resin composition, glycol diacetates such as ethylene glycol diacetate (boiling point: 191°C) are preferably glycol ethers or glycol ethers. Glycol ether acetates, more preferably glycol ethers.

Among these high-boiling point solvents, from the viewpoint of efficient residue suppression and suppression of bumping during VCD (vacuum pressure drying) in the color filter manufacturing process, it is preferable to use a solvent with a boiling point of 200°C or more and 340°C. The following high boiling point solvents (hereinafter sometimes referred to as "high boiling point solvent B"). The boiling point of the high-boiling point solvent B is not particularly limited as long as it is 200°C or more and 340°C or less, but it is preferably 210°C or more, more preferably 220°C or more, further preferably 230°C or more, and further preferably 320°C or less. , more preferably 300°C or lower, further preferably 280°C or lower. By setting it to the above-mentioned lower limit value or more, alkali solubility is improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned upper limit value, In the following, there is a tendency for the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process to be improved. For example, the boiling point of the high-boiling point solvent B is preferably 210°C to 320°C, more preferably 220°C to 300°C, and further preferably 230°C to 280°C. The high boiling point solvent B may be used alone or in combination of two or more types.

Specific examples of the high boiling point solvent B include glycol ethers such as diethylene glycol monoethyl ether (boiling point: 202°C); Diethylene glycol monoethyl ether acetate (boiling point: 217°C), diethylene glycol monobutyl ether acetate (boiling point: 245°C) and other glycol ether acetates; Diol diacetates such as 1,3-butanediol diacetate (boiling point: 232°C); Amines such as N-methylpyrrolidone (boiling point: 202°C), and glycol ethers or glycol ethers are preferred from the viewpoint of the solubility of the phthalocyanine compound (1) in the colored resin composition. Acetates, more preferably glycol ether acetates.

Among high-boiling-point solvents, it is preferable to use high-boiling-point solvent A alone from the viewpoint of moderate residue suppression and improvement of efficiency of VCD (vacuum pressure drying) in the color filter manufacturing step. Furthermore, from the viewpoint of efficient residue suppression and suppression of bumping during VCD (vacuum pressure drying) in the color filter manufacturing process, it is preferable to use the high boiling point solvent B alone. On the other hand, from the viewpoint of suppressing residues and taking into account both the improvement of the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process and the suppression of bumping during VCD (vacuum pressure drying), it is preferable to use a high boiling point in combination. Solvent A and high boiling point solvent B.

Moreover, in the colored resin composition of the present invention, the solvent (B) preferably contains a low-boiling-point solvent with a boiling point of less than 160° C. (hereinafter sometimes referred to as a “low-boiling-point solvent”). By containing a low boiling point solvent, the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process is improved, or the coating film is easily dried using VCD or heat drying, and the thickness of the coating film becomes thinner, thereby tending to have the following tendencies: During ultraviolet exposure, ultraviolet light reaches the inside of the coating film, thereby improving the hardening properties of the coating film and making pattern formation advantageous.

The boiling point of the low-boiling point solvent is not particularly limited as long as it does not reach 160°C, but it is preferably 150°C or lower, more preferably 140°C or lower, further preferably 130°C or lower, especially 120°C or lower, and more preferably The temperature is 80°C or higher, more preferably 90°C or higher, and still more preferably 100°C or higher. By setting the value below the above-mentioned upper limit, the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing step tends to be improved, and by setting it above the above-mentioned lower limit, the alkali solubility tends to be improved. .

Specific examples of low boiling point solvents include: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, ethyl pyruvate, methyl 3-methoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, dibutyl ether , Ethyl pyruvate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, methyl 3-methoxyisobutyrate , Methyl glycolate, methyl lactate, methyl 2-hydroxyisobutyrate, 2-methoxyethyl acetate, ethylene glycol methyl ether acetate, dibutyl ether, cyclopentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 1-methoxy-2-propanol, etc. Among these, from the viewpoint of solubility or storage stability of components of the colored resin composition other than the solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate are preferred, and more preferred It is propylene glycol monomethyl ether acetate.

The content ratio of the (B) solvent in the colored resin composition of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass. The content is preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 88 mass% or less. By setting the value above the lower limit, the storage stability and applicability of the colored resin composition tend to be improved, and by setting the value below the above upper limit, the film thickness during coating can be reduced to The tendency below a certain thickness. For example, the content ratio of the solvent is preferably 50 to 95 mass%, more preferably 60 to 95 mass%, further preferably 70 to 90 mass%, and particularly preferably 80 to 88 mass%.

Moreover, in the colored resin composition of the present invention, the content ratio of the above-mentioned high boiling point solvent in the solvent (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2 mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, particularly preferably 15 mass% or more, most preferably 20 mass% or more, and still more preferably 80 mass% or less. The content is 60 mass% or less, more preferably 40 mass% or less, and particularly preferably 30 mass% or less. By setting it to the above-mentioned lower limit value or more, alkali solubility is improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned upper limit value, In the following, there is a tendency for the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process to be improved. For example, the content ratio of the above-mentioned high boiling point solvent in the solvent (B) is preferably 0.5 to 80 mass %, more preferably 1 to 80 mass %, further preferably 2 to 60 mass %, and still more preferably 5 to 60 mass %. % by mass, particularly preferably 10 to 40 mass %, particularly preferably 15 to 40 mass %, and most preferably 20 to 30 mass %.

When the colored resin composition of the present invention contains the above-mentioned low-boiling point solvent, the content ratio of the above-mentioned low-boiling point solvent in the solvent (B) is not particularly limited, but is preferably 20 mass % or more, and more preferably 40 mass % or more. , more preferably 60 mass% or more, particularly preferably 70 mass% or more, and more preferably 99 mass% or less, more preferably 98 mass% or less, still more preferably 95 mass% or less. By setting the value above the above lower limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing step tends to be improved, and by setting the value below the above upper limit, the alkali solubility is improved, and the color filter The tendency of bumping during VCD (vacuum pressure drying) in the filter manufacturing process is suppressed. For example, the content ratio of the low-boiling-point solvent in the solvent (B) is preferably 20 to 99 mass%, more preferably 40 to 98 mass%, further preferably 60 to 95 mass%, and particularly preferably 70 to 95 mass%. %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent A and the above-mentioned low boiling point solvent, the content ratio of the above-mentioned high boiling point solvent A in the (B) solvent is not particularly limited, but is preferably It is 1 mass % or more, more preferably 5 mass % or more, further preferably 10 mass % or more, especially 15 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, and further The content is preferably 30% by mass or less, and particularly preferably 20% by mass or less. By setting it to the above-mentioned lower limit value or more, alkali solubility is improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned upper limit value, In the following, there is a tendency for the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process to be improved. For example, the content ratio of the high boiling point solvent A in the solvent (B) is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, further preferably 10 to 30 mass %, and particularly preferably 15 to 20 mass %. Mass %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent A and the above-mentioned low boiling point solvent, the content ratio of the low boiling point solvent in the (B) solvent is not particularly limited, but is preferably 50 Mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more, especially 80 mass % or more, and preferably 99 mass % or less, more preferably 95 mass % or less, still more preferably It is 90 mass % or less, especially 85 mass % or less. By setting the value above the above lower limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing step tends to be improved, and by setting the value below the above upper limit, the alkali solubility is improved, and the color filter The tendency of bumping during VCD (vacuum pressure drying) in the filter manufacturing process is suppressed. For example, the content ratio of the low-boiling-point solvent in the solvent (B) is preferably 50 to 99 mass%, more preferably 60 to 95 mass%, further preferably 70 to 90 mass%, and particularly preferably 80 to 85 mass%. %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent B and the above-mentioned low boiling point solvent, the content ratio of the above-mentioned high boiling point solvent B in the (B) solvent is not particularly limited, but is preferably It is 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, especially 2 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, and further The content is preferably 10% by mass or less, and particularly preferably 5% by mass or less. By setting it to the above-mentioned lower limit value or more, alkali solubility is efficiently improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned value, Below the upper limit, the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process tends to increase. For example, the content ratio of the high boiling point solvent B in the solvent (B) is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, further preferably 1 to 10 mass%, and particularly preferably 2 to 5 Mass %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent B and the above-mentioned low boiling point solvent, the content ratio of the low boiling point solvent in the (B) solvent is not particularly limited, but is preferably 80 Mass % or more, more preferably 85 mass % or more, still more preferably 90 mass % or more, especially 95 mass % or more, and preferably 99.9 mass % or less, more preferably 99.5 mass % or less, still more preferably It is 99 mass % or less, especially 98 mass % or less. By setting the value above the above lower limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing step tends to be improved, and by setting the value below the above upper limit, the alkali solubility is improved, and the color filter The tendency of bumping during VCD (vacuum pressure drying) in the filter manufacturing process is suppressed. For example, the content ratio of the low-boiling point solvent in the solvent (B) is preferably 80 to 99.9 mass%, more preferably 85 to 99.5 mass%, further preferably 90 to 99 mass%, and particularly preferably 95 to 98 mass%. %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent A, the above-mentioned high boiling point solvent B, and the above-mentioned low boiling point solvent, the content ratio of the above-mentioned high boiling point solvent A in the solvent (B) is equal to There is no particular limit, but it is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, especially 15 mass% or more, and preferably 50 mass% or less, more preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less. By setting it to the above-mentioned lower limit value or more, alkali solubility is improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned upper limit value, In the following, there is a tendency for the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process to be improved. For example, the content ratio of the high boiling point solvent A in the solvent (B) is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, further preferably 10 to 30 mass %, and particularly preferably 15 to 20 mass %. Mass %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent A, the above-mentioned high boiling point solvent B, and the above-mentioned low boiling point solvent, the content ratio of the above-mentioned high boiling point solvent B in the solvent (B) is equal to There is no particular limit, but it is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, especially 2 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, more preferably 10 mass% or less, particularly preferably 5 mass% or less. By setting it to the above-mentioned lower limit value or more, alkali solubility is efficiently improved, and the occurrence of bumping during VCD (vacuum pressure drying) in the color filter manufacturing step tends to be suppressed. Furthermore, by setting it to the above-mentioned value, Below the upper limit, the efficiency of VCD (vacuum pressure drying) in the color filter manufacturing process tends to increase. For example, the content ratio of the high boiling point solvent B in the solvent (B) is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, further preferably 1 to 10 mass%, and particularly preferably 2 to 5 Mass %.

When the (B) solvent in the colored resin composition of the present invention contains the above-mentioned high boiling point solvent A, the above-mentioned high boiling point solvent B and the above-mentioned low boiling point solvent, the content ratio of the low boiling point solvent in the (B) solvent is not particularly Limit, preferably 30 mass% or more, more preferably 45 mass% or more, further preferably 60 mass% or more, especially 75 mass% or more, and preferably 98.9 mass% or less, more preferably 94.5 mass% % or less, more preferably 89 mass% or less, particularly preferably 83 mass% or less. By setting the value above the above lower limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing step tends to be improved, and by setting the value below the above upper limit, the alkali solubility is improved, and the color filter The tendency of bumping during VCD (vacuum pressure drying) in the filter manufacturing process is suppressed. For example, the content ratio of the low-boiling-point solvent in the solvent (B) is preferably 30 to 98.9 mass%, more preferably 45 to 94.5 mass%, further preferably 60 to 89 mass%, and particularly preferably 75 to 83 mass%. %.

[1-3](C)Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film hardening by photopolymerization and solubility by a developer. As (C) the alkali-soluble resin, for example, Japanese Patent Application Laid-Open Nos. Hei 7-207211, Japanese Patent Application Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, and Japanese Patent Laid-Open No. Hei 11-140144 can be used. , well-known polymer compounds described in Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, etc., among which the following are preferred. Resins of (C-1) to (C-5), etc. (C-1): A copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, obtained by adding an unsaturated monobasic acid to at least part of the epoxy groups in the copolymer. A resin, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)") (C-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as "resin (C-2)") (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl portion of the above-mentioned resin (C-2) (hereinafter may be referred to as "resin (C-3)") (C-4) (meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)") (C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)") Among them, resin (C-1) is particularly preferred and will be described in detail below.

In addition, the resins (C-2) to (C-5) are not limited as long as they are dissolved in an alkaline developer to complete the target development process. Those described as the same items in Japanese Patent Application Publication No. 2009-025813.

(C-1) A copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, obtained by adding an unsaturated monobasic acid to at least part of the epoxy groups in the copolymer. Resin, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction One of the preferred aspects of the resin (C-1) is "5 to 90 mol% of epoxy group-containing (meth)acrylate and 10 to 95 mol% of other radically polymerizable monomers. A copolymer, a resin formed by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups in the copolymer, or adding 10 to 100 mol% of the hydroxyl groups produced by the addition reaction. Alkali-soluble resin obtained from polybasic acid anhydrides."

Examples of the epoxy group-containing (meth)acrylate include: (meth)acrylic acid glycidyl ester, (meth)acrylic acid 3,4-epoxybutyl ester, (meth)acrylic acid (3,4- Epoxycyclohexyl)methyl ester, (meth)acrylic acid 4-hydroxybutyl glycidyl ether, etc. Among them, glycidyl (meth)acrylate is preferred. One type of these epoxy group-containing (meth)acrylates may be used alone, or two or more types may be used in combination.

As another radical 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 preferred.

[Chemical 12]

In formula (V), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Furthermore, R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring. In 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 either saturated or unsaturated. The carbon number of the ring formed by connecting R ⁹⁵ and R ⁹⁷ is preferably 5 to 6.

Among them, examples of the structure represented by the general formula (V) include structures represented by the following formula (Va), (Vb), or (Vc). By introducing these structures into an alkali-soluble resin, when the colored resin composition of the present invention is used to form a color filter, the heat resistance of the colored resin composition is improved. The tendency of pixel intensity to increase.

Furthermore, one type of mono(meth)acrylate having a structure represented by general formula (V) may be used alone, or two or more types may be used in combination.

[Chemical 13]

As the mono(meth)acrylate having the structure represented by the above-mentioned general formula (V), as long as it has this structure, various known ones can be used. In particular, the mono(meth)acrylate represented by the following general formula (VI) is preferred. base) acrylate.

[Chemical 14]

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

In the copolymer of the epoxy group-containing (meth)acrylate and other radically polymerizable monomers, the content ratio of the repeating unit derived from the mono(meth)acrylate represented by the above general formula (VI) is: Among the repeating units derived from the above-mentioned other radically polymerizable monomers, 5 to 90 mol% is preferred, 10 to 70 mol% is more preferred, and 15 to 50 mol% is more preferred.

In addition, the radically polymerizable monomer other than the mono(meth)acrylate represented by the general formula (VI) is not particularly limited. Specific examples thereof include: styrene, styrene α -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives and other vinyl aromatics; butadiene, 2,3-dimethylbutadiene, isoprene, chlorine Butadiene and other dienes; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate , 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, (meth)acrylate )Hexyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isopropyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylate )Propargyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthraquinone (meth)acrylate, sunfloweryl (meth)acrylate, (meth)acrylate Furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, (meth)acrylate Toluyl acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro(meth)acrylate Isopropyl ester, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, (meth)acrylic acid (Meth)acrylates such as 2-hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate; (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-dimethylamide, (Meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthracene (meth)acrylamide such as amide; (meth)acrylamide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-ethylene vinyl pyrrolidinone, vinyl pyridine, vinyl acetate and other vinyl compounds; diethyl methylmaleate, diethyl maleate, diethyl fumarate, itaconic acid Unsaturated dicarboxylic acid diesters such as diethyl ester; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N -(4-Hydroxyphenyl)maleimide and other monomaleimines; N-(meth)acrylylphthalimide, etc.

Among these other radically polymerizable monomers, from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition, it is preferable to contain one selected from the group consisting of styrene, benzyl (meth)acrylate, and monobutyl. One or more of the group consisting of enediamides. Preferred are especially repeating units derived from other radically polymerizable monomers, which are derived from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide. The content ratio of one or more repeating units is 1 to 70 mol%, more preferably 3 to 50 mol%.

Furthermore, the copolymerization reaction of the above-mentioned epoxy group-containing (meth)acrylate and the above-mentioned other radically polymerizable monomers adopts a known solution polymerization method. The solvent used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used. Examples of the solvent include: ethylene glycol monoalkyl ether acetates such as cellosolve acetate and butyl cellosolve acetate; diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbinol Diethylene glycol monoalkyl ether acetate esters such as bis alcohol acetate; propylene glycol monoalkyl ether acetate esters; acetate esters such as ethyl acetate, isopropyl acetate, dipropylene glycol monoalkyl ether acetate esters; Ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers ethers; dipropylene glycol dialkyl ethers; 1,4-dioxane, tetrahydrofuran and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; benzene, toluene , xylene, octane, decane and other hydrocarbons; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; Dimethylformamide, N-methylpyrrolidone, etc. These solvents may be used alone, or two or more types may be used in combination.

The usage amount of these solvents is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass relative to 100 parts by mass of the copolymer obtained. By setting the usage amount of the solvent within the above range, control of the molecular weight of the copolymer tends to become easier. In addition, 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 ones classified as ketone peroxide, peroxyketal, hydrogen peroxide, diallyl peroxide, diacetyl peroxide, peroxyester, and diacetyl peroxide. Carbonates.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, and tert-butyl peroxybenzoate. Trihexyl peroxy(2-ethylhexanoic acid) tert-butyl ester, peroxy(2-ethylhexanoic acid) tert-hexyl ester, 1,1-bis(tert-butylperoxy)-3 ,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyl-3, 3-isopropyl hydroperoxide, hydroperoxide Tert-butyl, dicumyl peroxide, dicumyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Ester, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxy)3,3,5-trimethyl cyclohexane, 1,1-bis(third hexylperoxy)3,3,5-trimethylcyclohexane, etc.

Examples of the azo compound catalyst include azobisisobutyronitrile, azodimethylamide, and the like. Among these, one or two or more radical polymerization initiators with appropriate half-lives according to the polymerization temperature can be used. The usage amount of the radical polymerization initiator 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 monomers used in the copolymerization reaction.

The copolymerization reaction can be carried out by dissolving the monomers and radical polymerization initiators used in the copolymerization reaction in a solvent and raising the temperature while stirring. Alternatively, the monomers added with the radical polymerization initiator can be added dropwise until the temperature is raised. in a stirred solvent. Alternatively, a radical polymerization initiator may be added to the solvent, and the monomer may be added dropwise during the temperature rise process. Reaction conditions can be freely changed depending on the target molecular weight.

In the present invention, the copolymer of the above-mentioned epoxy group-containing (meth)acrylate and the above-mentioned other radically polymerizable monomer preferably contains a repeating compound derived from the epoxy group-containing (meth)acrylate. 5 to 90 mol% of units and 10 to 95 mol% of repeating units derived from other radically polymerizable monomers, and more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, Particularly preferred is one containing 30 to 70 mol% of the former and 70 to 30 mol% of the latter.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to above the lower limit, the addition amount of the unsaturated monobasic acid or polybasic acid anhydride described below tends to become sufficient. , On the other hand, by setting the content ratio of repeating units derived from other radically polymerizable monomers to the above-mentioned lower limit or more, heat resistance and strength tend to become sufficient. Then, the epoxy group part of the copolymer of (meth)acrylate containing epoxy resin and other radically polymerizable monomers is reacted with unsaturated monobasic acid (polymerizable component) and polybasic acid anhydride (alkali-soluble component) .

As the unsaturated monobasic acid added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having ethylenically unsaturated double bonds. Specific examples include: (meth)acrylic acid; crotonic acid, o-/m-/p-vinylbenzoic acid; α-position substituted by a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group, etc. Monocarboxylic acids such as (meth)acrylic acid, etc. Among them, (meth)acrylic acid is preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.

By adding such a component, polymerizability can be imparted to the resin (C-1). The unsaturated monobasic acid is usually added to 10 to 100 mol% of the epoxy groups of the above-mentioned copolymer, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. Ear%. By making it the said lower limit value or more, the stability with time of a colored resin composition tends to become favorable. In addition, as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be used.

Furthermore, known ones can be used as the polybasic acid anhydride added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer. Examples include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chloro-bridged anhydride and other dibasic acid anhydrides; metaphenylene Anhydrides of tricarboxylic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and other acids with more than three yuan. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferred. One type of these polybasic acid anhydrides may be used alone, or two or more types may be used in combination.

By adding such a component, alkali solubility can be imparted to the resin (C-1). These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding unsaturated monobasic acids to the epoxy groups of the copolymers, preferably 20 to 90 mol%. , preferably the addition is between 30 and 80 mol%. By setting the value below the above-mentioned upper limit, the residual film rate during development tends to be good, and by setting it above the above-mentioned lower limit, the solubility tends to become sufficient. In addition, as a method of adding polybasic acid anhydride to a hydroxyl group, a well-known method can be used.

Furthermore, in order to improve the sensitivity, after adding the above-described polybasic acid anhydride, glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to part of the carboxyl groups generated. . In order to improve developability, a glycidyl ether compound that does not have a polymerizable unsaturated group may be added to part of the generated carboxyl groups.

Furthermore, the two can also be added. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. Commercially available products include, for example, the trade names "DENACOL EX-111", "DENACOL EX-121", "DENACOL EX-141", "DENACOL EX-145", "DENACOL EX-146" and "DENACOL EX-146" manufactured by Nagase ChemteX Corporation. DENACOL EX-171", "DENACOL EX-192", etc.

In addition, the structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 or Japanese Patent Application Laid-Open No. 2001-89533, and is known. The polystyrene-reduced weight average molecular weight (Mw) of the resin (C-1) measured by GPC is not particularly limited, but is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. By setting it as above the said lower limit value, heat resistance and film strength tend to become favorable, and by setting it as below the said upper limit value, the solubility to a developer tends to become favorable. Furthermore, as a standard for molecular weight distribution, the ratio of weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.0 to 5.0.

On the other hand, from the viewpoint of coating film curability upon ultraviolet exposure, among (C) alkali-soluble resins, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain (hereinafter sometimes Called "(c1) Acrylic copolymer resin"). (c1) The partial structure of the acrylic copolymer resin including a side chain having an ethylenically unsaturated group is not particularly limited, from the viewpoint of both the hardening properties of the coating film during ultraviolet exposure and the alkali solubility during alkaline development. That is, it is preferable to have a partial structure represented by the following general formula (I), for example.

[Chemical 15]

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. *Indicates bonding key.

Moreover, among the partial structures represented by the above formula (I), from the viewpoint of sensitivity or alkaline developability, a partial structure represented by the following general formula (I') is preferred.

[Chemical 16]

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

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , 1 of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid One or more species. Among these, from the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and homogeneous acid. Promellitic acid, trimellitic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(c1) The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, and more preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, especially 50 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% Mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, particularly preferably 75 mol% or less, most preferably 70 mol% or less. By setting the value above the lower limit, the curability of the coating film during ultraviolet exposure tends to be improved, and by setting it below the above upper limit, the alkali solubility during alkaline development tends to be improved. For example, the content ratio of the partial structure represented by the general formula (I) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 85 mol%, still more preferably It is 40-80 mol%, preferably 50-75 mol%, and most preferably 50-70 mol%.

(c1) The content ratio of the partial structure represented by the general formula (I′) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, and more preferably It is 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, especially 50 mol% or more, and more preferably 95 mol% or less, still more preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 75 mol% or less, most preferably 70 mol% or less. By setting the value above the lower limit, the curability of the coating film during ultraviolet exposure tends to be improved, and by setting it below the above upper limit, the alkali solubility during alkaline development tends to be improved. For example, the content ratio of the partial structure represented by the above general formula (I') is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, and still more preferably Preferably, it is 40-80 mol%, especially 50-75 mol%, and most preferably 50-70 mol%.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains the partial structure represented by the above general formula (I), the other partial structures included are not particularly limited, and in the case of alkaline development From the viewpoint of alkali solubility, for example, it is also preferred to have a partial structure represented by the following general formula (II).

[Chemical 17]

In the above formula (II), 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 above formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Examples of the alkyl group in R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, especially 8 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and further It is better to be below 14, and especially preferably below 12. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these, from the viewpoint of developability, bicyclopentyl or dodecyl is preferred, and bicyclopentyl is more preferred. In addition, examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, Carboxyl group, acryl group, methacryl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the aromatic ring group in R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, especially 18 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group can be a single ring or a condensed ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, and pyrene ring. , benzopyrene ring, phenyl ring, triphenylene ring, acenaphthylene ring, fluoranthracene ring, fluoranthene ring and other bases. In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, Pyrazole ring, imidazole ring, dioxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring , Furanofuran ring, thienofuran ring, benzisinozole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, trisulfazone ring, quinoline ring , isoquinoline ring, azoline ring, quinoline ring, phenanthridine ring, phenidine ring, quinazoline ring, quinazolinone ring, azulene ring and other bases. Among these, from the viewpoint of developability, a phenyl ring group or a naphthyl ring group is preferred, and a phenyl ring group is more preferred. Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, and epoxy groups. , oligoethylene glycol group, phenyl group, carboxyl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkenyl group in R ⁴ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, 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 value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkenyl group include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 2-penten-1-yl. base, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among these, from the viewpoint of developability, vinyl or allyl is preferred, and vinyl is more preferred.

In addition, examples of substituents that the alkenyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, From the viewpoint of developability, carboxyl groups and the like are preferably hydroxyl groups and oligoethylene glycol groups.

As mentioned above, R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Among these, from the viewpoint of developability and film strength, R 4 represents more Preferably it is an alkyl group or an alkenyl group, more preferably it is an alkyl group.

(c1) The content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 5 Mol% or more, more preferably 10 Mol% or more, especially 20 Mol% or more, and preferably 70 Mol% or less, more preferably 60 Mol% or less, still more preferably 50 Mol% Mol% or less, preferably less than 40 mol%. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, the storage stability of a colored resin composition tends to improve. The content ratio of the partial structure represented by the above-mentioned general formula (II) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 20 mol%. 40 mol%.

When the (c1) acrylic copolymer resin contains a partial structure represented by the above general formula (I), as the other included partial structure, the phthalocyanine compound (1) and (c1) the acrylic copolymer resin are From the viewpoint of the alkali solubility of the obtained phthalocyanine compound (1), it is preferable that it contains a partial structure represented by the following general formula (III).

[Chemical 18]

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, or a halogen atom, An alkoxy group, a thiol group which may have a substituent, or an alkylthio group which may have a substituent. t represents an integer from 0 to 5.

(R ⁶ ) In the above formula (III), R ⁶ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, which may have a substituent. an alkoxy group, a thiol group, or an alkylthio group that may have a substituent. 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, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, Especially preferably below 12. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these, from the viewpoint of heat resistance, a dicyclopentyl group or a dodecyl group is preferred, and a dicyclopentyl group is more preferred. In addition, examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, Carboxyl group, acryl group, methacryl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkenyl group in R ⁶ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, 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 value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkenyl group include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 2-penten-1-yl. base, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among these, from the viewpoint of exposure sensitivity during ultraviolet exposure, vinyl or allyl is preferred, and vinyl is more preferred.

In addition, examples of substituents that the alkenyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, From the viewpoint of developability, carboxyl groups and the like are preferably hydroxyl groups and oligoethylene glycol groups.

Examples of the alkynyl group in R ⁶ include linear, branched or cyclic alkynyl groups. The carbon number is preferably 2 or more, preferably 22 or less, 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 value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkynyl group include: 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, and 2-methyl-3-butyn-2-yl. , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, etc.

In addition, examples of substituents that the alkynyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, From the viewpoint of developability, carboxyl groups and the like are preferably hydroxyl groups and oligoethylene glycol groups.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferred from the viewpoint of the storage stability of the (c1) acrylic copolymer resin.

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, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, particularly preferably 12 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and the like.

In addition, examples of substituents that the alkoxy group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. , carboxyl group, acrylyl group, methacrylyl group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

Examples of the alkylthio group in R ⁶ include linear, branched or cyclic alkylthio groups. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, particularly preferably 12 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in a solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved.

Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, and the like. Among these, from the viewpoint of developability, a methylthio group or an ethylthio group is preferred.

In addition, the substituents that the alkyl group in the alkylthio group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group Alcohol group, phenyl group, carboxyl group, acrylic group, methacrylic group, etc., from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferred.

As mentioned above, 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, or a thiol group, Or an alkylthio group which may have a substituent, among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

In the above formula (III), t represents an integer from 0 to 5, and from the viewpoint of ease of production, t is preferably 0.

(c1) The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and more preferably 2 Mol% or more, more preferably 5 Mol% or more, especially 8 Mol% or more, and preferably 50 Mol% or less, more preferably 40 Mol% or less, still more preferably 30 Mol%. Mol% or less, preferably less than 20 mol%. By setting the value to be not less than the above lower limit, the affinity between the phthalocyanine compound (1) and (c1) acrylic copolymer resin tends to be improved, and the alkali solubility tends to be improved, and by being below the above upper limit, there is a tendency that As the proportion of other parts of the structure increases, alkali solubility tends to increase. For example, the content ratio of the partial structure represented by the general formula (III) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, further preferably 5 to 30 mol%, and particularly preferably 8~20 mol%.

In the case where (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), the other included partial structures are also included from the viewpoint of developability. Preferably, it has a partial structure represented by the following general formula (IV).

[Chemical 19]

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (IV), the content ratio is not particularly limited, but is preferably 5 mol% or more. More preferably, it is 10 mol% or more, still more preferably, it is 20 mol% or more, and it is more preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, the storage stability of a colored resin composition tends to improve. For example, in the case of having a partial structure represented by the above general formula (IV), the content ratio is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%. %.

On the other hand, the acid value of (C) the alkali-soluble resin is not particularly limited, but it is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, more preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, the storage stability of a colored resin composition tends to improve. For example, the acid value of (C) the alkali-soluble resin is preferably 10 to 300 mgKOH/g, more preferably 30 to 300 mgKOH/g, further preferably 40 to 250 mgKOH/g, and still more preferably 50 to 200 mgKOH /g, especially 60-150 mgKOH/g.

(C) The weight average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, still more preferably 7,000 or more, especially Preferably it is 8000 or more, and usually it is 30000 or less, Preferably it is 20000 or less, More preferably, it is 15000 or less, Still more preferably, it is 10000 or less. By setting it as above the said lower limit value, heat resistance and coating film hardening property tend to improve, and by setting it as below the said upper limit value, alkali solubility tends to improve. For example, the weight average molecular weight (Mw) of (C) the alkali-soluble resin is preferably from 1,000 to 30,000, more preferably from 2,000 to 30,000, further preferably from 4,000 to 20,000, further preferably from 6,000 to 20,000, and particularly preferably from 7,000 to 7,000. 15,000, the best is 8,000 to 10,000.

The content ratio of (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited. It is usually 1 mass % or more, preferably 5 mass % or more, in the total solid content of the colored resin composition. More preferably, it is 10 mass % or more, further preferably 20 mass % or more, still more preferably 25 mass % or more, especially 30 mass % or more, and usually 80 mass % or less, preferably 60 mass % or less. , more preferably 50 mass% or less, further preferably 40 mass% or less. By setting it to the above lower limit or more, a strong film can be obtained and the adhesion to the substrate tends to be excellent. In addition, by setting it below the above-mentioned upper limit, the permeability of the developer to the exposed portion is low, and the surface smoothness and sensitivity of the pixels can be suppressed from deteriorating. For example, the content ratio of (C) alkali-soluble resin is preferably 1 to 80 mass %, more preferably 5 to 80 mass %, further preferably 10 to 60 mass %, even more preferably 20 to 60 mass %, especially Preferably it is 25-50% by mass, and most preferably 30-40% by mass.

[1-4](D) Photopolymerization initiator The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing (D) a photopolymerization initiator, film curability by photopolymerization can be obtained. (D) The photopolymerization initiator can also be used in the form of a mixture (photopolymerization initiating system) with an accelerator (chain transfer agent) and an optional additive such as a sensitizing dye. The photopolymerization initiator is a component that has the function of directly absorbing light or being sensitized by light to undergo a decomposition reaction or hydrogen abstraction reaction to generate polymerization active free radicals.

Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. Sho 59-152396 and Japanese Patent Laid-Open No. Sho 61-151197; or Japanese Patent Laid-Open Nos. N-aryl-α-amino acids such as hexaarylbimidazole derivatives, halomethyl mesostriphetamine derivatives, N-phenylglycine, and N-aryl-α described in the Public Gazette No. 10-39503 - Radical active agents such as amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone compounds; oxime esters described in Japanese Patent Application Laid-Open No. 2000-80068 Starting agents, etc.

Specific examples of photopolymerization initiators usable in the present invention are listed below. 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-mesotriene, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) )-Mesesine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-meso-tris, 2-(4-ethoxycarbonylnaphthyl)-4,6 - Bis(trichloromethyl)-s-tris-tris and other halomethylated tris-s derivatives;

2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl) Vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4 -Halomethylated 㗁adiazole derivatives such as 㗁oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-㗁adiazole; 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 imidazole derivatives such as (4'-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone, Michlerone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromodiphenyl Methyl ketone, 2-carboxybenzophenone and other benzophenone derivatives; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxy Cyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecane phenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one, 1,1,1-trichloromethyl-(p-butyl Acetophenone derivatives such as basephenyl)ketone; 9-oxosulfide𠮿 , 2-ethyl-9-oxosulfide𠮿 , 2-isopropyl-9-oxosulfide𠮿 , 2-chloro-9-oxosulfide𠮿 , 2,4-dimethyl-9-oxosulfide𠮿 , 2,4-diethyl-9-oxosulfide𠮿 , 2,4-diisopropyl-9-oxysulfide𠮿 Etc-9-oxysulfur𠮿 derivative;

Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenyl acridine and 9-(p-methoxyphenyl) acridine; 9,10-dimethylbenzophenidate and other benzophine derivatives; Anthrone derivatives such as benzanthrone; Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-diphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorobenzene base, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, bicyclo Pentadienyl-Ti-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3 ,4,5,6-pentafluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,6-difluoro- 3-(Pyrrol-1-yl)-phenyl and other titanocene derivatives;

2-Methyl-1[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linylbenzene methyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate , 4-dimethylaminobenzoic acid isopentyl ester, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2 ,5-Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzyl)coumarin, 4-(diethylamine) base) α-amine alkyl benzophenone compounds such as chalcone; 1,2-Octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methyl oxime ester compounds such as benzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime).

Among these, from the viewpoint of sensitivity and surface properties, an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferred. Since the oxime ester compound has a structure that absorbs ultraviolet rays, transmits light energy, and generates free radicals, it has high sensitivity in a small amount and is relatively stable to heat reactions. A small amount of the oxime ester compound can achieve a highly sensitive colored resin. Design of the composition. In particular, from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, an oxime ester compound having a carbazole ring which may have a substituent is preferred.

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

[Chemistry 20]

In the above formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ^21b represents an optional substituent containing an aromatic ring or a heteroaromatic ring. R ^22a represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

The number of carbon atoms in the alkyl group in R ^21a is not particularly limited. From the viewpoint of solubility in a solvent or sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 20 or less. Preferably it is 15 or less, more preferably 10 or less, still more preferably 5 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, and the like. Examples of substituents that the alkyl group may have include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group, 4-(2-methoxy-1-methyl)ethoxy-2 -Methylphenyl or N-acetyl-N-acetyloxyamine group, etc. are preferably unsubstituted from the viewpoint of ease of synthesis.

Examples of the aromatic ring group in R ^21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the colored resin composition, it is preferably 5 or more. Moreover, from the viewpoint of developability, 30 or less is preferable, 20 or less is more preferable, 12 or less is further more preferable, and 8 or less is especially preferable.

Specific examples of the aromatic ring group include phenyl, naphthyl, pyridyl, furyl, and fluoryl. Among these, from the viewpoint of developability, phenyl, naphthyl, and fluoryl are preferred. group, more preferably phenyl or fluoryl. Examples of substituents that the aromatic ring group may have include: hydroxyl group, alkyl group that may have a substituent, alkoxy group that may have a substituent, carboxyl group, halogen atom, amine group, amide group, alkyl group, etc. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is more preferred. Moreover, examples of the substituent in the alkyl group which may have a substituent or the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.

R ^21b is an optional substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoint of solubility in a solvent or sensitivity to exposure, preferred examples include: a carbazolyl group which may have a substituent; a carbazolyl group which may have a substituent; 9-oxosulfide𠮿 A group, an optionally substituted diphenyl sulfide group or an optionally substituted fluorine group, and a group obtained by connecting these groups to a carbonyl group. Among them, from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, a carbazolyl group which may have a substituent, or a carbazolyl group which may have a substituent connected to a carbonyl group is preferred. The foundation of success.

The number of carbon atoms in the alkyl group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 20 or less. 15 or less, more preferably 10 or less, still more preferably 5 or less. Specific examples of the alkyl group include an acetyl group, a propyl group, a butyl group, and the like. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

The number of carbon atoms of the aryl group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 20 or less. Below 15, preferably below 10. Specific examples of the arylyl group include benzyl group, naphthoyl group, and the like. Examples of substituents that the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a amide group, an alkyl group, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

Among the compounds represented by the above-mentioned general formula (I-1), from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, the following general formula (I-2) or (I-3) can be mentioned ) represented by the compound.

[Chemistry 21]

[Chemistry 22]

In the above formula (I-2) or (I-3), R ^21a and R ^22a have the same meaning as in the above general formula (I-1). R ^23a represents an alkyl group which may have a substituent. R ^24a represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a nitro group. The benzene ring constituting the carbazole ring can further be condensed with the aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms in the alkyl group in R ^23a is not particularly limited. From the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less. More preferably, it is 10 or less, and still more preferably, it is 5 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, cyclohexyl, and the like. Examples of the substituent that the alkyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred. Among these, R ^23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and ease of synthesis.

The number of carbon atoms in the alkyl group in R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less. More preferably, it is 10 or less, and still more preferably, it is 5 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, cyclohexyl, and the like. Examples of the substituent that the alkyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

The number of carbon atoms in the aryl group in R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less. , preferably 15 or less, more preferably 10 or less, still more preferably 9 or less. Specific examples of the arylyl group include benzyl group, naphthoyl group, and the like. Examples of the substituent that the aryl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like. From the viewpoint of ease of synthesis, an ethyl group is preferred.

The number of carbon atoms in the heteroaromatic group in R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20. or less, preferably 15 or less, more preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include furancarbonyl group, thiophenecarbonyl group, pyrrolylcarbonyl group, pyridinecarbonyl group, and the like. Examples of substituents that the heteroaryl group may have include carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, nitro, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred. Among these, from the viewpoint of sensitivity, R ^24a is preferably an arylyl group which may have a substituent, and more preferably a benzyl group.

The benzene ring constituting the carbazole ring can further be condensed with the aromatic ring to form a polycyclic aromatic ring.

Commercially available products of this type of oxime ester compound include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qianli Electronic New Materials Co., Ltd., and N manufactured by ADEKA. -1919, NCI-930, NCI-831, etc.

Specific examples of the oxime ester compound include compounds exemplified below, but are not limited to these compounds.

[Chemistry 23]

[Chemistry 24]

[Chemical 25]

Each of these photopolymerization initiators may be used individually by 1 type, or in mixture of 2 or more types.

In addition to the (D) photopolymerization initiator, a chain transfer agent may be used. A chain transfer agent is a compound that has the function of receiving generated free radicals and transferring the received free radicals to other compounds. As the chain transfer agent, various compounds can be used as long as they have the above-mentioned functions. Examples thereof include mercapto group-containing compounds and carbon tetrachloride. In view of the tendency of a higher chain transfer effect, the chain transfer agent is more preferably used. Compounds with sulfhydryl groups. The reason is believed to be that the S-H bonding energy is small, which leads to easy bond breaking and hydrogen abstraction reaction or chain transfer reaction. Effective for improving sensitivity and surface hardening.

Examples of mercapto group-containing compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoethazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H )-Quazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto-containing compounds with aromatic rings; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionic acid) ester), butylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate) , trimethylolpropane trithioglycolate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butylene glycol bis ( 3-Mercaptobutyrate), Ethylene Glycol Bis(3-Mercaptobutyrate), Trimethylolpropane Tris(3-Mercaptobutyrate), Pentaerythritol Tetrakis(3-Mercaptobutyrate), Pentaerythritol Tris( 3-Mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione Among aliphatic mercapto group-containing compounds, especially from the viewpoint of surface smoothness, compounds having a plurality of mercapto groups are preferred.

Among them, among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, 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-tris-2,4,6( 1H,3H,5H)-trione.

Furthermore, in terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate) are preferred. ester), pentaerythritol tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate) , 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis( 3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate). These may be used individually by 1 type, and may be used in combination of 2 or more types.

In the colored resin composition of the present invention, the content ratio of (D) photopolymerization initiator is not particularly limited. In the total solid content of the colored resin composition, it is preferably 1 mass % or more, more preferably 2 Mass% or more, more preferably 3 mass% or more, still more preferably 4 mass% or more, especially 5 mass% or more, and preferably 15 mass% or less, more preferably 10 mass% or less, still more preferably Preferably, it is 8 mass % or less, especially 6 mass % or less. By setting it to the above-mentioned lower limit value or more, the patterning characteristics after development tend to be ensured, and by setting it below the above-mentioned upper limit value, it is possible to suppress the decrease in transmittance caused by excessive addition of the photopolymerization initiator. tendency. For example, the content ratio of (D) the photopolymerization initiator is preferably 1 to 15 mass %, more preferably 2 to 15 mass %, further preferably 3 to 10 mass %, and still more preferably 4 to 8 mass %. , especially preferably 5 to 6% by mass.

When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited. In the total solid content of the colored resin composition, it is preferably 0.01 mass % or more, more preferably 0.1 mass %. More preferably, it is 0.2 mass % or more, further more preferably 0.5 mass % or more, still more preferably 1 mass % or more, especially 1.5 mass % or more, and more preferably 5 mass % or less, more preferably 3 mass% or less, more preferably 2 mass% or less. By setting it within the above range, storage stability and pattern formation ability during alkaline development tend to be ensured. When a chain transfer agent is contained, for example, the content ratio is preferably 0.01 to 5 mass%, more preferably 0.1 to 5 mass%, further preferably 0.2 to 3 mass%, and still more preferably 0.5 to 3 mass%, More preferably, it is 1 to 2 mass %, especially 1.5 to 2 mass %.

[1-5]Other solid components The colored resin composition of the present invention may further contain solid components other than the above components as necessary. Examples of such components include photopolymerizable monomers, dispersants, dispersion aids, surfactants, and the like.

[1-5-1] Photopolymerizable monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it is preferably an addition-polymerizable compound having at least one vinyl double bond (hereinafter referred to as an “ethylene compound”). The vinyl compound is a compound having an vinyl double bond that undergoes addition polymerization and hardens due to the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with active light. In addition, the monomer in the present invention means a concept opposite to a so-called polymer substance, and means that in addition to the monomer in a narrow sense, it also includes the concept of dimers, trimers, and oligomers. In the present invention, it is particularly preferable to use a polyfunctional vinyl monomer having two or more vinyl double bonds per molecule. The number of ethylenic double bonds of the polyfunctional vinyl monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, and more preferably 8 or less. The best number is less than 7. By setting the value above the lower limit, the sensitivity tends to be high, and by setting the value below the upper limit, the solubility in the solvent tends to be improved.

Examples of the vinyl compound include unsaturated carboxylic acid, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids. , an ester obtained by the esterification reaction of unsaturated carboxylic acid and polycarboxylic acid, aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds and other polyhydroxy compounds, making polyisocyanate compounds and (meth)acrylyl group-containing Vinyl compounds with urethane skeleton formed by the reaction of hydroxyl compounds.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate and other acrylates. Examples of these acrylic esters include methacrylates in which the acrylic acid part is replaced with a methacrylic acid part, itaconic acid esters in which the itaconic acid part is replaced, and butyl esters in which the acrylic acid part is replaced. Acrylic acid ester, or maleic acid ester replaced by maleic acid part, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, and resorcin dimethacrylate. acrylate, pyrogallol triacrylate, etc. The ester obtained by the esterification reaction of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound is not necessarily a single substance, but can also be a mixture. Representative examples include: the condensate of acrylic acid, phthalic acid, and ethylene glycol; the condensate of acrylic acid, maleic acid, and diethylene glycol; and the condensate of methacrylic acid, terephthalic acid, and pentaerythritol. Materials; condensates of acrylic acid, adipic acid, butylene glycol and glycerin, etc.

Examples of the vinyl compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acrylyl group-containing hydroxy compound include hexamethylene diisocyanate and trimethylhexamethylene. aliphatic diisocyanates such as methyl diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloxymethyl)propane, 3-hydroxy(1,1,1-trimethylacryloxymethyl) Reactant of hydroxyl compounds containing (meth)acrylyl groups such as propane.

In addition, useful examples of the vinyl compound used in the present invention include: acrylamides such as ethylidenebisacrylamide; allyl esters such as diallyl phthalate; phthalate Divinyl formate and other vinyl-containing compounds. In addition, the vinyl 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. It is preferred that the monomer has an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The functional monomer is particularly preferably one in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol.

One type of these monomers may be used alone. Since it is difficult to use a single compound for production, two or more types may be mixed and used. Moreover, if necessary, a polyfunctional monomer not having an acid group and a polyfunctional monomer having an acid group may be used together as monomers. The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. By setting the value above the above lower limit, the development and dissolution characteristics tend to be improved. By setting the value below the above upper limit, manufacturing and processing become better, and the photopolymerization performance and the surface of the pixel can be easily smoothed. The tendency of sexual hardening to become better. Therefore, when two or more polyfunctional monomers with different acidic groups are used together, or when a polyfunctional monomer without an acidic group is used together, it is preferable that the acidic groups of all the polyfunctional monomers fall into the above-mentioned Adjust within the range.

In the present invention, a more preferred polyfunctional monosystem having an acid group is the succinate ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. A mixture of main ingredients. This multifunctional monomer can also be used in combination with other multifunctional monomers. In addition, what is described in paragraphs [0056] and [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can also be used.

Furthermore, in the present invention, from the viewpoint of improving the chemical resistance of the pixel or the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in Japanese Patent Laid-Open No. 2013-195971 . From the viewpoint of both the sensitivity of the coating film and the shortening of the development time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974.

When the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is not particularly limited. It is usually 0 mass % or more in the total solid content of the colored resin composition. It is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, especially 20 mass% or more, and usually 70 mass% or less, preferably 60 mass% or less. More preferably, it is 50 mass % or less, still more preferably 40 mass % or less, especially 30 mass % or less. By setting it as above the said lower limit value, the curability of a coating film tends to become high, and by setting it as below the said upper limit value, there exists a tendency to suppress the fall of alkali developability. For example, when the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is preferably 0 to 70 mass%, more preferably 5 to 60 mass%, and still more preferably 10 to 50 mass%, particularly preferably 15 to 40 mass%, most preferably 20 to 30 mass%.

[1-5-2]Dispersant, dispersing aid When the colored resin composition of the present invention contains a pigment as the (A) colorant, it is preferred to contain a dispersant in order to stably disperse the pigment. Among dispersants, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, Sorbitan aliphatic ester dispersant, aliphatic modified polyester dispersant. Specific examples of these dispersants include: represented by trade names, EFKA (registered trademark, manufactured by BASF Corporation), DisperBYK (registered trademark, manufactured by BYK-Chemie Corporation), Disparlon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), those listed in Japanese Patent Application Laid-Open No. 2013-119568, etc.

Among polymer dispersants, from the viewpoint of dispersibility or storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred. As a block copolymer having a functional group containing a nitrogen atom, it is preferable to include an A block having a quaternary ammonium salt group and/or an amine group in the side chain and a block B having no quaternary ammonium salt group and/or an amine group. Block A-B block copolymer and/or B-A-B block copolymer.

Examples of the functional group containing a nitrogen atom include a primary to tertiary amine group or a quaternary ammonium salt group. From the viewpoint of dispersibility or storage stability, it is preferred to have a primary to tertiary amine group, and more preferably to have a quaternary ammonium salt group. Tertiary amine group. The structure of the repeating unit having a tertiary amine group in the block copolymer is not particularly limited. From the viewpoint of dispersibility or storage stability, a repeating unit represented by the following general formula (1) is preferred.

[Chemical 26]

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent. R ¹ and R ² Can bond with each other to form a cyclic structure. R ³ is a hydrogen atom or methyl group. X is a bivalent linking base.

The carbon number of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, more preferably 6 or less, still more preferably 4 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, propyl, Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included.

The carbon number of the aryl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred. base, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The carbon number of the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, still more preferably 9 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylene, phenylbutylene, phenylisopropylene, and the like. Among these, phenylmethylene is preferred. base, phenylethylidene, phenylpropyl, or phenylbutyl, more preferably phenylmethylene, or phenylethylidene.

Among these, from the viewpoint of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are preferably each independently an alkyl group that may have a substituent, and more preferably are methyl or ethyl. base.

Examples of the substituent that the alkyl group, aralkyl group or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzyl group, a hydroxyl group, etc., from the viewpoint of ease of synthesis. , preferably unsubstituted.

Furthermore, in the above formula (1), examples of the cyclic structure formed by R ¹ and R ² bonding to each other include nitrogen-containing heterocyclic monocyclic rings with 5 to 7 members or the condensation of two of them. The condensed ring. The nitrogen-containing heterocyclic ring is preferably not aromatic, and is more preferably a saturated ring. Specific examples include the following (IV).

[Chemical 27]

These cyclic structures may further have substituents.

In the above formula (1 ⁾ , examples of the divalent linking group R ¹⁴ -group [wherein R ¹³ and R ¹⁴ are a single bond, an alkylene group with 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group with 2 to 10 carbon atoms)], etc., preferably -COO -R ¹⁴ -base.

Moreover, the content ratio of the repeating unit represented by the above formula (1) in all the repeating units of the above-mentioned block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20% or more, most preferably 25 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less. When it is within the above range, both dispersion stability and high brightness tend to be achieved. For example, the content ratio of the repeating units represented by the above formula (1) in all the repeating units of the above-mentioned block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and still more preferably It is preferably 10 to 70 mol%, more preferably 15 to 70 mol%, even more preferably 20 to 50%, and most preferably 25 to 40 mol%.

Furthermore, from the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (2).

[Chemical 28]

In the above formula (2), R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an alkyl group which may have a substituent, and R ¹² is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

The carbon number of the optionally substituted alkyl group in R ¹¹ of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Furthermore, it is more preferable that it is 4 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, propyl, Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included. Examples of optional substituents include halogen atoms, alkoxy groups, benzyl groups, hydroxyl groups, and the like. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

In addition, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less, and more preferably 10 or less, from the viewpoint of compatibility and dispersibility with binder components such as solvents. The best value is below 5.

Moreover, the content ratio of the repeating unit represented by the above formula (2) in all the repeating units of the above-mentioned block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. When the content is within the above range, there is a tendency to achieve both compatibility with binder components such as solvents and dispersion stability. For example, the content ratio of the repeating units represented by the above formula (2) in all the repeating units of the above-mentioned block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably Preferably, it is 4 to 10 mol%.

Furthermore, from the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (3).

[Chemical 29]

In the above formula (3), R ⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁹ is a hydrogen atom or a methyl group.

The carbon number of the optionally substituted alkyl group in R ⁸ of the above formula (3) is not particularly limited, but is usually 1 or more, preferably 1 or more, and is preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Among these, methyl, ethyl, propyl, Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Moreover, it may be either linear or branched. Furthermore, cyclic structures such as cyclohexyl group and cyclohexylmethyl group may be included.

The carbon number of the aryl group which may have a substituent in R ⁸ of the above formula (3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred. base, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The carbon number of the optionally substituted aralkyl group in R ⁸ of the above formula (3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylene, phenylbutylene, phenylisopropylene, and the like. Among these, phenylmethylene is preferred. base, phenylethylidene, phenylpropyl, or phenylbutyl, more preferably phenylmethylene, or phenylethylidene.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group. Examples of substituents that the alkyl group in R ⁸ may have include a halogen atom, an alkoxy group, and the like. In addition, examples of substituents that the aryl group or aralkyl group may have include chain alkyl groups, halogen atoms, alkoxy groups, and the like. In addition, the chain alkyl group represented by R ⁸ includes both linear and branched chains.

Moreover, the content ratio of the repeating unit represented by the above formula (3) in all the repeating units of the above-mentioned block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less. When it is within the above range, both dispersion stability and high brightness tend to be achieved. For example, the content ratio of the repeating units represented by the above formula (3) in all the repeating units of the above-mentioned block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably The best value is 50 to 70 mol%.

The block copolymer may have repeating units other than the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). Examples of such repeating units include repeating units derived from the following monomers: styrenic monomers such as styrene and α-methylstyrene; and (meth)acrylic acid salts such as (meth)acrylic acid chloride. Monomers; (meth)acrylamide-based monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ether; N-methacrylamide, etc.

From the viewpoint of further improving dispersion, a block containing an A block having a repeating unit represented by the above general formula (1) and a B block not having a repeating unit represented by the above general formula (1) is preferred. segment copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Furthermore, it is more preferable that the B block has a repeating unit represented by the above general formula (2) and a repeating unit represented by the above general formula (3).

Furthermore, the A block may contain a repeating unit other than the repeating unit represented by the above general formula (1). Examples of such repeating units include the above-mentioned (meth)acrylate derived units. Repeating units of monomers, etc. The content of repeating units other than the repeating units represented by the above general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably in the A block Does not contain this repeating unit.

The B block may also contain a repeating unit represented by the above-mentioned general formula (2) and a repeating unit other than the repeating unit represented by the above-mentioned general formula (3). Examples of such repeating units include the following units: Repeating units of the body: styrenic monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylamide; (meth)acrylamide, N-hydroxy (Meth)acrylamide monomers such as methacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; N-methacrylamide, etc. The content of the repeating units represented by the above general formula (2) and the repeating units other than the repeating units represented by the above general formula (3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 Mol%, preferably no repeating unit in the B block.

Furthermore, in terms of dispersibility, the acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH/g. The acid value here represents the number of mg of KOH required to neutralize 1 g of the solid content of the dispersant.

Furthermore, from the viewpoint of dispersibility and developability, the amine value of the above-mentioned block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, further preferably 70 mgKOH/g or more, and further More preferably, it is 90 mgKOH/g or more, particularly preferably 100 mgKOH/g or more, most preferably 110 mgKOH/g or more, and more preferably, it is 150 mgKOH/g or less, still more preferably 130 mgKOH/g or less. The amine value here represents the amine value converted from the effective solid content, and is a value expressed by the mass of KOH equivalent to the amount of alkali per 1 g of the solid content of the dispersant. For example, the amine value of the above-mentioned block copolymer is preferably 30 to 150 mgKOH/g, more preferably 50 to 150 mgKOH/g, still more preferably 70 to 150 mgKOH/g, still more preferably 90 to 130 mgKOH/g. g, especially preferably 100-130 mgKOH/g, and optimally 110-130 mgKOH/g.

In addition, the molecular weight of the block copolymer is preferably in the range of 1,000 to 30,000 in terms of polystyrene-reduced weight average molecular weight (hereinafter sometimes referred to as "Mw"). When the coating is within the above range, the dispersion stability becomes good, and dry foreign matter tends to be less likely to occur when coating is performed using a slit nozzle method.

The above-mentioned block copolymer can be produced by a known method, for example, it can be produced by living polymerization of a monomer into which each of the above-mentioned repeating units is introduced. As a living polymerization method, Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, or 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), 18, 1037 (1986), Koichi Roshi, Koichi Hatada , Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987), etc.

When the colored resin composition of the present invention contains a dispersant, the content ratio of the dispersant is not particularly limited, but it is preferably 0.001 mass % or more, and more preferably 0.01 mass % in the total solid content of the colored resin composition. % or more, more preferably 0.1 mass % or more, particularly preferably 1 mass % or more, and preferably 25 mass % or less, more preferably 20 mass % or less, further preferably 15 mass % or less, particularly preferably 10% by mass or less. By setting it as above the said lower limit value, the dispersibility or storage stability tends to improve, and by setting it as below the said upper limit value, there exists a tendency for electrical reliability or developability to improve. For example, the content ratio of the dispersant in the total solid content of the colored resin composition is preferably 0.001 to 25 mass %, more preferably 0.01 to 20 mass %, further preferably 0.1 to 15 mass %, and particularly preferably 1～10% by mass.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the pigment. It is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, especially 20 parts by mass or more, and more preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass. parts or less, preferably 30 parts by mass or less. By setting it within the above range, a colored resin composition having excellent dispersion stability and high brightness tends to be obtained. For example, when a pigment and a dispersant are contained, the content ratio of the dispersant relative to 100 parts by mass of the pigment is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 50 parts by mass. parts, more preferably 15 to 40 parts by mass, even more preferably 20 to 30 parts by mass.

In addition, when the colored resin composition of the present invention contains a pigment, in order to improve the dispersibility of the pigment and improve the dispersion stability, a pigment derivative or the like may be included as a dispersion aid. Examples of pigment derivatives include: azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, isoindoline-based, dioxin-based, Derivatives of anthraquinone series, indanthroline series, perylene series, pyrenone series, diketopyrrolopyrrole series, dimethacin series pigments, etc. Examples of substituents of the pigment derivative include sulfonic acid group, sulfonamide group and its quaternary salt, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group, etc. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., preferably include a sulfonamide group and its quaternary salt, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, these substituents may be substituted in plural on one pigment skeleton, or may be a mixture of compounds with different numbers of substitutions. Specific examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, and sulfonic acid derivatives of isoindoline pigments. Sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, sulfonic acid derivatives of dimethacin pigments, etc.

[1-5-3] Surfactant As the surfactant, various surfactants, such as anionic, cationic, nonionic, and amphoteric surfactants, can be used. However, since the possibility of adversely affecting various properties is low, it is preferable to use a nonionic surfactant. active agent. The content ratio of the surfactant is not particularly limited. It is used in the following range in the total solid content of the colored resin composition: usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more. It is more preferably 0.1 mass% or more, and usually 10 mass% or less, preferably 1 mass% or less, further preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less. For example, when a surfactant is contained, for example, the content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and further preferably 0.001 to 10% by mass, based on the total solid content of the colored resin composition. Preferably, it is 0.05-0.5 mass %, More preferably, it is 0.1-0.3 mass %.

[2] Preparation of colored resin composition Next, a method for preparing the colored resin composition (hereinafter, sometimes referred to as a photoresist) of the present invention will be described.

When preparing one containing a pigment as a colorant, first, specific amounts of the pigment, solvent and dispersant are respectively weighed, and in the dispersion treatment step, the pigment is dispersed to prepare a pigment dispersion liquid. In this dispersion treatment step, a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc. can be used. By performing this dispersion treatment, the pigment is finely divided, so the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

When dispersing a pigment, as mentioned above, it is preferable to appropriately use a dispersion aid, a dispersion resin, etc. in combination. When using a sand mill for dispersion processing, it is preferred to use glass beads or zirconia beads with a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to a range of 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. Furthermore, the precise dispersion time varies depending on the composition of the pigment dispersion and the size of the sand mill device, so it can be adjusted appropriately.

A solvent, an alkali-soluble resin, a photopolymerization initiator, and optional components other than the above are mixed with the pigment dispersion liquid obtained by the above-mentioned dispersion treatment to prepare a uniform dispersion solution. Furthermore, fine contaminants may be mixed in each step of the dispersion treatment and mixing. Therefore, it is preferable to filter the obtained pigment dispersion through a filter or the like.

When a pigment is not used as a colorant, a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and optional components other than the above can be mixed to obtain a homogeneous solution. It is preferable to filter the obtained solution through a filter or the like.

[3] Manufacturing of color filter substrate Next, the color filter of the present invention will be described. The color filter of the present invention has pixels formed using the colored resin composition of the present invention. The colored resin composition of the present invention is preferably a colored resin composition for forming pixels of a color filter.

[3-1] Transparent substrate (support) As long as the transparent substrate of the color filter is transparent and has moderate strength, its material is not particularly limited. Examples of materials include: polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; and thermoplastic resin sheets of polycarbonate, polymethylmethacrylate, and polyurethane. Materials; thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, or various glasses. Among them, from the viewpoint of heat resistance, glass or heat-resistant resin is preferred.

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

[3-2]Black matrix The color filter of the present invention can be manufactured by disposing a black matrix on the above-mentioned transparent substrate to form pixel images usually of red, green, and blue. The above-mentioned colored resin composition is preferably used as a coating liquid for forming green pixels (photoresist patterns) among red, green, and blue pixels (hereinafter may be abbreviated as "green photoresist"). Use green photoresist to coat, heat and dry, image expose, and develop on the resin black matrix formation surface formed on the transparent substrate, or on the metal black matrix formation surface formed using chromium compounds and other light-shielding metal materials. and thermal hardening processes to form pixel images.

The black matrix is formed on a transparent substrate using a light-shielding metal film or a colored resin composition for black matrix. As the light-shielding metal material, metal chromium, chromium compounds such as chromium oxide and chromium nitride, nickel and tungsten alloys, etc. can be used, or a plurality of these materials can be laminated in a layered form. These metal light-shielding films are usually formed by sputtering. After forming the required pattern into a film shape using a positive photoresist, for chromium, ceric ammonium nitrate is mixed with perchloric acid and/or nitric acid. For other materials, use an etching solution corresponding to the material for etching, and finally use a special stripper to peel off the positive photoresist, thereby forming a black matrix.

In this case, first, thin films of the metal or metal/metal oxide are formed on the transparent substrate by evaporation or sputtering. Next, after forming a coating film of the colored resin composition on the film, the coating film is exposed and developed using a photomask with repeated patterns such as stripes, mosaics, triangles, etc. to form a photoresist image. Thereafter, the coating film is etched to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, black colorants containing carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc. may be used alone or in plural, or red, green, and blue appropriately selected from inorganic or organic pigments and dyes may be used. A black matrix is formed in the same manner as the method for forming red, green, and blue pixel images described below by mixing a colored resin composition with a black colorant.

[3-3]The formation of pixels A colored resin composition of one color among red, green, and blue is coated on a transparent substrate provided with a black matrix, and after drying, a photomask is overlapped on the coating film, and the photomask is interposed, and the image is exposed , development, thermal hardening or light hardening as needed to form a pixel image. This operation is performed separately on the colored resin compositions of three colors: red, green, and blue, whereby a color filter image can be formed.

The colored resin composition for color filters can be coated by spin coating, wire bar coating, flow coating, die coating, roll coating, spray coating, or the like. Among them, the nozzle coating method is preferable from the comprehensive viewpoints of significantly reducing the amount of coating liquid used, being completely unaffected by the mist attached during spin coating, and suppressing the generation of foreign matter.

If the thickness of the coating film is too large, it may become difficult to develop the pattern and adjust the gap in the liquid crystal unitization step. On the other hand, if it is too small, it may be difficult to increase the pigment concentration, making it impossible to achieve the desired results. Color performance. The thickness of the coating film is in the following range based on the film thickness after drying: usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less. More preferably, it is 5 μm or less.

[3-4] Drying of coating film The drying of the coating film after the colored resin composition is applied to the substrate is preferably performed by a drying method using a hot plate, an IR (infrared ray, infrared) oven, or a convection oven. It is usually heated again for drying after pre-drying. Pre-drying conditions can be appropriately selected based on the types of solvent components mentioned above, the performance of the dryer used, etc. The drying temperature and drying time can be selected according to the type of solvent components, the performance of the dryer used, etc. Specifically, the drying temperature is in the following range: usually above 40°C, preferably above 50°C, and usually 80°C. ℃ or lower, preferably 70 ℃ or lower; the drying time is in the following range: usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

The temperature condition for reheat drying is preferably a temperature higher than the pre-drying temperature, specifically within the following range: usually above 50°C, preferably above 70°C, and usually below 200°C, preferably below 160°C. ℃ or lower, preferably 130 ℃ or lower. Moreover, the drying time also depends on the heating temperature, and is set in the following range: usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, especially 5 minutes. The higher the drying temperature is, the better the adhesion to the transparent substrate will be. However, if it is too high, the alkali-soluble resin may decompose and cause thermal polymerization, resulting in poor development. Furthermore, as the drying step of the coating film, a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature can also be used.

[3-5]Exposure steps Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. At this time, if necessary, in order to prevent the decrease in sensitivity of the photopolymerizable layer caused by oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer and then exposed. The light source used for the above image exposure is not particularly limited. Examples of light sources include: 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 other light sources; or argon ion lasers , YAG (Yttrium Aluminum Garnet, Yttrium Aluminum Garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser light sources. Optical filters can also be used when using light of a specific wavelength.

[3-6]Developing step The color filter of the present invention can be developed by using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after subjecting a coating film using the colored resin composition of the present invention to image exposure using the above light source. Thereby, an image is formed on the substrate and manufactured. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Examples of basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic alkaline compounds; or mono, di or triethanolamine, mono, di or trimethylamine, mono, di or triethylamine Ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Organic alkaline compounds. These basic compounds may also be a mixture of two or more types.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceryl alkyl esters, etc. Nonionic surfactants; anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts, etc. ; Alkyl betaines, amino acids and other amphoteric surfactants.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. Organic solvents can be used together with aqueous solutions. The conditions for the development treatment are not particularly limited. The development temperature is in the following range: usually 10°C or higher, preferably 15°C or higher, and more preferably 20°C or higher, and usually 50°C or lower, with 45°C being preferred. ° C or lower, and more preferably 40 ° C or lower. As the development method, any method such as immersion development method, spray development method, brush development method, ultrasonic development method, etc. can be used.

[3-7] Thermal hardening treatment The developed color filter is thermally hardened. Regarding the thermal hardening treatment conditions at this time, the temperature is selected within the following range: usually above 100°C, preferably above 150°C, and usually below 280°C, preferably below 250°C; the time is above 5 minutes , select the range below 60 minutes. Through this series of steps, the formation of a patterned image of one color is completed. This step is repeated in sequence to pattern black, red, green, and blue to form a color filter. Furthermore, the order of patterning of the four colors is not limited to the above order.

[3-8] Formation of transparent electrode The color filter of the present invention can directly form ITO (Indium Tin Oxides, indium tin oxide) and other transparent electrodes on the image, and is used as a part of components such as color displays and liquid crystal display devices to improve surface smoothness or durability. , you can also install top coatings such as polyamide and polyimide on the image if necessary. In addition, in some applications such as in-plane alignment driving mode (IPS (In-Plane Switching, lateral electric field effect) mode), transparent electrodes may not be formed.

[4] Image display device (panel) Next, the image display device of the present invention will be described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, as image display devices, a liquid crystal display device and an organic EL display device will be described in detail.

[4-1] Liquid crystal display device The manufacturing method of the liquid crystal display device of this invention is demonstrated. The liquid crystal display device of the present invention usually forms an alignment film on the above-mentioned color filter of the present invention, and after spreading spacers on the alignment film, it is bonded to a counter substrate to form a liquid crystal unit, and the liquid crystal unit is injected into the formed liquid crystal unit. LCD and connected to the counter electrode to complete. The alignment film is suitably a resin film such as polyimide. The alignment film is usually formed by gravure printing and/or flexographic printing, and the thickness of the alignment film is set to several 10 nm. After the alignment film is hardened by thermal baking, the surface is treated by ultraviolet irradiation or a rubbing cloth to form a surface state that can adjust the slope of the liquid crystal.

The size of the spacer used corresponds to the gap (gap) between the spacer and the opposing substrate, which is usually 2 to 8 μm. A photosensitive spacer (PS) of a transparent resin film can also be formed on the color filter substrate by photolithography and effectively used to replace the spacer. As the counter substrate, an array substrate is usually used, and a TFT (Thin Film Transistor) substrate is particularly preferred.

The bonding gap with the counter substrate varies depending on the purpose of the liquid crystal display device, and is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is hardened by UV (ultraviolet, ultraviolet) irradiation and/or heating, thereby sealing the periphery of the liquid crystal cell. After the liquid crystal unit with a sealed periphery is cut into panel units, the pressure is reduced in a vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal to leak air in the chamber, thereby injecting liquid crystal into the liquid crystal unit. The degree of pressure reduction in the liquid crystal cell is in the following range: usually 1×10 ^-2 Pa or more, preferably 1×10 ^-3 or more, and usually 1×10 ^-7 Pa or less, preferably 1×10 ^- Below ⁶ Pa. Moreover, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is within the following range: usually 30°C or higher, preferably 50°C or higher, and usually 100°C or lower, preferably 90°C or lower.

The heating and holding during pressure reduction is usually in the range of 10 minutes to 60 minutes, and then the liquid crystal is immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal has been injected, UV curable resin is cured to seal the liquid crystal injection port, thereby completing a liquid crystal display device (panel). The type of liquid crystal is not particularly limited and may be any of previously known lyotropic liquid crystals, thermotropic liquid crystals, etc., such as aromatic systems, aliphatic systems, and polycyclic compounds. Among thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, etc. are known, and any of them may be used.

[4-2] Organic EL display device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1 , on the transparent support substrate 10 , the organic protective layer 30 and the inorganic oxide film 40 are separated by the organic EL display device of the present invention. The organic light-emitting body 500 is laminated on the blue color filter on which the pixel 20 is formed using the colored resin composition, thereby producing a multi-color organic EL element.

As a lamination method of the organic light-emitting body 500, there can be cited: 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. method; or a method of bonding the organic light-emitting body 500 formed on other substrates to the inorganic oxide film 40, etc. The organic EL element 100 fabricated in the above manner can be applied to a passively driven organic EL display device or an actively driven organic EL display device. [Example]

Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example as long as it does not deviate from the summary.

<Phthalocyanine Compound A> Phthalocyanine compound A having the following chemical structure synthesized based on Example 30 of Japanese Patent Application Laid-Open No. 05-345861 was used.

[Chemical 30]

Et in the formula represents ethyl group.

<Phthalocyanine compound B> Mix 5.00 g (18.8 mmol) of tetrachlorophthalonitrile, 3.32 g (18.8 mmol) of 2-cyclohexyl-5-methylphenol, 3.89 g (28.2 mmol) of potassium carbonate and 50 mL of acetonitrile and heat to 70°C , stir in this state for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and concentrated. The obtained residue was recrystallized using acetonitrile to obtain 4.70 g of a mixture of intermediate A and intermediate B (yield 59%, purity 77.9%, intermediate A/intermediate B = 73/23). In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 31]

Mix 3.00 g (7.15 mmol) of the mixture of intermediate A and intermediate B, 0.69 g (2.14 mmol) of zinc iodide and 7.2 g of benzonitrile, and react at 170°C for 6.5 hours. After the reaction was completed, the reaction solution was cooled and poured into 20 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50° C. to obtain 2.62 g (yield 84%) of phthalocyanine compound B.

[Chemical 32]

1 mg of phthalocyanine compound B was dissolved in 100 mL of DMSO (dimethylstyrene). For the visible light absorption spectrum, a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies) was used, using 1 cm The measurement was carried out using a square quartz trough. The maximum absorption wavelength was 651.0 nm, and the Mohr absorption coefficient (ε) was 4.08×10 ⁵ .

<Phthalocyanine compound C> Mix 4.00 g (20 mmol) of tetrafluorophthalonitrile, 2.90 g (5.0 mmol) of potassium fluoride and 10 mL of acetone. After cooling in an ice bath, add 6.65 g (40 mmol) of ethyl parahydroxybenzoate. Acetone (30 mL) solution was stirred in this state for 5 hours. After the reaction, the reaction solution was filtered and concentrated, 60 mL of ethanol was added, and the precipitated precipitate was filtered, separated, and dried to obtain 6.20 g (yield 63%, purity 97.6%) of intermediate C. In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 33]

Et in the formula represents ethyl group.

Mix 3.01 g (6.11 mmol) of intermediate C, 0.246 g (1.83 mmol) of copper (II) chloride and 7.2 g of benzonitrile, and react at 160°C for 7 hours. After the reaction was completed, the reaction solution was cooled and poured into 40 mL of methanol. The generated solid content was filtered, washed with methanol, and dried under reduced pressure at 50°C. The obtained solid was purified by medium pressure fractionation liquid chromatography (the developing solvent was a mixed solvent of chloroform and methanol, gradient of 100:0 to 92:8 (volume ratio)), thereby obtaining 1.13 g (yield 40%) phthalocyanine compound C.

[Chemical 34]

Et in the formula represents ethyl group.

1 mg of phthalocyanine compound C was dissolved in 100 mL of THF (tetrahydrofuran), and the visible light absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies) using a 1 cm square quartz cell. The measurement was carried out and the result was that the maximum absorption wavelength was 695.0 nm and the Mohr absorption coefficient (ε) was 1.11×10 ⁵ .

<Phthalocyanine compound D> Mix 5.00 g (25.0 mmol) of tetrafluorophthalonitrile, 6.90 g (50.0 mmol) of potassium carbonate and 50 mL of acetonitrile. A solution of 8.21 g (50.0 mmol) of 4-tertiary amylphenol in acetonitrile (30 mL) was added at room temperature. After stirring for 5 hours, the mixture was heated to 80°C and stirred for a further 2 hours. The reaction solution was cooled and filtered, acetonitrile was distilled from the filtrate using a rotary evaporator, and ethanol was added for recrystallization. The obtained solid was filtered, and 7.20 g (yield 59%, purity 91.4%) of intermediate D was obtained by vacuum drying. In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 35]

¹ H-NMR (CDCl ₃ ) δ : 0.66 (t, 6H), 1.25 (s, 12H), 1.60 (q, 4H), 6.71 (d, 4H), 7.20 (d, 4H)

Mix 4.95 g (10.5 mmol) of intermediate D, 1.00 g (3.14 mmol) of zinc iodide and 10 g of benzonitrile, and react at 160°C for 6 hours. After the reaction was completed, the reaction solution was cooled and poured into 100 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50° C. to obtain 4.46 g (yield 84%) of phthalocyanine compound D.

[Chemical 36]

1 mg of phthalocyanine compound D was dissolved in 100 mL of DMSO, and the visible light absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies) using a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 701.0 nm, and the Mohr absorption coefficient (ε) was 1.248×10 ⁵ .

<Phthalocyanine compound E> Mix 5.00 g (25.0 mmol) of tetrafluorophthalonitrile, 6.90 g (50.0 mmol) of potassium carbonate and 85 mL of acetone and cool in an ice bath. A solution of 7.60 g (50.0 mmol) of methyl parahydroxybenzoate in acetone (30 mL) was added at 2 to 4°C, and the mixture was stirred for 6 hours. The reaction liquid was filtered, acetone was distilled off from the filtrate using a rotary evaporator, and ethanol was added for recrystallization. The obtained solid was filtered, and 7.20 g (yield 62%, purity 91.5%) of intermediate E was obtained by vacuum drying. In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 37]

Me in the formula represents methyl group.

¹ H-NMR (CDCl ₃ ) δ : 3.91 (s, 6H), 6.80 (d, 4H), 7.97 (d, 4H)

Mix 5.00 g (10.8 mmol) of intermediate E, 1.03 g (3.23 mmol) of zinc iodide and 12 mL of benzonitrile, and react at 170°C for 9 hours. After the reaction was completed, the reaction solution was cooled and poured into 20 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50° C. to obtain 4.46 g (yield 85%) of phthalocyanine compound E.

[Chemical 38]

Me in the formula represents methyl group.

¹ H-NMR (DMSO-d ₆ ) δ : 3.82 (s, 24H), 7.25 (d, 16H), 7.78 (d, 16H)

1 mg of phthalocyanine compound E was dissolved in 100 mL of DMSO, and the visible light absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies) using a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 665.0 nm, and the Mohr absorption coefficient (ε) was 1.190×10 ⁵ .

<Phthalocyanine compound F> Mix 3.02 g (15.0 mmol) of tetrafluorophthalonitrile, 4.14 g (30.0 mmol) of potassium carbonate and 50 mL of acetone and cool in an ice bath. A solution of 5.40 g (30.0 mmol) n-propyl parahydroxybenzoate in acetone (30 mL) was added at 2 to 4°C, and stirred in this state for 5 hours. The reaction liquid was filtered, acetone was distilled off from the filtrate using a rotary evaporator, and ethanol was added for recrystallization. The obtained solid was filtered, and 4.0 g (yield 51%, purity 95.9%) of intermediate F was obtained by vacuum drying. In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 39]

n-Pr in the formula represents n-propyl group.

¹ H-NMR (CDCl ₃ ) δ : 1.03 (t, 6H), 1.78 (m, 4H), 4.29 (t, 4H), 6.82 (d, 4H), 7.98 (d, 4H)

Mix 1.00 g (2.15 mmol) of intermediate F, 0.21 g (0.65 mmol) of zinc iodide and 2.4 mL of benzonitrile, and react at 170°C for 13 hours. After the reaction was completed, the reaction solution was cooled and poured into 20 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50° C. to obtain 0.33 g (yield 29%) of phthalocyanine compound F.

[Chemical 40]

n-Pr in the formula represents n-propyl group.

¹ H-NMR (DMSO-d ₆ ) δ : 0.94 (t, 24H), 1.88 (m, 16H), 4.16 (t, 16H), 7.25 (d, 16H), 7.78 (d, 16H)

1 mg of phthalocyanine compound F was dissolved in 100 mL of DMSO (dimethylstyrene). For the visible light absorption spectrum, a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Co., Ltd.) was used, using 1 cm The measurement was carried out using a square quartz trough, and the maximum absorption wavelength was 665.0 nm, and the Mohr absorption coefficient (ε) was 1.202×10 ⁵ .

<Phthalocyanine compound G> Mix 2.00 g (10 mmol) of tetrafluorophthalonitrile, 1.45 g (2.5 mmol) of potassium fluoride and 5 mL of acetone. After cooling in an ice bath, add methyl 3-(4-hydroxyphenyl)propionate. A solution of 3.78 g (21 mmol) in acetone (5 mL) was stirred in this state for 5 hours. After the reaction, the reaction solution was extracted with chloroform-water, and the organic layer was extracted with saturated brine, and subjected to medium-pressure fractionation liquid chromatography (the developing solvent was a mixed solvent of hexane and ethyl acetate, 94:6~ The concentrated product was purified (gradient of 73:27 (volume ratio)) to obtain 3.00 g (yield 58%, purity 97.8%) of intermediate G. In addition, the purity is an area % value calculated based on the results of high performance liquid chromatography analysis.

[Chemical 41]

¹ H-NMR (CDCl ₃ ) δ : 2.58 (t, 2H), 2.90 (t, 2H), 3.67 (s, 3H), 6.70 (d, 2H), 7.09 (d, 2H)

Mix 1.04 g (2.00 mmol) of intermediate G, 0.19 g (0.6 mmol) of zinc iodide and 2 mL of benzonitrile, and react at 160°C for 8 hours. After the reaction is completed, the reaction solution is cooled and purified by medium pressure fractionation liquid chromatography (the developing solvent is a mixed solvent of chloroform and methanol, gradient of 100:0 to 93:7 (volume ratio)), whereby 0.75 g (yield 70%) of phthalocyanine compound G was obtained.

[Chemical 42]

1 mg of phthalocyanine compound G was dissolved in 100 mL of DMSO, and the visible light absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies) using a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 700.0 nm, and the Mohr absorption coefficient (ε) was 2.278×10 ⁵ .

＜Dispersant A: Dispersant "BYK-LPN6919" manufactured by BYK-Chemie Corporation＞ A methacrylic AB block copolymer containing an A block having a functional group containing nitrogen atoms and a B block having a solvophilic group. It has repeating units of the following formulas (2a) and (3a), and does not have the repeating unit of the following formula (1a). The amine value is 120 mgKOH/g and the acid value is below 1 mgKOH/g.

The content ratios of the following formulas (2a) and (3a) in all the repeating units are 33.3 mol% and 6.7 mol% respectively.

[Chemical 43]

＜Preparation of Green Pigment Dispersion 1＞ A stainless steel container was filled with 11.0 parts by mass of C.I. Pigment Green 58, 1.6 parts by mass of dispersant A in terms of solid content, and 3.3 parts by mass of alkali-soluble resin A and 84.1 described below in terms of solid content. 225 parts by mass of propylene glycol monomethyl ether acetate as a solvent (also including the solvent derived from dispersant A and the solvent derived from alkali-soluble resin A), 0.5 mm diameter zirconia beads, using a paint shaker Allow to disperse for 6 hours. After the dispersion is completed, the beads and the dispersion liquid are separated with a filter to prepare a green pigment dispersion liquid 1.

＜Preparation of Green Pigment Dispersion 2＞ A stainless steel container was filled with 11.0 parts by mass of C.I. Pigment Green 59, 1.6 parts by mass of dispersant A in terms of solid content, and 3.3 parts by mass of alkali-soluble resin A and 84.1 described below in terms of solid content. 225 parts by mass of propylene glycol monomethyl ether acetate as a solvent (also including the solvent derived from dispersant A and the solvent derived from alkali-soluble resin A), 0.5 mm diameter zirconia beads, using a paint shaker Allow to disperse for 6 hours. After the dispersion is completed, the beads and the dispersion liquid are separated with a filter to prepare a green pigment dispersion liquid 2.

<Alkali-soluble resin A> While 145 parts by mass of propylene glycol monomethyl ether acetate was replaced with nitrogen, the mixture was stirred and the temperature was raised to 120°C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and then heated at 120° C. Continue stirring for 2 hours. Next, the inside of the reaction container was replaced with air, 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120° C. for 6 hours. Thereafter, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours. After cooling to room temperature, an alkali-soluble resin A having a polystyrene-converted weight average molecular weight Mw measured by GPC of 8000 and an acid value of 80 mgKOH/g was obtained.

<Photopolymerizable Monomer A> A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Photopolymerizable monomer B> Succinic anhydride modified product of the reaction product of dipentaerythritol and acrylic acid

＜Photopolymerization initiator A＞ Oxime ester compounds with the following chemical structures (4-Acetyloxyimino-5-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-5-pentoxyvalerate methyl ester )

[Chemical 44]

Me in the formula represents methyl group.

＜Surfactant A＞ MEGAFAC (registered trademark) F-559 (made by DIC Corporation)

<Preparation of colored resin composition> Each component was mixed so that the ratio in the solid content and the ratio in the solvent described in Tables 1 and 2 would be achieved, and each colored resin composition having a content ratio of the total solid content of 15% by mass was prepared. "Ratio of solid content" means the ratio (mass %) of the solid content of each component to all solid content. In addition, "ratio in solvent" means the ratio (mass %) of various solvents in all solvents, and the amounts of various solvents also include solvents derived from alkali-soluble resins or pigment dispersions. In addition, the content ratio of C.I. Pigment Green 58 and C.I. Pigment Green 59 in Comparative Examples 7 and 8 was set to 40.0 mass % in the total solid content.

[Table 1] Type of ingredients Details of ingredients Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Solid content ratio Colorants Phthalocyanine compound A 40 40 40 40 40 40 40 40 40 40 40 40 Phthalocyanine compound D 40 Phthalocyanine compound E 40 Phthalocyanine compound F 40 Phthalocyanine compound G 40 alkali soluble resin Alkali soluble resin A 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 Photopolymerizable monomer Photopolymerizable monomer A 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 Photopolymerizable monomer B 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 10.4 Photopolymerization initiator Photopolymerization initiator A 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 surfactant Surfactant A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ratio in solvent Solvent PGME PGMEA 90.0 77.0 90.0 77.0 90.0 77.0 90.0 77.0 90.0 77.0 90.0 84.0 40.0 40.0 90.0 90.0 CHN EEP 10.0 23.0 10.0 10.0 10.0 10.0 MBA 10.0 23.0 8.0 14.0 MMBAC 10.0 23.0 NMP 50.0 50.0 DEGEA 10.0 23.0 2.0 2.0 DEGBEA 10.0 23.0

[Table 2] Type of ingredients Details of ingredients Comparative example 1 2 3 4 5 6 7 8 Solid content ratio Colorants/pigment dispersions Phthalocyanine compound A 40.0 40.0 40.0 40.0 Phthalocyanine compound B 40.0 Phthalocyanine compound C 40.0 Green pigment dispersion 1 60.3 Green Pigment Dispersion 2 60.3 alkali soluble resin Alkali soluble resin A 33.3 33.3 33.3 33.3 33.3 33.3 16.9 16.9 Photopolymerizable monomer Photopolymerizable monomer A 10.4 10.4 10.4 10.4 10.4 10.4 8.9 8.9 Photopolymerizable monomer B 10.4 10.4 10.4 10.4 10.4 10.4 8.9 8.9 Photopolymerization initiator Photopolymerization initiator A 5.8 5.8 5.8 5.8 5.8 5.8 4.9 4.9 surfactant Surfactant A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ratio in solvent Solvent PGME 10.0 23.0 PGMEA 100.0 90.0 77.0 90.0 100.0 80.0 100.0 100.0 CHN 10.0 EEP MBA MMBAC NMP 20.0 DEGEA DEGBEA

In addition, the details of various solvents listed in Table 1 and Table 2 are as listed in Table 3. The boiling point (°C) in the table is the value at 1013.25 hPa.

[table 3] Solvent type CAS No. Boiling point(℃) PGME Propylene glycol monomethyl ether 107-98-2 120 PGMEA Propylene glycol monomethyl ether acetate 108-65-6 146 CHN cyclohexanone 108-94-1 156 EEP Ethyl 3-ethoxypropionate 763-69-9 170 MBA 3-methoxybutyl acetate 4435-53-4 171 MMBAC 3-Methoxy-3-methylbutyl acetate 103429-90-9 187 NMP N-methyl-2-pyrrolidone 872-50-4 202 DEGEA Diethylene glycol monoethyl ether acetate 112-15-2 217 DEGBEA Diethylene glycol monobutyl ether acetate 124-17-4 245

<Evaluation of alkaline development time and residue on glass substrate> The above-mentioned colored resin composition was coated on a 50 mm square, 0.7 mm thick glass substrate (manufactured by AGC, AN100) using a spin coater so that the film thickness after drying became 2.3 μm, and then dried at 80°C. The evaluation substrate was obtained in 3 minutes. The evaluation substrate was developed using a 0.4% by mass potassium hydroxide aqueous solution at 23°C, and the time until the coating film was dissolved and the substrate surface was exposed (dissolution time) was measured.

Next, the evaluation substrate obtained through the same procedure was developed using a 0.4 mass% potassium hydroxide aqueous solution at 23°C for twice the dissolution time, and then sprayed for 10 seconds at a water pressure of 1 kg/cm ² It was washed with water to prepare a residue evaluation substrate 1. Moreover, except that the time of the development process was changed to 60 seconds, the residue evaluation board|substrate 2 was produced by the same procedure.

Visually observe the residue evaluation substrate 1, measure the area of the 50 mm square glass substrate where no residue is seen (A), and the area of the portion where the residue is visible (B), and calculate the residue generation area ratio (%) = (B) /{(A)＋(B)}×100 evaluation. The results are shown in Table 4.

[Table 4] Colorants Solvent ratio (%) Dissolution time (seconds) Residue area(%) PGME PGMEA CHN EEP MBA MMBAC NMP DEGEA DEGBEA Substrate 1 Example 1 Phthalocyanine compound A 90.0 10.0 18 3 2 Phthalocyanine compound A 77.0 23.0 18 2 3 Phthalocyanine compound A 90.0 10.0 17 3 4 Phthalocyanine compound A 77.0 23.0 16 2 5 Phthalocyanine compound A 90.0 10.0 9 2 6 Phthalocyanine compound A 77.0 23.0 9 0 7 Phthalocyanine compound A 90.0 10.0 9 1 8 Phthalocyanine compound A 77.0 23.0 9 0 9 Phthalocyanine compound A 90.0 10.0 8 0 10 Phthalocyanine compound A 77.0 23.0 9 0 11 Phthalocyanine compound A 90.0 8.0 2.0 10 2 12 Phthalocyanine compound A 84.0 14.0 2.0 10 1 13 Phthalocyanine compound D 40.0 10.0 50.0 9 0 14 Phthalocyanine compound E 40.0 10.0 50.0 10 0 15 Phthalocyanine compound F 90.0 10.0 12 2 16 Phthalocyanine compound G 90.0 10.0 13 2 Comparative example 1 Phthalocyanine compound A 100.0 8 8 2 Phthalocyanine compound A 10.0 90.0 8 9 3 Phthalocyanine compound A 23.0 77.0 8 9 4 Phthalocyanine compound A 90.0 10.0 11 6 5 Phthalocyanine compound B 100.0 9 11 6 Phthalocyanine compound C 80.0 20.0 10 12 7 CI Pigment Green 58 100.0 twenty four 2 8 CI Pigment Green 59 100.0 42 3

Next, the residue evaluation substrate 2 was also visually observed, and the residue generation area ratio (%) was evaluated in the same manner as the residue evaluation substrate 1. The results showed that Example 1 was 1%, Example 2 was 0%, and Example 3 is 1%, Example 4 is 0%, Example 5 is 0%, Example 6 is 0%, Example 7 is 0%, Example 8 is 0%, Example 9 is 0%, and Example 10 is 0%, Example 11 is 1%, Example 12 is 0%, Example 13 is 0%, Example 14 is 0%, Example 15 is 1%, and Example 16 is 1%.

<Evaluation of Color Characteristics> Example 1, Example 4, Example 8, Example 13, Example 14, Example 15, Example 16, Comparative Example 5, Comparative Example 6, and Comparative Example 7 were prepared using a spin coater. , and the colored resin composition of Comparative Example 8 was coated on a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC Corporation), and then dried at 80° C. for 3 minutes. Secondly, the entire surface was exposed using a 2 kW high-pressure mercury lamp with an exposure dose of 40 mJ/cm ² . Thereafter, development was performed using a 0.4% by mass potassium hydroxide aqueous solution at 23°C. Next, spray water washing was performed for 10 seconds with a water pressure of 3 kg/cm ² to prepare a colored resin composition-coated substrate. Thereafter, a thermal hardening process was performed at 230° C. for 30 minutes to produce a colored substrate with a film thickness of 2.0 μm. The transmission spectrum of the obtained colored substrate was measured with a C light source using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the chromaticity (sx, sy) and brightness were calculated. The chromaticity of Example 1 is sx=0.220, sy=0.460, the brightness LY is 58.7, the chromaticity of Example 4 is sx=0.220, sy=0.460, the brightness LY is 58.8, and the chromaticity of Example 8 is sx=0.220 , sy=0.460, brightness LY is 58.7. Moreover, the chromaticity of Example 13 is sx=0.249, sy=0.355, and the luminance LY is 65.4. The chromaticity of Example 14 is sx=0.266, sy=0.341, the luminance LY is 79.9, and the chromaticity of Example 15 is sx. =0.224, sy=0.459, the brightness LY is 58.3. The chromaticity of Example 16 is sx=0.228, sy=0.466, and the brightness LY is 57.3. The chromaticity of Comparative Example 5 is sx=0.219, sy=0.425, the brightness LY is 50.0, the chromaticity of Comparative Example 6 is sx=0.297, sy=0.428, the brightness LY is 47.3, and the chromaticity of Comparative Example 7 is sx=0.238 , sy=0.556, the brightness LY is 51.6. The chromaticity of Comparative Example 8 is sx=0.172, sy=0.483, and the brightness LY is 38.5.

Moreover, the surfaces of the colored substrates of Examples 1 to 12 produced by the same procedure were visually observed, and no foreign matter was observed.

As can be seen from Table 4, in the colored resin composition containing the phthalocyanine compound (1), when a high-boiling point solvent with a boiling point of 160° C. or higher is not included as in Comparative Examples 1 to 4, a large amount of residue is generated on the glass substrate. The phthalocyanine compound (1) has high solubility in a solvent and does not require a dispersion treatment step. Therefore, it is considered that there is almost no dispersant or alkali-soluble resin around the phthalocyanine compound (1). In the colored resin composition, the phthalocyanine compound (1) ) has a weakened affinity with alkali-soluble resins. In particular, it is thought that the molecules of the phthalocyanine compound (1) are easily associated with each other due to the π-π interaction between the phthalocyanine rings and the π-π interaction between the groups represented by the above formula (2), and furthermore, because it has an atomic radius Smaller fluorine atoms lead to denser packing of molecules and weaker affinity with alkali-soluble resins. During alkaline development, it is difficult for the alkaline developer to penetrate into the phthalocyanine compound (1), thereby causing alkali dissolution. The properties are reduced and residues tend to remain on the glass substrate.

In contrast, as in Examples 1 to 16, when the colored resin composition containing the phthalocyanine compound (1) contains a high boiling point solvent with a boiling point of 160° C. or higher, almost no residue is generated on the glass substrate, especially As in Examples 6, 8, 9 and 10, when the boiling point of the solvent is high or when the content ratio of the solvent with a boiling point of 160° C. or higher is high, no residue is generated on the glass substrate at all. The reason is thought to be that by containing a high-boiling solvent with a boiling point of 160°C or higher, drying of the coating film during the alkaline development step is suppressed, and the coating film is in a fully moist state. The alkaline developer fully penetrates into the coating film to promote neutralization. After the reaction, the phthalocyanine compound (1) is also fully dissolved in the alkaline developer, and residues derived from the colored resin composition are not easily generated on the glass substrate.

On the other hand, according to the comparison between Comparative Example 1 and Comparative Examples 5 and 6 in Table 4, the phthalocyanine compounds B and C that do not satisfy the above formula (1) have a larger residue area value than the phthalocyanine compound (1). . The reason is considered to be that the phthalocyanine compound B has a chlorine atom instead of a fluorine atom, so the polarity of the phthalocyanine compound becomes low, resulting in a low solubility in a highly polar developer (alkaline aqueous solution). In addition, the reason is considered to be that the central metal of the phthalocyanine compound C is copper, which lowers the ionization tendency of the phthalocyanine compound and lowers its solubility in the developer (alkaline aqueous solution). Moreover, as mentioned above, compared with Comparative Example 5 and Comparative Example 6, Example 1 has higher brightness. This is considered to be because the phthalocyanine compound (1) contained in Example 1 has a fluorine atom, which increases the polarity of the phthalocyanine compound, thereby increasing the solubility in the solvent in the colored resin composition, and the phthalocyanine compounds interact with each other. The aggregation and the like are suppressed, and the reason for this is thought to be that the crystal form is optimized because the central metal is zinc.

Moreover, as in Comparative Examples 7 and 8, it is considered that in the colored resin composition containing the green pigment instead of the phthalocyanine compound (1), there is a large amount of dispersing resin or dispersing agent near the green pigment in the colored resin composition, and the alkali The affinity of the soluble resin becomes stronger, so the green pigment has higher alkali solubility. Although it does not contain high-boiling solvents with a boiling point above 160°C, the residue is not easy to remain on the glass substrate.

10:Transparent support substrate 20: pixels 30: Organic protective layer 40: Inorganic oxide film 50:Transparent anode 51: Hole injection layer 52: Hole transport layer 53: Luminous layer 54:Electron injection layer 55:Cathode 100: Organic EL element 500: Organic luminophore

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

Claims (7)

A colored resin composition, characterized in that it contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and the (A) colorant contains A phthalocyanine compound having a chemical structure represented by the following general formula (1), the solvent (B) above contains a high boiling point solvent having a boiling point of 160°C or higher at 1013.25 hPa,

(In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2); wherein, more than one of A ¹ to A ¹⁶ represents a fluorine atom, and One or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2)) [Chemical Formula 2]

(In formula (2), X represents a divalent linking group; the benzene ring in formula (2) can have any substituent; * represents a bond). The colored resin composition according to claim 1, wherein the content ratio of the above-mentioned (B) solvent in the colored resin composition is 50% by mass or more. The colored resin composition of claim 1 or 2, wherein the content ratio of the high boiling point solvent in the solvent (B) is 0.5% by mass or more. The colored resin composition according to claim 1 or 2, wherein the content ratio of the above-mentioned phthalocyanine compound is 5 mass % or more based on the total solid content. The colored resin composition of claim 1 or 2, wherein the (D) photopolymerization initiator contains an oxime ester photopolymerization initiator. A color filter having pixels produced using the colored resin composition according to any one of claims 1 to 5. An image display device having the color filter of claim 6.