KR20210131990A - Colored resin composition, color filter, and image display device - Google Patents

Abstract

(식 (1) 중, A¹ ∼ A¹⁶ 은 각각 독립적으로, 수소 원자, 불소 원자, 또는 하기 일반식 (2) 로 나타내는 기를 나타낸다. 단, A¹ ∼ A¹⁶ 중 1 개 이상은 불소 원자를 나타내고, 또한 A¹ ∼ A¹⁶ 중 1 개 이상은 하기 일반식 (2) 로 나타내는 기를 나타낸다.)

(식 (2) 중, X 는 2 가의 연결기를 나타낸다. 식 (2) 중의 벤젠 고리는 임의의 치환기를 갖고 있어도 된다. * 는 결합손을 나타낸다.)Provided is a colored resin composition having high luminance and suppressed generation of residues. The colored resin composition of this invention is a colored resin composition containing (A) a coloring agent, (B) a solvent, (C) alkali-soluble resin, and (D) a photoinitiator, The said (A) coloring agent is the following general formula ( The phthalocyanine compound which has the chemical structure shown by 1) is contained, and the said (B) solvent contains the high boiling point solvent whose boiling point in 1013.25 hPa is 160 degreeC or more.

(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). However, ^{at least one of A 1} to A ¹⁶ represents a fluorine atom. and, ^{at least one of A 1} to A ¹⁶ represents a group represented by the following general formula (2).)

(In Formula (2), X represents a divalent coupling group. The benzene ring in Formula (2) may have arbitrary substituents. * 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.

Full contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-030548, filed with the Japanese Patent Office on February 22, 2019, Japanese Patent Application 2019- filed with the Japanese Patent Office on June 27, 2019 119240, the entire contents of the specification, claims, drawings, and abstracts, and some or all of the contents disclosed in documents cited in this specification, etc., are cited herein, and are incorporated herein by reference.

Conventionally, as a method of manufacturing the color filter used for a liquid crystal display device etc., the pigment dispersion method, the dyeing method, the electrodeposition method, and the printing method are known. Among them, the pigment dispersion method having characteristics excellent on average from the viewpoints of spectral characteristics, durability, pattern shape, precision, and the like is most widely adopted.

In recent years, higher luminance, higher contrast and higher color gamut have been demanded for color filters. As a colorant that determines the color of a color filter, a pigment is generally used from the viewpoint of heat resistance, light resistance, etc., but as a pigment, the market demand cannot be satisfied especially for high luminance. The review is being actively conducted. For a green pixel, examination using a specific phthalocyanine compound as dye is performed (for example, refer patent documents 1 - 3).

Japanese Patent Laid-Open No. 2009-051896 International Publication No. 2014/157387 Japanese Patent Laid-Open No. 2014-43556

As a result of this inventor examining, in the colored resin composition described in patent document 1 and patent document 2, it discovered that a brightness|luminance was not enough practically. Moreover, in the colored resin composition described in patent document 3, alkali developability in the alkali image development process at the time of color filter manufacture is not enough, and it turns out that the residue derived from a colored resin composition generate|occur|produces on a glass substrate. paid

Then, this invention aims at providing the colored resin composition by which the luminance was high and generation|occurrence|production of the residue was suppressed.

As a result of this inventor earnestly examining, by using a specific phthalocyanine compound as a coloring agent, and using the solvent more than a specific boiling point as a solvent, it discovers that the said subject can be solved, and led to this invention.

That is, this invention has the following structures.

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

Said (A) coloring agent contains the phthalocyanine compound which has a chemical structure represented by following General formula (1),

Said (B) solvent contains the high boiling point solvent whose boiling point in 1013.25 hPa is 160 degreeC or more, The colored resin composition characterized by the above-mentioned.

[Formula 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). However, ^{at least one of A 1} to A ¹⁶ represents a fluorine atom. and, ^{at least one of A 1} to A ¹⁶ represents a group represented by the following general formula (2).)

[Formula 2]

(In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have an arbitrary 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 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 (B) solvent is 0.5 mass% or more.

[4] The colored resin composition according to any one of [1] to [3], wherein the content of the phthalocyanine compound is 5 mass% or more in the total solid content.

[5] The colored resin composition according to any one of [1] to [4], wherein the (D) photoinitiator contains an oxime ester-based photoinitiator.

[6] A color filter having a pixel manufactured 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].

ADVANTAGE OF THE INVENTION According to this invention, a brightness|luminance is high and the colored resin composition by which generation|occurrence|production of the residue was suppressed can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic which shows an example of the organic electroluminescent display element which has a color filter of this invention.

Although the structural requirements of this invention etc. are demonstrated in detail below, these are an example of embodiment of this invention, and are not limited to these content.

In this invention, "weight average molecular weight" means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In the present invention, "amine number" means an amine value in terms of effective solid content unless otherwise specified, and is a value expressed by the amount of base per 1 g of solid content of the dispersing agent and the mass of equivalent KOH.

In the present invention, "C.I." means a color index.

In addition, in the present invention, "(meth)acryl", "(meth)acrylate", etc. mean "acryl and/or methacryl", "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 other than a solvent component contained in a pigment dispersion liquid or a colored resin composition.

Moreover, in this invention, the numerical range shown using "-" means a range including the numerical values described before and after "-".

[1] Components of the colored resin composition

Each structural component of the colored resin composition of this invention is demonstrated below. The colored resin composition according to the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photoinitiator as essential components, and further summarized, other additives other than the above components, etc. These may be combined.

Hereinafter, each component is demonstrated.

[1-1] (A) Colorant

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

[Formula 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). However, ^{at least one of A 1} to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Formula 4]

In Formula (2), X represents a divalent coupling group. The benzene ring in Formula (2) may have arbitrary substituents. * indicates a bond.

The (A) coloring agent contained in the colored resin composition of this invention contains a phthalocyanine compound (1). Since the phthalocyanine compound (1) has a group represented by the above general formula (2), it has high solubility in a solvent and does not require a dispersion treatment step, or the amount of a dispersing agent required in the dispersion treatment step can be greatly reduced. have. Therefore, in the colored resin composition, around the phthalocyanine compound (1), there is no dispersant or alkali-soluble resin, or only a very small amount exists, and in the colored resin composition, the phthalocyanine compound (1) and the alkali-soluble resin It is thought that the affinity of

In particular, in the phthalocyanine compound (1), molecules are easily associated with each other due to π-π interaction between phthalocyanine rings and π-π interaction between groups represented by the general formula (2), and has a small atomic radius. It is thought that the affinity with alkali-soluble resin is weakened while packing of molecules becomes more dense by having a fluorine atom, and a brightness|luminance becomes high.

On the other hand, during the alkali developing step, the interaction between the alkali developer and the phthalocyanine compound (1) is small, and the phthalocyanine compound (1) is not sufficiently dissolved in the alkali developer, and on the glass substrate, on the other hand, the solubility in the solvent is high. It is thought that there exists a tendency which becomes easy to remain|survive.

Then, in the colored resin composition of this invention, drying of the coating film at the time of an alkali image development process is suppressed by containing the high boiling point solvent in 1013.25 hPa or more, boiling point in 1013.25 hPa, it becomes a fully wet state, and alkali developing solution becomes a coating film. It is thought that it permeates fully to the inside, a neutralization reaction is accelerated|stimulated, and it becomes difficult to generate|occur|produce the residue derived from a colored resin composition on a glass substrate.

(A ¹ to A ¹⁶ )

In the 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). However, ^{at least one of A 1} to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Formula 5]

In Formula (2), X represents a divalent coupling group. The benzene ring in Formula (2) may have arbitrary substituents. * indicates a bond.

(X)

X in the said General formula (2) represents a bivalent coupling group. Although it does not specifically limit as a bivalent linking group, An oxygen atom, a sulfur atom, or -N(R ^a1 )- group (R ^a1 represents a hydrogen atom or a C1-C6 aliphatic hydrocarbon group) is mentioned. Among these, an oxygen atom or a sulfur atom is preferable from a stability viewpoint at the time of baking of a phthalocyanine compound (1), and an oxygen atom is more preferable.

(Substituent which the benzene ring may have)

Moreover, the benzene ring in Formula (2) may have arbitrary substituents. Although it does not specifically limit as a substituent, A halogen atom, an alkyl group (-R ^A group (provided that R ^A represents an alkyl group)), an alkoxy group (-OR ^A group (provided that R ^A represents an alkyl group)), an alkoxycarbonyl group ^(a group -COOR (where, R ^a represents an alkyl group)), an aryl group (-R ^B group (where, R ^B is an aryl group)), an aryloxy group (-OR ^B group (where, R ^B is represents an aryl group)), an aryloxycarbonyl group (-COOR group ^B (where, R ^B is an aryl group)) may be mentioned the alkyl group (-R ^a contained groups these groups) or aryl group (-R ^B group) may be further substituted with these substituents. Among these, an alkoxycarbonyl group is preferable from a viewpoint of the solubility with respect to a solvent, and a brightness|luminance.

The alkyl group contained in these groups may be linear, branched, or cyclic, but is preferably linear from the viewpoint of solubility in solvents.

Although carbon number of an alkyl group is not specifically limited, Usually, 1 or more and 2 or more are preferable, and 6 or less are preferable, 5 or less are more preferable, 4 or less are still more preferable. By setting it more than the said lower limit, lipophilicity improves and the solubility with respect to the solvent of a phthalocyanine compound (1) tends to improve, Moreover, by using below the said upper limit, hydrophilicity improves, and containing a phthalocyanine compound (1) There exists a tendency for the solubility with respect to the alkaline developing solution of a colored resin composition to improve.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Compatibility of lipophilicity and hydrophilicity, that is, solubility in solvent of phthalocyanine compound (1) and phthalocyanine compound A methyl group or an ethyl group is preferable from a viewpoint of making the solubility with respect to the alkali developing solution of the colored resin composition containing (1) compatible, and an ethyl group is more preferable.

Moreover, an aromatic hydrocarbon ring group may be sufficient as the aryl group contained in these groups, and an aromatic heterocyclic group may be sufficient as it.

Although carbon number of an aryl group is not specifically limited, Usually, 4 or more and 6 or more are preferable, and 12 or less are preferable, 10 or less are more preferable, 8 or less are still more preferable. By using more than the said lower limit, the solubility with respect to the solvent of the phthalocyanine compound (1) tends to improve, Moreover, there exists a tendency for the color change resulting from an aryl group to be suppressed by using below the said upper limit.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include groups having one free valence, such as a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring.

Moreover, as an aromatic heterocyclic ring in an aromatic heterocyclic group, a monocyclic ring may be sufficient as it and a condensed ring may be sufficient as it. Aromatic heterocyclic groups include, for example, a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an iso oxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, Benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H- 2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolizine ring, benzoimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1, and groups such as an 8-naphthyridine ring, a purine ring and a pteridine ring.

When the benzene ring in formula (2) has an arbitrary substituent, the number of substitutions is not particularly limited, but the polarity of the phthalocyanine compound (1), that is, the lipophilicity that affects the solubility of the phthalocyanine compound (1) in a solvent And it is preferable that the substitution number is 1 with respect to one benzene ring from a viewpoint of hydrophilic coexistence which affects the solubility with respect to the alkali developing solution of the colored resin composition containing a phthalocyanine compound (1).

In addition, when the benzene ring in formula (2) has an arbitrary substituent, the substitution position may be the o-position, the m-position, or the p-position may be sufficient, but the polarity of the phthalocyanine compound (1), that is, From the viewpoint of coexistence of lipophilicity affecting the solubility of the phthalocyanine compound (1) in a solvent and the hydrophilicity affecting the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, the p-position is desirable.

Although ^{at least one of A 1} to A ¹⁶ represents a fluorine atom, the lipophilicity which affects the luminance and the solubility to the solvent of the phthalocyanine compound (1) and the alkali development solubility of the colored resin composition containing the phthalocyanine compound (1) From the viewpoint of compatibility of hydrophilicity affecting It is preferable, and 10 or less are more preferable. For example, A ¹ ~ A ¹⁶ of, fluorine atom 1 to 14, far preferably from 2 to 14 is more preferred, and 4 to 12, more preferably, 6 to 10 is particularly preferred.

^At least one of A ¹ to A 16 represents a fluorine atom, and the brightness and polarity of the phthalocyanine compound (1), that is, the lipophilicity that affects the solubility of the phthalocyanine compound (1) in a solvent, and the phthalocyanine compound (1) ) from the viewpoint of hydrophilicity coexistence affecting the alkali development solubility of the colored resin composition containing, ^{at least one of A 1} to A ⁴ is a fluorine atom, and at least one of A ⁵ to A ⁸ is a fluorine atom, It is preferable that at least one of A ⁹ to A ¹² is a fluorine atom, and at least one of A ¹³ to A ^{16 is a fluorine atom, two or more of A 1} to A ⁴ are fluorine atoms, and A ⁵ to A and two or more of the ^eight fluorine atoms, a ⁹ and a ~ two or more of the ¹² is a fluorine atom, it is also preferable that at least two of a ¹³ ~ a ¹⁶ is a fluorine atom.

^At least one of A ¹ to A 16 represents a group represented by the general formula (2), and from the viewpoint of solubility in a solvent, two or more are preferable, four or more are more preferable, and six or more are still more preferable. and 14 or less are preferable, 12 or less are more preferable, and 10 or less are still more preferable. For example, A ¹ ~ A of ^16, and the group represented by the general formula (2) from 1 to 14, far preferably from 2 to 14 is more preferred, and 4 to 12, more preferably, is 6-10 are particularly preferred .

In addition, ^{at least one of A 1} to A ¹⁶ represents a group represented by the general formula (2), and from the viewpoint of solubility in a solvent, ^{at least one of A 1} to A ⁴ is a group represented by the general formula (2). , ^{at least one of A 5} to A ⁸ is a group represented by the general formula (2), ^{at least one of A 9} to A ¹² is a group represented by the general formula (2), and A ¹³ to A ¹⁶ It is preferable that at least one of them is a group represented by the general formula (2), at least two of ^{A 1} to A ^{4 are groups represented by the general formula (2), and at least two of A 5} to A ⁸ are the groups described above. is a group represented by the general formula (2), ^{two or more of A 9} to A ¹² are groups represented by the general formula (2), and ^{two or more of A 13} to A ¹⁶ are represented by the general formula (2) It is more preferable that it is a group.

In particular, from the viewpoint of color tone, luminance, and solubility in solvents required for a color filter, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ are the formulas (2) It is a group represented by , and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are particularly preferably a fluorine atom.

As a specific example of a phthalocyanine compound (1), the following are mentioned, for example.

[Formula 6]

Et in the formula represents ethyl.

[Formula 7]

[Formula 8]

[Formula 9]

As a manufacturing method of a phthalocyanine compound (1), a well-known method is employable, for example, the method of Unexamined-Japanese-Patent No. 5-345861 is employable.

(A) The coloring agent may contain other coloring agents other than the phthalocyanine compound (1). As another coloring agent, a pigment and dye are mentioned. Among these, when using the colored resin composition of this invention for a green pixel use, it is preferable to use a green pigment, green dye, a yellow pigment, yellow dye, etc.

As a green pigment, C.I. Pigment Green 7, 36, 58, 59, 62, 63, etc. are mentioned, From a viewpoint of luminance, C.I. Pigment Green 58 is preferred.

As the green dye, among those classified as dyes in the color index, C.I. As a solvent dye, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and C.I. As an acid dye, C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. As a mordant dye, C.I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned. Among these, from the viewpoint of suppressing dye decomposition at the time of thermal firing, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 is preferred.

As a yellow pigment, C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36 , 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87 , 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134 , 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169 , 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198 , 199, 200, 202, 203, 204, 205, 206, 207, 208, and a 1:1 complex with nickel of azobarbituric acid represented by the following formula (i) or a compatible isomer thereof, when another compound is inserted The compound formed (Hereinafter, "the nickel azo complex represented by Formula (i)" may be called) etc. are mentioned.

[Formula 10]

Moreover, as another compound inserted into the 1:1 complex with nickel of azobarbituric acid represented by said formula (i), or its compatible isomer, the compound etc. which are represented by following formula (ii) are mentioned.

[Formula 11]

Among these, from the viewpoint of high luminance and high color gamut, C.I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and nickel azo complexes represented by formula (i) are preferable, and C.I. Pigment yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by formula (i) are more preferable.

Examples of the yellow dye include barbiturate azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. As the specific example, the specific compound of Unexamined-Japanese-Patent No. 2010-168531 is mentioned.

Among those classified as dyes in the color index, C.I. As a solvent dye, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 etc. are mentioned. Also C.I. As an acid dye, 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 a derivative thereof can be heard Also C.I. As a direct dye, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, and 141 dyes. Also, C.I. As a mordant dye, C.I. Dyes, such as Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, are mentioned, Preferably 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 and derivatives thereof.

Among these, from the viewpoint of suppressing dye decomposition during thermal firing, C.I. It is preferable that it is at least 1 sort(s) selected from the group which consists of Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 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, and more preferably 0.04 µm or less. At the time of atomization of the pigment, a method such as solvent salt milling is preferably used.

Although the content rate of (A) coloring agent in the colored resin composition of this invention is not specifically limited, 5 mass % or more is preferable in the total solid of a colored resin composition, 10 mass % or more is more preferable, 20 mass % or more This is more preferable, more preferably 30 mass% or more, even more preferably 35 mass% or more, particularly preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less. and 45 mass % or less is especially preferable. If it is set to more than the said lower limit, there exists a tendency for color characteristics, such as a brightness|luminance and a color gamut, to improve, and there exists a tendency for pattern formability to become favorable by setting it as below the said upper limit. For example, as for the content rate of (A) coloring agent, 5-70 mass % is preferable, 10-60 mass % is more preferable, 20-50 mass % is still more preferable, 30-45 mass % is still more It is preferable, and 35-45 mass % is especially preferable.

Although the content rate of the phthalocyanine compound (1) in the colored resin composition of this invention is not specifically limited, 5 mass % or more is preferable in the total solid of a colored resin composition, 10 mass % or more is more preferable, 20 mass % More preferably, 30 mass% or more is still more preferable, 35 mass% or more is particularly preferable, 70 mass% or less is preferable, 60 mass% or less is more preferable, 50 mass% or less is still more preferable, , 45 mass% or less is particularly preferable. If it is set to more than the said lower limit, there exists a tendency for color characteristics, such as a brightness|luminance and a color gamut, to improve, and there exists a tendency for pattern formability to become favorable by setting it as below the said upper limit.

In the case of containing other coloring agents, the content ratio is not particularly limited, but in the total solid content of the colored resin composition, 0.1 mass % or more is preferable, 1 mass % or more is more preferable, and 3 mass % or more is still more preferable, 5 mass % or more is still more preferable, 10 mass % or more is especially preferable, 60 mass % or less is preferable, 50 mass % or less is more preferable, 40 mass % or less is still more preferable, 30 mass % or less is Especially preferred. If it is set to more than the said lower limit, there exists a tendency for color characteristics, such as a brightness|luminance and a color gamut, to improve, Moreover, there exists a tendency for pattern formability to become favorable by setting it as below the said upper limit.

[1-2] (B) Solvent

(B) A solvent dissolves or disperse|distributes a coloring agent, alkali-soluble resin, a photoinitiator, and other components in the colored resin composition of this invention, and has the function of adjusting a viscosity.

As such (B) solvent, what is necessary is just what can melt|dissolve or disperse|distribute each component.

The colored resin composition of this invention WHEREIN: (B) The solvent contains the high boiling point solvent (Hereinafter, it may call a "high boiling point solvent") whose boiling point in 1013.25 hPa is 160 degreeC or more. By containing the high boiling point solvent in this way, the drying of the coating film during the alkali development step is suppressed, and it becomes a sufficiently wet state, the alkali developer sufficiently penetrates into the coating film interior, and the neutralization reaction is promoted, and the phthalocyanine compound (1) is contained It is thought that it can make it difficult to generate|occur|produce the residue on a glass substrate even if it is a coating film to do.

The boiling point of the high boiling point solvent at 1013.25 hPa (hereinafter, simply abbreviated as "boiling point" unless otherwise specified) is usually 160°C or higher, preferably 165°C or higher, more preferably 170°C or higher. , more preferably 180 °C or higher, even 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 higher. Hereinafter, more preferably, it is 280 degrees C or less. By using more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bumpiness at the time of VCD (pressure-drying) in a color filter manufacturing process to be suppressed, Moreover, by using below the said upper limit, VCD (reduced-pressure drying) in a color filter manufacturing process. drying) tends to improve. For example, 160-340 degreeC is preferable, as for the boiling point of the said high boiling point solvent, 165-340 degreeC is more preferable, 170-300 degreeC is still more preferable, 180-300 degreeC is still more preferable, 190- 300 degreeC is especially preferable, 200-280 degreeC is especially preferable, and 220-280 degreeC is the most preferable. The high boiling point solvent may be used individually by 1 type, and may use 2 or more types together.

Moreover, the vapor pressure in 20 degreeC of the said high boiling point solvent is although it does not specifically limit, Preferably it is 1 Pa or more, More preferably, it is 5 Pa or more, More preferably, it is 10 Pa or more, More preferably, it is 2000 Pa or less. , More preferably, it is 1500 Pa or less, More preferably, it is 1000 Pa or less, Especially preferably, it is 500 Pa or less. By using more than the said lower limit, the efficiency of VCD (pressure drying) in the color filter manufacturing process tends to improve, and alkali solubility improves by setting it as below the said upper limit, Dolby at the time of VCD (pressure drying) in a color filter manufacturing process. occurrence tends to be suppressed. For example, 1-2000 Pa is preferable, as for the vapor pressure in 20 degreeC of the said high boiling point solvent, 1-1500 Pa is more preferable, 5-1000 Pa is still more preferable, 10-500 Pa is especially preferable. do.

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.), diethylene glycol diethyl ether (boiling point: 188 ° C.) °C), diethylene glycol monoethyl ether (boiling point: 202 °C), 3-ethoxyethyl propionate (boiling point: 170 °C), 3-methoxybutyl acetate (boiling point: 171 °C), 3-methoxy-3-methyl glycol ethers such as butyl acetate (boiling point: 187°C);

glycol ether acetates such as ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C), diethylene glycol monoethyl ether acetate (boiling point: 217°C), and diethylene glycol monobutyl ether acetate (boiling point: 245°C);

glycol diacetates such as ethylene glycol diacetate (boiling point: 191°C) and 1,3-butylene glycol diacetate (boiling point: 232°C);

amides such as N-methylpyrrolidone (boiling point: 202°C); These are mentioned, From a soluble viewpoint in the colored resin composition of a phthalocyanine compound (1), glycol ethers and glycol ether acetates are preferable, and glycol ethers are more preferable.

Among these high boiling point solvents, high boiling point solvents having a boiling point of 160°C or more and less than 200°C (hereinafter referred to as "high boiling point solvent A") from the viewpoint of moderate residue suppression and improvement of the efficiency of VCD (reduced pressure drying) in the color filter manufacturing process. ) is preferably used.

The boiling point of the high boiling point solvent A is not particularly limited as long as it is 160°C or more and less than 200°C, but 165°C or more is preferable, 170°C or more is more preferable, 175°C or more is still more preferable, and 195°C or less is preferable. , 190°C or lower is more preferable, and 185°C or lower is still more preferable. By setting it to more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (pressure drying) in a color filter manufacturing process Efficiency tends to improve. For example, 165 degreeC - 195 degreeC are preferable, as for the boiling point of high boiling point solvent A, 170 degreeC - 190 degreeC are more preferable, 175 degreeC - 185 degreeC are still more preferable. The high boiling point solvent A may be used individually by 1 type, and may use 2 or more types together.

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), diethylene glycol diethyl ether (boiling point: 188°C) °C), 3-ethoxyethyl propionate (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);

glycol diacetates such as ethylene glycol diacetate (boiling point: 191°C); These are mentioned, From a soluble viewpoint in the colored resin composition of a phthalocyanine compound (1), glycol ethers and glycol ether acetates are preferable, and glycol ethers are more preferable.

Among these high boiling point solvents, high boiling point solvents having a boiling point of 200°C or higher and 340°C or lower (hereinafter referred to as "high boiling point solvent B") ') is preferably used.

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 210°C or more is preferable, 220°C or more is more preferable, 230°C or more is still more preferable, and 320°C or less is preferable. , 300°C or less is more preferable, and 280°C or less is still more preferable. By setting it to more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (pressure drying) in a color filter manufacturing process Efficiency tends to improve. For example, 210 degreeC - 320 degreeC are preferable, as for the boiling point of the high boiling point solvent B, 220 degreeC - 300 degreeC are more preferable, 230 degreeC - 280 degreeC are still more preferable. The high boiling point solvent B may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the high boiling point solvent B include glycol ethers such as diethylene glycol monoethyl ether (boiling point: 202°C);

glycol ether acetates such as diethylene glycol monoethyl ether acetate (boiling point: 217°C) and diethylene glycol monomonobutyl ether acetate (boiling point: 245°C);

glycol diacetates such as 1,3-butylene glycol diacetate (boiling point: 232°C);

amides such as N-methylpyrrolidone (boiling point: 202°C); These are mentioned, From a soluble viewpoint in the colored resin composition of a phthalocyanine compound (1), glycol ethers and glycol ether acetates are preferable, and glycol ether acetates are more preferable.

Among the high boiling point solvents, it is preferable to use the high boiling point solvent A independently from a viewpoint of moderate residual suppression and the efficiency improvement of VCD (pressure drying) in a color filter manufacturing process. Moreover, it is preferable to use independently the high boiling point solvent B from a viewpoint of effective residue suppression and the Dolby generation|occurrence|production suppression at the time of VCD (pressure drying) in a color filter manufacturing process. On the other hand, high boiling point solvent A and high boiling point solvent B are used together from a viewpoint of making both the efficiency improvement of VCD (reduced-pressure drying) in a color filter manufacturing process, and suppression of bumpy generation|occurrence|production at the time of VCD (reduced-pressure drying) suppressing a residue on the other hand. It is preferable to do

Moreover, the colored resin composition of this invention WHEREIN: It is preferable that (B) solvent contains the low boiling point solvent (Hereinafter, it may call a "low boiling point solvent") whose boiling point is less than 160 degreeC. By containing a low boiling point solvent, the efficiency of VCD (pressure drying) in the color filter manufacturing process is improved, or the coating film is easily dried by VCD or heat drying, and the thickness of the coating film becomes thin, so that ultraviolet light reaches the inside of the coating film during ultraviolet exposure. There exists a tendency for coating-film sclerosis|hardenability to become high by reaching|attaining, and for pattern formation to become advantageous.

The boiling point of the low-boiling solvent is not particularly limited as long as it is less than 160°C, but 150°C or less is preferable, 140°C or less is more preferable, 130°C or less is still more preferable, 120°C or less is particularly preferable, and 80°C or less. or more is preferable, 90 degreeC or more is more preferable, and 100 degreeC or more is still more preferable. There exists a tendency for the efficiency of VCD (pressure drying) in a color filter manufacturing process to improve by using below the said upper limit, and alkali solubility tends to improve by setting it as more than the said lower limit.

Specific examples of the low boiling point solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, Butyrate n-propyl, butyrate i-propyl, 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-methoxyisobutylate, methyl glycolate, methyl lactate, methyl-2-hydroxy Isobutylate, 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. are mentioned. Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate are preferable from a viewpoint of the solubility with respect to the structural component of colored resin compositions other than a solvent, and storage stability, and propylene glycol monomethyl ether acetate. is more preferable.

Although the content rate of the (B) solvent in the colored resin composition of this invention is not specifically limited, Preferably it is 50 mass % or more, More preferably, it is 60 mass % or more, More preferably, it is 70 mass % or more, Especially preferably Preferably it is 80 mass % or more, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less, More preferably, it is 88 mass % or less. There exists a tendency which the storage stability and applicability|paintability of a colored resin composition can be improved by using more than the said lower limit, and there exists a tendency which can make the film thickness at the time of application|coating below fixed by using below the said upper limit. For example, 50-95 mass % is preferable, as for the content rate of a solvent, 60-95 mass % is more preferable, 70-90 mass % is still more preferable, 80-88 mass % is especially preferable.

Moreover, the colored resin composition of this invention WHEREIN: Although the content rate of the said high boiling point solvent in (B) solvent is not specifically limited, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more, More preferably preferably 2 mass % or more, even 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 preferably It is 80 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 40 mass % or less, Especially preferably, it is 30 mass % or less. By setting it to more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (pressure drying) in a color filter manufacturing process Efficiency tends to improve. For example, as for the content rate of the said high boiling point solvent in (B) solvent, 0.5-80 mass % is preferable, 1-80 mass % is more preferable, 2-60 mass % is still more preferable, 5 -60 mass % is more preferable, 10-40 mass % is especially preferable, 15-40 mass % is especially preferable, 20-30 mass % is the most preferable.

When the colored resin composition of this invention contains the said low boiling point solvent, (B) Although the content rate of the said low boiling point solvent in a solvent is not specifically limited, Preferably it is 20 mass % or more, More preferably, it is 40 mass %. or more, more preferably 60 mass% or more, particularly preferably 70 mass% or more, and preferably 99 mass% or less, more preferably 98 mass% or less, still more preferably 95 mass% or less. By using more than the said lower limit, the efficiency of VCD (pressure drying) in the color filter manufacturing process tends to improve, and alkali solubility improves by setting it as below the said upper limit, Dolby at the time of VCD (pressure drying) in a color filter manufacturing process. occurrence tends to be suppressed. For example, 20-99 mass % is preferable, as for the content rate of the said low boiling point solvent in (B) solvent, 40-98 mass % is more preferable, 60-95 mass % is still more preferable, 70- 95 mass % is especially preferable.

When the (B) solvent in the colored resin composition of the present invention contains the high boiling point solvent A and the low boiling point solvent, the content ratio of the high boiling point solvent A in the (B) solvent is not particularly limited, 1 mass % or more is preferable, 5 mass % or more is more preferable, 10 mass % or more is still more preferable, 15 mass % or more is especially preferable, 50 mass % or less is preferable, and 40 mass % or less is preferable. More preferably, 30 mass % or less is still more preferable, and 20 mass % or less is especially preferable. By setting it to more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (pressure drying) in a color filter manufacturing process Efficiency tends to improve. For example, 1-50 mass % is preferable, as for the content rate of the said high boiling point solvent A in (B) solvent, 5-40 mass % is more preferable, 10-30 mass % is still more preferable, 15-20 mass % is especially preferable.

When (B) solvent in the colored resin composition of this invention contains the said high boiling point solvent A and the said low boiling point solvent, The content rate of the low boiling point solvent in (B) solvent is although it does not specifically limit, 50 mass % or more is preferable, 60 mass % or more is more preferable, 70 mass % or more is still more preferable, 80 mass % or more is especially preferable, 99 mass % or less is preferable, 95 mass % or less is more preferable, , 90 mass % or less is more preferable, and 85 mass % or less is especially preferable. By using more than the said lower limit, the efficiency of VCD (pressure drying) in the color filter manufacturing process tends to improve, and alkali solubility improves by setting it as below the said upper limit, Dolby at the time of VCD (pressure drying) in a color filter manufacturing process. occurrence tends to be suppressed. For example, as for the content rate of the said low boiling point solvent in (B) solvent, 50-99 mass % is preferable, 60-95 mass % is more preferable, 70-90 mass % is still more preferable, 80-99 mass % is more preferable. 85 mass % is especially preferable.

When the (B) solvent in the colored resin composition of the present invention contains the high boiling point solvent B and the low boiling point solvent, the content ratio of the high boiling point solvent B in the (B) solvent is not particularly limited, 0.1 mass % or more is preferable, 0.5 mass % or more is more preferable, 1 mass % or more is still more preferable, 2 mass % or more is especially preferable, 20 mass % or less is preferable, 15 mass % or less is preferable. More preferably, 10 mass % or less is still more preferable, and 5 mass % or less is especially preferable. By setting it more than the said lower limit, alkali solubility improves efficiently, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (reducing-pressure drying) in a color filter manufacturing process ) tends to improve the efficiency. For example, 0.1-20 mass % is preferable, as for the content rate of the said high boiling point solvent B in (B) solvent, 0.5-15 mass % is more preferable, 1-10 mass % is still more preferable, 2-5 mass % is especially preferable.

When (B) solvent in the colored resin composition of this invention contains the said high boiling point solvent B and the said low boiling point solvent, Although the content rate of the low boiling point solvent in (B) solvent is not specifically limited, 80 mass % or more is preferable, 85 mass % or more is more preferable, 90 mass % or more is still more preferable, 95 mass % or more is especially preferable, 99.9 mass % or less is preferable, and 99.5 mass % or less is more preferable, , 99 mass % or less is more preferable, and 98 mass % or less is especially preferable. By using more than the said lower limit, the efficiency of VCD (pressure drying) in the color filter manufacturing process tends to improve, and alkali solubility improves by setting it as below the said upper limit, Dolby at the time of VCD (pressure drying) in a color filter manufacturing process. occurrence tends to be suppressed. For example, as for the content rate of the said low boiling point solvent in (B) solvent, 80-99.9 mass % is preferable, 85-99.5 mass % is more preferable, 90-99 mass % is still more preferable, 95-99 mass % is more preferable. 98 mass % is especially preferable.

When (B) solvent in the colored resin composition of this invention contains the said high boiling point solvent A, the said high boiling point solvent B, and the said low boiling point solvent, (B) content rate of the said high boiling point solvent A in a solvent Although not specifically limited, 1 mass % or more is preferable, 5 mass % or more is more preferable, 10 mass % or more is still more preferable, 15 mass % or more is especially preferable, and 50 mass % or less is preferable, , 40 mass % or less is more preferable, 30 mass % or less is still more preferable, and 20 mass % or less is especially preferable. By setting it to more than the said lower limit, alkali solubility improves, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (pressure drying) in a color filter manufacturing process Efficiency tends to improve. For example, as for the content rate of the said high boiling point solvent A in (B) solvent, 1-50 mass % is preferable, 5-40 mass % is more preferable, 10-30 mass % is still more preferable, 15-20 mass % is especially preferable.

When (B) solvent in the colored resin composition of this invention contains the said high boiling point solvent A, the said high boiling point solvent B, and the said low boiling point solvent, (B) content rate of the said high boiling point solvent B in a solvent Although not specifically limited, 0.1 mass % or more is preferable, 0.5 mass % or more is more preferable, 1 mass % or more is still more preferable, 2 mass % or more is especially preferable, and 20 mass % or less is preferable, , 15 mass % or less is more preferable, 10 mass % or less is still more preferable, and 5 mass % or less is especially preferable. By setting it more than the said lower limit, alkali solubility improves efficiently, and there exists a tendency for the generation|occurrence|production of the bump at the time of VCD (pressure drying) in a color filter manufacturing process to be suppressed, Moreover, by setting it below the said upper limit, VCD (reducing-pressure drying) in a color filter manufacturing process ) tends to improve the efficiency. For example, 0.1-20 mass % is preferable, as for the content rate of the said high boiling point solvent B in (B) solvent, 0.5-15 mass % is more preferable, 1-10 mass % is still more preferable, 2-5 mass % is especially preferable.

When (B) solvent in the colored resin composition of this invention contains the said high boiling point solvent A, the said high boiling point solvent B, and the said low boiling point solvent, the content rate of the low boiling point solvent in (B) solvent is specifically limited However, 30 mass % or more is preferable, 45 mass % or more is more preferable, 60 mass % or more is still more preferable, 75 mass % or more is especially preferable, and 98.9 mass % or less is preferable, and 94.5 mass % or less is preferable. % or less is more preferable, 89 mass % or less is still more preferable, and 83 mass % or less is especially preferable. By using more than the said lower limit, the efficiency of VCD (pressure drying) in the color filter manufacturing process tends to improve, and alkali solubility improves by setting it as below the said upper limit, Dolby at the time of VCD (pressure drying) in a color filter manufacturing process. occurrence tends to be suppressed. For example, as for the content rate of the said low boiling point solvent in (B) solvent, 30-98.9 mass % is preferable, 45-94.5 mass % is more preferable, 60-89 mass % is still more preferable, 75- 83 mass % is especially preferable.

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

The colored resin composition of this invention contains (C) alkali-soluble resin. (C) By containing alkali-soluble resin, the film hardening by photopolymerization and the solubility by a developing solution can be made compatible.

(C) As alkali-soluble resin, For example, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-300922, Unexamined-Japanese-Patent No. 11-140144, for example. Although known high molecular compounds described in publications such as Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 2000-56118, and Japanese Patent Application Laid-Open No. 2003-233179 can be used, among them, preferred are Resins of the following (C-1)-(C-5), etc. are mentioned.

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

(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) Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter referred to as “resin (C-3)” in some cases)

(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 these, resin (C-1) is particularly preferable, 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 by an alkaline developer and have solubility to such an extent that the target development treatment can be performed, respectively, in JP-A-2009-025813 What is described as the same item in , can be preferably employed.

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

As one of the preferable aspects of the resin (C-1), "10 to 10 epoxy groups which the copolymer has with respect to a copolymer of 5 to 90 mol% of an epoxy group-containing (meth)acrylate and 10 to 95 mol% of another radically polymerizable monomer. Alkali-soluble resin obtained by adding polybasic acid anhydride to resin formed by adding an unsaturated monobasic acid to -100 mol%, or 10-100 mol% of the hydroxyl groups produced|generated by the addition reaction" is mentioned.

As the epoxy group-containing (meth)acrylate, for example, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether. Especially, glycidyl (meth)acrylate is preferable. These epoxy group containing (meth)acrylates may be used individually by 1 type, and may use 2 or more types together.

As another radically polymerizable monomer copolymerized with an epoxy-group containing (meth)acrylate, the mono(meth)acrylate which has a structure represented by the following general formula (V) is preferable.

[Formula 12]

Equation (Ⅴ) of, R ⁹¹ ~ R ⁹⁸ are, each independently, represent a hydrogen atom, or an alkyl group having a carbon number of 1 to 3, respectively. Further, R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be linked to each other to form a ring.

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

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

By introducing these structures into the alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the strength of a pixel formed using the colored resin composition tends to increase. have.

In addition, the mono(meth)acrylate which has a structure represented by General formula (V) may be used individually by 1 type, and may use 2 or more types together.

[Formula 13]

As the mono(meth)acrylate having a structure represented by the general formula (V), various known mono(meth)acrylates can be used as long as they have the structure. In particular, mono(meth)acrylates represented by the following general formula (VI) are desirable.

[Formula 14]

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

In the copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, the content rate of the repeating unit derived from the mono(meth)acrylate represented by the general formula (VI) is, in the other radically polymerizable monomer, Among the repeating units derived from it, 5-90 mol% is preferable, 10-70 mol% is more preferable, 15-50 mol% is still more preferable.

In addition, although it does not specifically limit as another radically polymerizable monomer other than the mono(meth)acrylate represented by the said general formula (VI), Specifically, For example, ?-, o-, m of styrene and styrene vinyl aromatics such as -, p-alkyl, nitro, cyano, amide and ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; (meth)methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl , (meth) acrylate pentyl, (meth) acrylate neopentyl, (meth) acrylate isoamyl, (meth) acrylate hexyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate lauryl, (meth) acrylate dodecyl , (meth) cyclopentyl acrylate, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid dicyclohexyl, (meth) acrylate isobornyl, (meth) acrylate adamantyl, ( Meth) acrylic acid propargyl, (meth) acrylic acid phenyl, (meth) acrylate naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylate piperonyl, (meth) acrylic acid furyl, ( Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid 1,1,1 -trifluoroethyl, (meth)acrylic acid perfluoroethyl, (meth)acrylic acid perfluoro-n-propyl, (meth)acrylic acid perfluoroisopropyl, (meth)acrylic acid triphenylmethyl, (meth)acrylic acid cumyl (meth)acrylic acid esters, such as (meth)acrylic acid 3-(N,N- dimethylamino) propyl, (meth)acrylic acid 2-hydroxyethyl, and (meth)acrylic acid 2-hydroxypropyl; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di (meth)acrylic acid amides, such as isopropylamide and (meth)acrylic acid anthracenylamide; vinyl compounds such as anilide (meth)acrylate, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Monomaleimides, such as N-phenyl maleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N-(4-hydroxyphenyl) maleimide; N-(meth)acryloylphthalimide etc. are mentioned.

Among these other radically polymerizable monomers, it is preferable to contain at least one selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition. . In particular, in the repeating unit derived from another radically polymerizable monomer, the content ratio of the repeating unit derived from at least one selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide is 1 to 70 moles. %, and more preferably 3 to 50 mol%.

In addition, a well-known solution polymerization method is applied to the copolymerization reaction of the said epoxy-group containing (meth)acrylate and the said other radically polymerizable monomer. The solvent to be used will not be specifically limited if it is inactive to radical polymerization, The organic solvent normally used can be used.

Examples of the solvent include ethylene glycol monoalkyl ether acetates such as cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; Acetic acid esters, such as ethyl acetate, isopropyl acetate, and dipropylene glycol monoalkyl ether acetate; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; Dimethylformamide, N-methylpyrrolidone, etc. are mentioned. These solvents may be used independently and may use 2 or more types together.

The usage-amount of these solvents is 30-1000 mass parts normally with respect to 100 mass parts of copolymers obtained, Preferably it is 50-800 mass parts. Control of the molecular weight of a copolymer tends to become easy by making the usage-amount of a solvent into the said range.

The radical polymerization initiator used for 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 those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy- 2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2 ,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylperoxide, dicumylhydroperoxide, acetyl peroxide, bis(4-t- Butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy) 3 and 3,5-trimethylcyclohexane and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

Moreover, as an azo compound catalyst, azobisisobutyronitrile, azobiscarbonamide, etc. are mentioned.

Among these, one type or two or more types of radical polymerization initiators of suitable half-life are used according to polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 mass parts normally with respect to a total of 100 mass parts of the monomer used for a copolymerization reaction, Preferably it is 1-10 mass parts.

The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used for the copolymerization reaction in a solvent and raising the temperature while stirring, or may be carried out by dropping the monomer to which the radical polymerization initiator has been added into the solvent heated and stirred. Moreover, you may add a radical polymerization initiator in a solvent, and you may drip a monomer in what was heated up. Reaction conditions can be freely changed according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth)acrylate and the other radically polymerizable monomer is derived from 5 to 90 mol% of the repeating unit derived from the epoxy group-containing (meth)acrylate and other radically polymerizable monomers. It is preferably composed of 10 to 95 mol% of the repeating unit, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 70 mol% of the former and 70 to 30 mol% of the latter Especially preferred.

When the content rate of the repeating unit derived from the epoxy group-containing (meth)acrylate is equal to or greater than the lower limit, the amount of the unsaturated monobasic acid or polybasic acid anhydride to be added tends to be sufficient, and on the other hand, derived from other radically polymerizable monomers. When the content rate of the repeating unit to be used is equal to or more than the lower limit, heat resistance and strength tend to be sufficient.

Then, an unsaturated monobasic acid (polymerizable component) and polybasic acid anhydride (alkali-soluble component) are made to react with the epoxy group part of the copolymer of an epoxy resin containing (meth)acrylate and another radically polymerizable monomer.

A well-known thing can be used as an unsaturated monobasic acid added to an epoxy group, For example, the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

Specific examples include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meth) in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. Monocarboxylic acids, such as acrylic acid, etc. are mentioned. Among them, (meth)acrylic acid is preferable. These 1 type may be used independently and may use 2 or more types together.

By adding such a component, polymerizability can be provided to resin (C-1).

Although these unsaturated monobasic acids are added to 10-100 mol% of the epoxy groups which the said copolymer has normally, Preferably it is 30-100 mol%, More preferably, it is added to 50-100 mol%. By using more than the said lower limit, there exists a tendency for the temporal stability of a colored resin composition to become favorable. In addition, as a method of adding an unsaturated monobasic acid to the epoxy group of a copolymer, a well-known method is employable.

In addition, as a polybasic acid anhydride added to the hydroxyl group produced|generated when an unsaturated monobasic acid is added to the epoxy group of a copolymer, a well-known thing can be used.

For example, dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and anhydrides of tribasic or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Especially, tetrahydrophthalic anhydride and/or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be provided to resin (C-1).

These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups produced by adding an unsaturated monobasic acid to the epoxy group of the copolymer, but preferably 20 to 90 mol%, more preferably 30 to 80 added to mole %. By using below the said upper limit, there exists a tendency for the residual-film rate at the time of image development to become favorable, and there exists a tendency for solubility to become sufficient by setting it as more than the said lower limit. In addition, as a method of adding a polybasic acid anhydride to a hydroxyl group, a well-known method is employable.

Moreover, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, you may add glycidyl (meth)acrylate or the glycidyl ether compound which has a polymerizable unsaturated group to a part of the produced|generated carboxyl group.

Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to a part of the produced|generated carboxyl group.

Moreover, you may add these both.

As a specific example of the glycidyl ether compound which does not have a polymerizable unsaturated group, the glycidyl ether compound etc. which have a phenyl group or an alkyl group are mentioned. As a commercial item, for example, "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX" manufactured by Nagase Chemtex Co., Ltd. under the trade names, for example. -146", "Denacall EX-171", "Denacall EX-192", etc.

Moreover, regarding the structure of such resin, it describes in, for example, Unexamined-Japanese-Patent No. 8-297366 and Unexamined-Japanese-Patent No. 2001-89533, and it is already well-known.

Although the weight average molecular weight (Mw) of polystyrene conversion measured by GPC of resin (C-1) is not specifically limited, 3000-100000 are preferable and 5000-50000 are especially preferable. By using more than the said lower limit, there exists a tendency for heat resistance and film strength to become favorable, and there exists a tendency for the solubility with respect to a developing solution to become favorable by using below the said upper limit. Moreover, as for ratio of weight average molecular weight (Mw)/number average molecular weight (Mn) as a reference|standard of molecular weight distribution, 2.0-5.0 are preferable.

On the other hand, from the viewpoint of coating film curability at the time of UV exposure, (C) among alkali-soluble resins, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain (hereinafter referred to as "(c1) acrylic copolymer resin") there) is preferred.

(c1) Although the partial structure containing the side chain which has an ethylenically unsaturated group which the acrylic copolymer resin has is not specifically limited, From a viewpoint of coexistence of the coating-film hardening at the time of ultraviolet exposure and alkali solubility at the time of alkali development, for example, It is preferable to have a partial structure represented by the following general formula (I).

[Formula 15]

In formula (I), R<^1> and R<^2> respectively independently represent a hydrogen atom or a methyl group. * indicates a bond.

Moreover, among the partial structures represented by the said Formula (I), the partial structure represented by the following general formula (I') from a viewpoint of a sensitivity and alkali developability is preferable.

[Formula 16]

In formula (I'), R<^1> and R<^2> respectively 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 the polybasic acid or anhydride thereof. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorend. 1 type(s) or 2 or more types selected from an acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are mentioned.

Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetracarboxylic acid is more preferable. hydrophthalic acid and biphenyltetracarboxylic acid.

(c1) Although the content rate of the partial structure represented by the said General formula (I) contained in the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain is not specifically limited, 10 mol% or more is preferable, and 20 mol% or more is more Preferably, 30 mol% or more is more preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 95 mol% or less is preferable, and 90 mol% or less is more preferable, 85 mol% or less is more preferable, 80 mol% or less is still more preferable, 75 mol% or less is especially preferable, and 70 mol% or less is most preferable. By setting it as more than the said lower limit, there exists a tendency for coating-film sclerosis|hardenability at the time of ultraviolet exposure to improve, and by setting it as below the said upper limit, there exists a tendency for alkali solubility at the time of alkali development to improve. For example, 10-95 mol% is preferable, as for the content rate of the partial structure represented by the said General formula (I), 20-90 mol% is more preferable, 30-85 mol% is still more preferable, 40- 80 mol% is more preferable, 50-75 mol% is especially preferable, and 50-70 mol% is the most preferable.

(c1) Although the content rate of the partial structure represented by the said General formula (I') contained in the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain is not specifically limited, 10 mol% or more is preferable, 20 mol% or more More preferably, 30 mol% or more is more preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 95 mol% or less is preferable, and 90 mol% or less is more preferable and 85 mol% or less is more preferable, 80 mol% or less is still more preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. By setting it as more than the said lower limit, there exists a tendency for coating-film sclerosis|hardenability at the time of ultraviolet exposure to improve, and by setting it as below the said upper limit, there exists a tendency for alkali solubility at the time of alkali development to improve. For example, 10-95 mol% is preferable, as for the content rate of the partial structure represented by the said General formula (I'), 20-90 mol% is more preferable, 30-85 mol% is still more preferable, 40 -80 mol% is more preferable, 50-75 mol% is especially preferable, and 50-70 mol% is the most preferable.

(c1) When the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain contains the partial structure represented by the said General formula (I), Although the partial structure contained is not specifically limited, The viewpoint of alkali solubility at the time of alkali development In , for example, it is also preferable to have a partial structure represented by the following general formula (II).

[Formula 17]

In the formula (II), R ³ represents a hydrogen atom or a methyl group, 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.

(R ⁴ )

In said Formula (II), R<^4> represents the alkyl group which may have a substituent, the aromatic ring group which may have a substituent, or the alkenyl group which may have a substituent.

Examples ^{of the alkyl group for R 4} include a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 8 or more, more preferably 20 or less, more preferably 18 or less, more preferably 16 or less. It is preferable, 14 or less are still more preferable, and 12 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group or a dodecanyl group is preferable from a developable viewpoint, and a dicyclopentanyl group is more preferable.

Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples ^{of the aromatic ring group for R 4} include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. 6 or more are preferable, and, as for the carbon number, 24 or less are preferable, 22 or less are more preferable, 20 or less are still more preferable, 18 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. and groups such as a ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Moreover, as an aromatic heterocyclic group in an aromatic heterocyclic group, a monocyclic ring or a condensed ring may be sufficient, For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, imi Dazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, Thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, and groups such as a quinoxaline ring, a phenanthrizine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene cyclic group or a naphthalene cyclic group is preferable from a developable viewpoint, and a benzene cyclic group is more preferable.

Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁴ include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, and a 3-pentene group. A -2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group, cyclohexenyl group, etc. are mentioned. Among these, a vinyl group or an allyl group is preferable from a developable viewpoint, and a vinyl group is more preferable.

Moreover, as a substituent which the alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As such, 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 them, an alkyl group or an alkenyl group is preferable from the viewpoint of developability and film strength, , an alkyl group is more preferable.

(c1) Although the content rate of the partial structure represented by the said General formula (II) in the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain is not specifically limited, 1 mol% or more is preferable, 5 mol% or more is more Preferably, 10 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is still more preferable, 40 mol% or less is particularly preferred. There exists a tendency for alkali solubility to improve by using more than the said lower limit, and there exists a tendency for the storage stability of a colored resin composition to improve by using below the said upper limit. 1 to 70 mol% is preferable, as for the content rate of the partial structure represented by the said General formula (II), 5-60 mol% is more preferable, 10-50 mol% is still more preferable, 20-40 mol% is Especially preferred.

(c1) When the acrylic copolymer resin contains a partial structure represented by the above general formula (I), as a partial structure to be contained, by improving the affinity of the phthalocyanine compound (1) and (c1) acrylic copolymer resin , it is preferable to contain a partial structure represented by the following general formula (III) from the viewpoint of alkali solubility of the phthalocyanine compound (1).

[Formula 18]

In the formula (III), R ⁵ represents a hydrogen atom or a methyl group, 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 hydroxy group, a carboxyl group, a halogen An atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group is shown. t represents the integer of 0-5.

(R ⁶ )

In the formula (III), R ⁶ is 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 hydroxy group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, A thiol group or the alkyl sulfide group which may have a substituent is represented.

Examples ^{of the alkyl group for R 6} include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, more preferably 14 or less. More preferably, 12 or less are particularly preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group or a dodecanyl group is preferable from a heat resistant viewpoint, and a dicyclopentanyl group is more preferable.

Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁶ include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, and a 3-pentene group. A -2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group, cyclohexenyl group, etc. are mentioned. Among these, a vinyl group or an allyl group is preferable from a viewpoint of the exposure sensitivity at the time of ultraviolet exposure, and a vinyl group is more preferable.

Moreover, as a substituent which the alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkynyl group for R ⁶ include a linear, branched or cyclic alkynyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkynyl group include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-penta Diyn-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, etc. are mentioned.

Moreover, as a substituent which the alkynyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As a halogen atom in R<^6> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Among these, a fluorine atom is preferable from a viewpoint of the storage stability of (c1) acrylic copolymer resin.

Examples ^{of the alkoxy group for R 6} include a linear, branched or cyclic alkoxy group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

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

Moreover, as a substituent which the alkoxy group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkyl sulfide group for R ⁶ include a linear, branched or cyclic alkyl sulfide group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. By using more than the said lower limit, there exists a tendency for lipophilicity to improve and the solubility to a solvent to improve, and by setting it as below the said upper limit, hydrophilicity to improve and there exists a tendency for alkali solubility to improve.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. Among these, a methyl sulfide group or an ethyl sulfide group is preferable from a developable viewpoint.

Moreover, as a substituent which the alkyl group in an alkyl sulfide group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, An acryloyl group, a methacryloyl group, etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As such, R ⁶ is 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 hydroxy group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or a substituent Although the alkylsulfide group which may have is shown, a hydroxyl group or a carboxyl group is preferable from a developable viewpoint among these, and a carboxyl group is more preferable.

Although t in said Formula (III) represents the integer of 0-5, it is preferable that t is 0 from a viewpoint of manufacturing easiness.

(c1) Although the content rate of the partial structure represented by the said General formula (III) in the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain is not specifically limited, 1 mol% or more is preferable, and 2 mol% or more is more Preferably, 5 mol% or more is more preferable, 8 mol% or more is particularly preferable, and 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is still more preferable, 20 mol% or less is particularly preferred. By setting it to more than the above lower limit, the affinity of the phthalocyanine compound (1) and (c1) acrylic copolymer resin improves, and alkali solubility tends to improve, and by setting it below the above upper limit, the content of other partial structures increases, , the alkali solubility tends to be improved. For example, 1-50 mol% is preferable, as for the content rate of the partial structure represented by the said General formula (III), 2-40 mol% is more preferable, 5-30 mol% is still more preferable, 8- 20 mol% is particularly preferable.

(c1) When the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain has the partial structure represented by the said General formula (I), it is a partial structure contained elsewhere, The part represented by the following general formula (IV) from a developable viewpoint. It is also preferable to have a structure.

[Formula 19]

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

(c1) Although the content rate in case the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain has the partial structure represented by the said General formula (IV) is not specifically limited, 5 mol% or more is preferable, 10 mol% or more More preferably, 20 mol% or more is more preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is still more preferable. There exists a tendency for alkali solubility to improve by using more than the said lower limit, and there exists a tendency for the storage stability of a colored resin composition to improve by using below the said upper limit. For example, 5-80 mol% is preferable, as for the content rate in the case of having the partial structure represented by the said General formula (IV), 10-70 mol% is more preferable, 20-60 mol% is still more preferable. do.

On the other hand, (C) although the acid value of alkali-soluble resin is not specifically limited, 10 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 40 mgKOH/g or more is still more preferable, 50 mgKOH/g or more is more preferable, 60 mgKOH/g or more is particularly preferable, 300 mgKOH/g or less is preferable, 250 mgKOH/g or less is more preferable, 200 mgKOH/g or more Below is more preferable, and 150 mgKOH/g or less is still more preferable. There exists a tendency for alkali solubility to improve by using more than the said lower limit, and there exists a tendency for the storage stability of a colored resin composition to improve by using below the said upper limit. For example, (C), 10-300 mgKOH/g is preferable, as for the acid value of alkali-soluble resin, 30-300 mgKOH/g is more preferable, 40-250 mgKOH/g is still more preferable, 50 -200 mgKOH/g is more preferable, and 60-150 mgKOH/g is especially preferable.

(C) Although the weight average molecular weight (Mw) of alkali-soluble resin is not specifically limited, Usually, 1000 or more, Preferably it is 2000 or more, More preferably, it is 4000 or more, More preferably, it is 6000 or more, More preferably, it is 7000. or more, particularly preferably 8000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, still more preferably 10000 or less. There exists a tendency for heat resistance and coating-film sclerosis|hardenability to improve by using more than the said lower limit, and there exists a tendency for alkali solubility to improve by using below the said upper limit. For example, (C) 1000-30000 are preferable, as for the weight average molecular weight (Mw) of alkali-soluble resin, 2000-30000 are more preferable, 4000-20000 are still more preferable, 6000-20000 are still more preferable, , 7000 to 15000 are particularly preferred, and 8000 to 10000 are most preferred.

Although the content rate of (C) alkali-soluble resin in the colored resin composition of this invention is not specifically limited, In total solid of a colored resin composition, it is 1 mass % or more normally, Preferably it is 5 mass % or more, More preferably is 10 mass % or more, more preferably 20 mass % or more, still more preferably 25 mass % or more, particularly preferably 30 mass % or more, and is usually 80 mass % or less, preferably 60 mass % or more. Hereinafter, more preferably, it is 50 mass % or less, More preferably, it is 40 mass % or less. By setting it as more than the said lower limit, a strong film|membrane is obtained and it exists in the tendency excellent also in adhesiveness to a board|substrate. Moreover, by setting it as below the said upper limit, the permeability of the developing solution with respect to an exposed part is low, and there exists a tendency which can suppress the deterioration of the surface smoothness and sensitivity of a pixel. For example, as for the content rate of (C) alkali-soluble resin, 1-80 mass % is preferable, 5-80 mass % is more preferable, 10-60 mass % is still more preferable, 20-60 mass % is It is still more preferable, 25-50 mass % is especially preferable, and 30-40 mass % is the most preferable.

[1-4] (D) Photoinitiator

The colored resin composition of this invention contains (D) a photoinitiator. (D) By containing a photoinitiator, the film|membrane curability by photoinitiation can be acquired.

(D) A photoinitiator can also be used as a mixture (photoinitiation system) with additives, such as an accelerator (chain transfer agent) and a sensitizing dye added as needed. The photopolymerization initiation system is a component having a function of directly absorbing light or photosensitizing, causing a decomposition reaction or a hydrogen extraction reaction, and generating polymerization active radicals.

As a photoinitiator, for example, the metallocene compound containing the titanocene compound described in each publication of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197, Unexamined-Japanese-Patent No. Hei 10 N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in -39503, N-aryl-α-amino acid salts, N-aryl-α -Radical activators, such as amino acid esters, (alpha)- aminoalkylphenone type compound, the oxime ester type initiator described in Unexamined-Japanese-Patent No. 2000-80068, etc. are mentioned.

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

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro halomethylated triazine derivatives such as romethyl)-s-triazine;

2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 ,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 halomethylated oxadiazole derivatives such as -furyl-1,3,4-oxadiazole;

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

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

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

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

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methyl Ethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- acetophenone derivatives such as 1-one and 1,1,1-trichloromethyl-(p-butylphenyl)ketone;

Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di thioxanthone derivatives such as isopropyl thioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

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

phenazine derivatives such as 9,10-dimethylbenzphenazine;

Anthrone derivatives, such as a benzanthrone;

Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclo Pentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-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, etc. strong derivatives;

2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1- One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoaceto Phenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-( α-aminoalkylphenone compounds such as 4-diethylaminobenzoyl)coumarin and 4-(diethylamino)chalcone;

1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole Oxime ester compounds such as -3-yl]-1-(O-acetyloxime).

Among these, it is preferable that it is an oxime ester type compound (oxime ester type photoinitiator) from a viewpoint of a sensitivity and surface property.

Since the oxime ester-based compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive in a small amount, and is stable to a thermal reaction, and is highly sensitive in a small amount. It is possible to design a colored resin composition of In particular, the oxime ester-type compound which has a carbazole ring which may have a substituent from a viewpoint of the light absorption with respect to i line|wire (365 nm) of an exposure light source is preferable.

As an oxime ester type compound, the compound represented by the following general formula (I-1) is mentioned, for example.

[Formula 20]

In the 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 including an aromatic ring or a heteroaromatic ring.

R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.

Although carbon number of the alkyl group in R ^21a is not specifically limited, From a viewpoint of the solubility with respect to a solvent and the sensitivity with respect to exposure, it is 1 or more normally, Preferably it is 2 or more, And Usually 20 or less, Preferably 15 or less. , More preferably, it is 10 or less, More preferably, it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group.

Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, or N-acetyl-N -acetoxyamino group etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

^Examples of the aromatic cyclic group for R 21a include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Although carbon number of an aromatic ring group is not specifically limited, From a soluble viewpoint with respect to a colored resin composition, it is preferable that it is 5 or more. Moreover, from a developable viewpoint, 30 or less are preferable, 20 or less are more preferable, 12 or less are still more preferable, 8 or less are especially preferable.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. Among them, a phenyl group, a naphthyl group or a fluorenyl group is preferable from the viewpoint of developability, and a phenyl group or A fluorenyl group is more preferable.

As the substituent which the aromatic ring group may have, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, etc. are mentioned, From the viewpoint of developability, a hydroxyl group, A carboxy group is preferable, and a carboxy group is more preferable. Moreover, as a substituent in the alkyl group which may have a substituent, or the alkoxy group which may have a substituent, a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group are mentioned.

Among these, in view of development, R ^21a is preferably an alkyl group which may have a substituent, more preferably unsubstituted alkyl group, more preferably a methyl group.

R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring, from the viewpoint of solubility in a solvent or sensitivity to exposure, a carbazolyl group which may have a substituent, a thioxanthonyl group which may have a substituent, The diphenylsulfide group which may have a substituent, the fluorenyl group which may have a substituent, and the group which connected these groups and a carbonyl group are mentioned preferably. Among these, the carbazolyl group which may have a substituent, or the group which linked the carbazolyl group which may have a substituent and a carbonyl group from a viewpoint of the light absorption with respect to i line|wire (365 nm) of an exposure light source is preferable.

Although ^{the number of carbon atoms of the alkanoyl group in R 22a} is not particularly limited, from the viewpoint of solubility and sensitivity to a solvent, usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.

As a substituent which the alkanoyl group may have, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Although ^{the number of carbon atoms of the aryl group in R 22a} is not particularly limited, from the viewpoint of solubility and sensitivity to a solvent, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, More preferably, it is 10 or less. Specific examples of the aryl group include a benzoyl group and a naphthoyl group.

As a substituent which the aryl group may have, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Among the compounds represented by the general formula (I-1), compounds represented by the following general formulas (I-2) or (I-3) are exemplified from the viewpoint of light absorptivity to i-line (365 nm) of the exposure light source. have.

[Formula 21]

[Formula 22]

In the formula (I-2) or (I-3), R ^21a and R ^22a have the same meaning as in the 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 aryloyl group which may have a substituent, a heteroaryloyl group which may have a substituent, or a nitro group.

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

Although ^{the number of carbon atoms of the alkyl group in R 23a} is not particularly limited, from the viewpoint of solubility in a solvent, usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, More preferably, it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.

As a substituent which the alkyl group may have, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Among these, as R ^23a , it is more preferable that it is an ethyl group from a viewpoint of the solubility with respect to a solvent, and synthetic|combination easiness.

Although ^{the number of carbon atoms of the alkyl group in R 24a} is not particularly limited, from the viewpoint of solubility in a solvent, usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, More preferably, it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.

As a substituent which the alkyl group may have, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Although carbon number of the aryl group in R ^24a is not specifically limited, From a viewpoint of solubility with respect to a solvent, it is 7 or more normally, Preferably it is 8 or more, More preferably, it is 9 or more, Moreover, it is normally 20 or less, Preferably Preferably it is 15 or less, More preferably, it is 10 or less, More preferably, it is 9 or less. Specific examples of the aryl group include a benzoyl group and a naphthoyl group.

As a substituent which the aryl group may have, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is an ethyl group.

Although ^{the number of carbon atoms of the heteroaryl group in R 24a} is not particularly limited, from the viewpoint of solubility in a solvent, usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, Preferably it is 15 or less, More preferably, it is 10 or less, More preferably, it is 9 or less. Specific examples of the heteroaryl group include a furancarbonyl group, a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group.

As a substituent which the heteroaryl group may have, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Among these, as R ^24a , from a viewpoint of a sensitivity, the arylloyl group which may have a substituent is preferable, and a benzoyl group is more preferable.

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

As a commercial item of such an oxime ester type compound, OXE-02, OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Strong Electronic New Materials, or N-1919 manufactured by ADEKA, Inc. , NCI-930, NCI-831, and the like.

As an oxime ester type compound, although a compound specifically illustrated below is mentioned, It is not limited to these compounds at all.

[Formula 23]

[Formula 24]

[Formula 25]

These photoinitiators may be used individually by 1 type, respectively, and may mix and use 2 or more types.

Moreover, in addition to (D) a photoinitiator, you may use a chain transfer agent further. A chain transfer agent is a compound which has the function of receiving the generated radical and transmitting the received radical to another compound.

As the chain transfer agent, as long as it is a compound having the above function, various substances can be used. For example, a mercapto group-containing compound, carbon tetrachloride, etc. are mentioned, and since the chain transfer effect tends to be high, it has a mercapto group. It is more preferable to use a compound. It is thought that this is because bond cleavage tends to occur because the S-H bond energy is small, and hydrogen extraction reaction and chain transfer reaction are likely to occur. It is effective for sensitivity improvement and surface hardening property.

As the mercapto group-containing compound, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 3-mercapto-1,2,4-triazole, 2-mercapto mercapto group-containing compounds having an aromatic ring, such as -4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethyl mercaptobenzene; Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3- Mercaptopropionate), butanediol bis (3-mercapto butyrate), ethylene glycol bis (3-mercapto butyrate), trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3 -mercaptobutylate), pentaerythritol tris(3-mercaptobutylate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4, and aliphatic mercapto group-containing compounds such as 6(1H,3H,5H)-trione, and compounds having a plurality of mercapto groups are particularly preferred from the viewpoint of surface smoothness.

Among them, 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and among the aliphatic mercapto group-containing compounds, trimethylolpropane Tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyl) rate), pentaerythritol tetrakis (3-mercaptobutylate), pentaerythritol tris (3-mercaptobutylate), 1,3,5-tris (3-mercaptobutyloxyethyl)-1,3 ,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

In terms of sensitivity, an aliphatic mercapto group-containing compound is preferable, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) , pentaerythritol tris (3-mercaptopropionate), trimethylol propane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), pentaerythritol tris (3-mer captobutylate) and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred; Pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutylate) are more preferable.

These may be used individually by 1 type, and may use 2 or more types together.

Colored resin composition of this invention WHEREIN: Although the content rate of (D) photoinitiator is not specifically limited, 1 mass % or more is preferable in the total solid of a colored resin composition, 2 mass % or more is more preferable, 3 mass % More preferably, 4 mass % or more is still more preferable, 5 mass % or more is especially preferable, 15 mass % or less is preferable, 10 mass % or less is more preferable, 8 mass % or less is still more It is preferable, and 6 mass % or less is especially preferable. By setting it as more than the said lower limit, there exists a tendency which the patterning characteristic after image development can be ensured, and there exists a tendency for the transmittance|permeability fall by the excess addition of a photoinitiator to be suppressed by setting it as below the said upper limit. For example, (D) 1-15 mass % is preferable, as for the content rate of a photoinitiator, 2-15 mass % is more preferable, 3-10 mass % is still more preferable, 4-8 mass % is more It is more preferable, and 5-6 mass % is especially preferable.

When the colored resin composition of this invention contains a chain transfer agent, the content rate is although it does not specifically limit, 0.01 mass % or more is preferable in the total solid of a colored resin composition, 0.1 mass % or more is more preferable, 0.2 mass or more This is more preferable, 0.5 mass % or more is still more preferable, 1 mass % or more is still more preferable, 1.5 mass % or more is especially preferable, 5 mass % or less is preferable, 3 mass % or less is more It is preferable, and 2 mass % or less is more preferable. There exists a tendency which can ensure storage stability and the patterning formation ability at the time of alkali development by setting it as the said range. When it contains a chain transfer agent, 0.01-5 mass % is preferable, as for the content rate, for example, 0.1-5 mass % is more preferable, 0.2-3 mass % is still more preferable, 0.5-3 mass % is still more preferable, 1 to 2 mass % is still more preferable, and 1.5 to 2 mass % is especially preferable.

[1-5] Other solid content

Solid content other than the said component can be further mix|blended with the colored resin composition of this invention as needed. As such a component, a photopolymerizable monomer, a dispersing agent, a dispersing auxiliary agent, surfactant, etc. are mentioned.

[1-5-1] Photopolymerizable monomer

The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “ethylenic compound”) is preferable. An ethylenic compound is a compound which has an ethylenic double bond which is addition-polymerized by the action of a photoinitiator and hardens when the colored resin composition of this invention receives irradiation of actinic light. In addition, the monomer in this invention means the concept relative to what is called a high molecular substance, and means the concept which also contains dimer, trimer, and an oligomer other than a monomer in a narrow meaning.

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has two or more ethylenic double bonds in 1 molecule. Although the number of ethylenic double bonds which a polyfunctional ethylenic monomer has is not specifically limited, Usually, it is 2 or more, Preferably it is 4 or more, More preferably, it is 5 or more, More preferably, it is 8 It is less than, More preferably, it is seven or less. There exists a tendency to become highly sensitive by using more than the said lower limit, and there exists a tendency for the solubility with respect to a solvent to improve by using below the said upper limit.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds and unsaturated carboxylic acids. Esters, esters obtained by esterification of unsaturated carboxylic acids with polyhydric carboxylic acids, aliphatic polyhydroxy compounds, and polyhydric hydroxy compounds such as aromatic polyhydroxy compounds, polyisocyanate compounds and (meth)acryloyl-containing hydroxy The ethylenic compound etc. which have the urethane skeleton in which the compound was made to react are mentioned.

As ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylolethane triacrylate, pentaerythritol di Acrylic acid esters, such as acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, are mentioned. can In addition, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester with a methacrylic acid moiety, an itaconic acid ester with an itaconic acid moiety, a crotonic acid ester with a crotonic acid moiety, or a maleic acid moiety. Maleic acid ester etc. are mentioned.

As ester of an aromatic polyhydroxy compound and unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, for example and the like.

The ester obtained by the esterification reaction of an unsaturated carboxylic acid, polyhydric carboxylic acid, and polyhydric hydroxy compound is not necessarily a single thing, and a mixture may be sufficient as it. Representative examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, and a condensate of butanediol and glycerin.

As an ethylenic compound which has urethane skeleton which made the polyisocyanate compound and the (meth)acryloyl group containing hydroxy compound react, For example, Aliphatic diisocyanate, such as hexamethylene diisocyanate and trimethyl hexamethylene diisocyanate; Alicyclic diisocyanate, such as cyclohexane diisocyanate and isophorone diisocyanate; Aromatic diisocyanates, such as tolylene diisocyanate and diphenylmethane diisocyanate, etc., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl ) a reaction product of a (meth)acryloyl group-containing hydroxy compound such as propane and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

In addition, as an ethylenic compound used for this invention, For example, Acrylamides, such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; Vinyl group-containing compounds, such as divinyl phthalate, etc. are useful.

Moreover, the monomer which has an acid value may be sufficient as an ethylenic compound. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional monomer in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. is preferred, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.

Although these monomers may be used individually by 1 type, since it is difficult to use a single compound on manufacture, you may mix and use 2 or more types. Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as a monomer as needed.

As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH/g, Especially preferably, it is 5-30 mgKOH/g. If the value is higher than or equal to the lower limit, the development and dissolution characteristics tend to be good, and when the value is lower than the upper limit, manufacturing and handling are improved, and curing properties such as photopolymerization performance and surface smoothness of pixels tend to be improved. Therefore, when using together 2 or more types of polyfunctional monomers of different acidic radicals, or when using together the polyfunctional monomer which does not have an acidic radical, it is preferable to adjust so that the acidic radicals as all polyfunctional monomers may fall within the said range.

In the present invention, the polyfunctional monomer having a more preferable acid group is a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toa Synthesis Co., Ltd. It is a mixture composed mainly of You can also use combining the other polyfunctional monomers of this polyfunctional monomer. Moreover, the thing described in Paragraph [0056] and [0057] of Unexamined-Japanese-Patent No. 2013-140346 can also be used.

Moreover, in this invention, it is preferable to use the polymerizable monomer of Unexamined-Japanese-Patent No. 2013-195971 from a viewpoint of making favorable the chemical-resistance of a pixel, or the linearity of the edge of a pixel. It is preferable to use the polymerizable monomer of Unexamined-Japanese-Patent No. 2013-195974 from a viewpoint of making the sensitivity of a coating film, and shortening of image development time compatible.

When the colored resin composition of the present invention contains a photopolymerizable monomer, the content rate of the photopolymerizable monomer is not particularly limited, but in the total solid content of the colored resin composition, usually 0 mass% or more, preferably 5 mass% or more, More preferably, it is 10 mass % or more, More preferably, it is 15 mass % or more, Especially preferably, it is 20 mass % or more, and it is 70 mass % or less normally, Preferably it is 60 mass % or less, More preferably, it is 50 mass % or less. It is mass % or less, More preferably, it is 40 mass % or less, Especially preferably, it is 30 mass % or less. There exists a tendency for sclerosis|hardenability of a coating film to become high by using more than the said lower limit, and there exists a tendency for the fall of alkali developability to be suppressed by using below the said upper limit. For example, when the colored resin composition of this invention contains a photopolymerizable monomer, 0-70 mass % is preferable, as for the content rate of a photopolymerizable monomer, 5-60 mass % is more preferable, 10-50 mass % is more preferable, 15-40 mass % is especially preferable, and 20-30 mass % is the most preferable.

[1-5-2] dispersing agent, dispersing aid

When the colored resin composition of this invention contains a pigment as (A) coloring agent, it is preferable to contain a dispersing agent for the purpose of disperse|distributing a pigment stably. Among the dispersants, the use of a polymer dispersant is preferable because of its excellent dispersion stability over time.

Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant. have. Specific examples of these dispersants include EFKA (registered trademark, manufactured by BASF Corporation), DisperBYK (registered trademark, manufactured by Bikchemi Corporation), Disparon (registered trademark, manufactured by Kusumoto Chemical Corporation), SOLSPERSE (registered trademark, Lubrizol (manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflo (manufactured by Kyoeisha Chemicals), and those described in JP 2013-119568 A are exemplified.

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

As a block copolymer which has a functional group containing a nitrogen atom, the AB block copolymer which consists of A block which has a quaternary ammonium base and/or an amino group in a side chain, and a B block which does not have a quaternary ammonium base and/or an amino group. and/or BAB block copolymers.

Examples of the functional group containing a nitrogen atom include a primary to tertiary amino group and a quaternary ammonium base, and from the viewpoint of dispersibility and storage stability, it is preferable to have a primary to tertiary amino group, and having a tertiary amino group more preferably.

Although the structure of the repeating unit which has a tertiary amino group in the said block copolymer is not specifically limited, From a viewpoint of dispersibility and storage stability, it is preferable that it is a repeating unit represented by the following general formula (1).

[Formula 26]

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

Although carbon number of the alkyl group which may have a substituent in said Formula (1) is not specifically limited, Usually, 1 or more, and 10 or less are preferable, 6 or less are more preferable, and 4 or less are still more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may also be included.

Although carbon number of the aryl group which may have a substituent in said Formula (1) is not specifically limited, Usually, 6 or more, and 16 or less are preferable, 12 or less are more preferable, and 8 or less are still more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di An ethylphenyl group is preferable, and a phenyl group, a methylphenyl group, or an ethylphenyl group is more preferable.

Although carbon number of the aralkyl group which may have a substituent in said Formula (1) is not specifically limited, Usually, it is 7 or more, and 16 or less are preferable, 12 or less are more preferable, and 9 or less are still more preferable. . Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from a viewpoint of dispersibility, storage stability, electrical reliability, and developability, ^{the alkyl group which R<1>} and R<^2> may each independently have a substituent is preferable, and a methyl group or an ethyl group is more preferable.

As a substituent which the alkyl group, aralkyl group, or aryl group in said Formula (1) may have, a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Moreover, in said Formula (1), as ^{a cyclic structure which R<1>} and R<^2> combine with each other and form, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensation formed by condensing two of these ring can be taken. It is preferable that it does not have aromaticity, and, as for a nitrogen-containing heterocyclic ring, if it is a saturated ring, it is more preferable. Specifically, the following (IV) is mentioned, for example.

[Formula 27]

These cyclic structures may further have a substituent.

In the formula (1), as the divalent linking group X, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ¹³ - group, a -COO-R ¹⁴ - group [ However, R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], preferably a -COO-R ¹⁴ - group am.

Moreover, 1 mol% or more is preferable, as for the content rate of the repeating unit represented by the said Formula (1) which occupies in all the repeating units of the said block copolymer, 5 mol% or more is more preferable, 10 mol% or more is still more preferable. and more preferably 15 mol% or more, particularly preferably 20 mol% or more, most preferably 25 mol% or more, more preferably 90 mol% or less, more preferably 70 mol% or less, and 50 mol% or less is more preferable, and 40 mol% or less is especially preferable. When it is in the said range, there exists a tendency for coexistence of dispersion stability and high brightness|luminance to become possible. For example, 1-90 mol% is preferable, as for the content rate of the repeating unit represented by said Formula (1) to all the repeating units of the said block copolymer, 5-90 mol% is more preferable, 10-70 mol% is more preferable, 15-70 mol% is still more preferable, 20-50 mol% is especially preferable, and 25-40 mol% is the most preferable.

Moreover, it is preferable that the said block copolymer has a repeating unit represented by following formula (2) from a viewpoint of improving the compatibility with respect to binder components, such as a solvent, of a dispersing agent, and improving dispersion stability.

[Formula 28]

In the 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 of 1-20.

^{Although carbon number of the alkyl group which may have a substituent in R<11>} of said Formula (2) is not specifically limited, Usually, 1 or more, 2 or more are preferable, 10 or less are preferable, and 6 or less are more preferable, , 4 or less are more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may also be included. A halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group etc. are mentioned as a substituent which you may have, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Moreover, from a viewpoint of compatibility and dispersibility with respect to binder components, such as a solvent, as for n in said Formula (2), 1 or more is preferable, 2 or more are more preferable, Moreover, 10 or less are preferable, and 5 or less are more preferably.

Moreover, 1 mol% or more is preferable, as for the content rate of the repeating unit represented by the said Formula (2) to all the repeating units of the said block copolymer, 2 mol% or more is more preferable, 4 mol% or more is still more preferable. and 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is still more preferable. When it is in the said range, there exists a tendency for compatibility with respect to binder components, such as a solvent, and coexistence of dispersion stability to become possible. For example, 1-30 mol% is preferable, as for the content rate of the repeating unit represented by the said Formula (2) to all the repeating units of the said block copolymer, 2-20 mol% is more preferable, 4-10 mol% is more preferable.

Moreover, it is preferable that the said block copolymer has a repeating unit represented by following formula (3) from a viewpoint of improving the compatibility with respect to binder components, such as a solvent, of a dispersing agent, and improving dispersion stability.

[Formula 29]

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

^{Although carbon number of the alkyl group which may have a substituent in R<8>} of said Formula (3) is not specifically limited, Usually, 1 or more, 1 or more, and 10 or less are preferable, and 6 or less are more preferable. do. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Moreover, either linear or branched type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may also be included.

^{Although carbon number of the aryl group which may have a substituent in R<8>} of said Formula (3) is not specifically limited, Usually, it is 6 or more, and 16 or less are preferable and 12 or less are more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di An ethylphenyl group is preferable, and a phenyl group, a methylphenyl group, or an ethylphenyl group is more preferable.

^{Although carbon number of the aralkyl group which may have a substituent in R<8>} of said Formula (3) is not specifically limited, Usually, it is 7 or more, and 16 or less are preferable, and 12 or less are more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, or a phenylmethylene group.

As a substituent which the alkyl group in R<^8> may have, a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which the aryl group or an aralkyl group may have, a linear alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. Further, the ^{linear alkyl group represented by R 8} includes both linear and branched chain types.

Moreover, 30 mol% or more is preferable, as for the content rate of the repeating unit represented by the said Formula (3) to all the repeating units of the said block copolymer, 40 mol% or more is more preferable, and 50 mol% or more is still more preferable. and 80 mol% or less is preferable, and 70 mol% or less is more preferable. When it is in the said range, there exists a tendency for coexistence of dispersion stability and high brightness|luminance to become possible. For example, 30-80 mol% is preferable, as for the content rate of the repeating unit represented by said Formula (3) to all the repeating units of the said block copolymer, 40-80 mol% is more preferable, 50-70 mol% is more preferable.

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

It is preferable that it is a block copolymer which has an A block which has a repeating unit represented by the said general formula (1) from a viewpoint of improving dispersibility, and a B block which does not have a repeating unit represented by the said general formula (1). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Moreover, it is more preferable that the B block has the repeating unit represented by the said General formula (2), and the repeating unit represented by the said General formula (3).

In addition, repeating units other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such repeating units include repeating units derived from the above-described (meth)acrylic acid ester monomer. have. The content of repeating units other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are not contained in the A block. It is best not to

A repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the formula (3) may be contained in the B block, and examples of such repeating units include styrene, α-methylstyrene, etc. system monomer; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide type monomers, such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine. The content in the B block of repeating units other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) is preferably 0 to 50 mol%, more preferably 0 to 20 mol% However, it is most preferred that such repeating units are not contained in the B block.

Moreover, the lower one is preferable from a dispersible point, and, as for the acid value of the said block copolymer, it is especially preferable that it is 0 mgKOH/g. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.

Further, from the viewpoint of dispersibility and developability, the amine titer of the block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more, and 90 mgKOH/g or more is more preferable, 100 mgKOH/g or more is particularly preferable, 110 mgKOH/g or more is most preferable, and 150 mgKOH/g or less is preferable, 130 mgKOH/g or more The following are more preferable. Here, the amine titer represents the amine titer in terms of the effective solid content, and is a value represented by the amount of the base per 1 g of the solid content of the dispersant and the mass of the equivalent KOH. For example, as for the amine titer of the said block copolymer, 30-150 mgKOH/g is preferable, 50-150 mgKOH/g is more preferable, 70-150 mgKOH/g is still more preferable, 90-130 mgKOH/g is more preferable, 100 to 130 mgKOH/g is particularly preferable, and 110 to 130 mgKOH/g is most preferable.

Moreover, as for the molecular weight of the said block copolymer, the range of 1000-30000 is preferable in polystyrene conversion weight average molecular weight (Hereinafter, it may be referred to as "Mw"). When it is in the said range, dispersion stability becomes favorable, and there exists a tendency for a dry foreign material to become more difficult to generate|occur|produce at the time of application|coating by a slit nozzle method.

Although the said block copolymer can be manufactured by a well-known method, For example, it can manufacture by living-polymerizing the monomer which introduce|transduces each said repeating unit. As the living polymerization method, Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, and 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 Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymers, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), et al. can be employed

When the colored resin composition of this invention contains a dispersing agent, The content rate of a dispersing agent is although it does not specifically limit, In total solid of a colored resin composition, 0.001 mass % or more is preferable, 0.01 mass % or more is more preferable, 0.1 mass % or more % or more is more preferable, 1 mass % or more is particularly preferable, and 25 mass % or less is preferable, 20 mass % or less is more preferable, 15 mass % or less is still more preferable, 10 mass % or less is especially desirable. There exists a tendency for dispersibility and storage stability to improve by using more than the said lower limit, and there exists a tendency for electrical reliability and developability to improve by using below the said upper limit. For example, as for the content rate of a dispersing agent, 0.001-25 mass % is preferable in total solid of a colored resin composition, 0.01-20 mass % is more preferable, 0.1-15 mass % is still more preferable, 1-10 % by mass is particularly preferred.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content of the dispersant is not particularly limited, but with respect to 100 parts by mass of the pigment, preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more, Especially preferably, it is 20 mass parts or more, More preferably, it is 70 mass parts or less, More preferably, 50 mass parts or less is still more preferable. Preferably it is 40 mass parts or less, Especially preferably, it is 30 mass parts or less. By setting it in the said range, it is excellent in dispersion stability, and there exists a tendency for the high-luminance colored resin composition to be obtained. For example, when containing a pigment and a dispersing agent, 0.5-70 mass parts is preferable with respect to 100 mass parts of pigment, as for the content rate of a dispersing agent, 5-70 mass parts is more preferable, 10-50 mass parts is still more preferable, , 15-40 mass parts is more preferable, and 20-30 mass parts is especially preferable.

Moreover, when the colored resin composition of this invention contains a pigment, you may contain the pigment derivative etc. as a dispersing auxiliary agent for the improvement of the dispersibility of a pigment, and the improvement of dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perylene. Derivatives, such as a non-type, a diketopyrrolopyrrole type, and a dioxazine type pigment, are mentioned. As a substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are added directly to the pigment skeleton or an alkyl group, an aryl group, a heterocyclic group, etc. What is bonded through is mentioned, Preferably a sulfonamide group, its quaternary salt, and a sulfonic acid group are mentioned, More preferably, it is a sulfonic acid group. Moreover, two or more of these substituents may be substituted by one pigment frame|skeleton, and the mixture of the compound from which the number of substitutions differs may be sufficient as it. Specific examples of the pigment derivative include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, The sulfonic acid derivative of a diketopyrrolopyrrole pigment, the sulfonic acid derivative of a dioxazine pigment, etc. are mentioned.

[1-5-3] Surfactant

As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but it is preferable to use nonionic surfactants from the viewpoint of low possibility of adversely affecting various properties. do. Although the content rate of surfactant is not specifically limited, Usually 0.001 mass % or more in the total solid of a colored resin composition, Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more, More preferably, it is 0.1 mass % or more. , In addition, it is usually used in the range of 10 mass% or less, preferably 1 mass% or less, more 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 rate of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 1 mass%, with respect to the total solid content of the colored resin composition, 0.05-0.5 mass % is still more preferable, and 0.1-0.3 mass % is still more preferable.

[2] Preparation of colored resin composition

Next, the method of preparing the colored resin composition (it may be called a resist hereafter) which concerns on this invention is demonstrated.

When preparing the thing containing a pigment as a colorant, first, each predetermined amount of a pigment, a solvent, and a dispersing agent are measured, and a dispersion treatment process WHEREIN: A pigment is disperse|distributed and a pigment dispersion liquid is prepared. In this dispersion treatment process, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. can be used. Since the pigment is finely divided by performing this dispersion process, the application|coating characteristic of a colored resin composition improves, and the transmittance|permeability of the pixel in the color filter board|substrate of a product improves.

When dispersing a pigment, as mentioned above, it is preferable to use a dispersing auxiliary agent, a dispersing resin, etc. together suitably.

When dispersing treatment using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature at the time of the dispersion treatment is usually set to 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. In addition, since appropriate time differs according to the composition of a pigment dispersion liquid, the size of the apparatus of a sand grinder, etc., what is necessary is just to adjust dispersion time suitably.

A solvent, an alkali-soluble resin, a photoinitiator, and components other than the above are mixed in some cases with the pigment dispersion liquid obtained by the said dispersion process, and it is set as a uniform dispersion solution. In addition, in each process of a dispersion processing process and mixing, since fine dust may mix, it is preferable to filter the obtained pigment dispersion liquid with a filter etc.

When the colorant does not contain a pigment, a uniform solution can be obtained by mixing a colorant, a solvent, an alkali-soluble resin, a photoinitiator, and, in some cases, components other than the above. It is preferable to filter the obtained solution with a filter etc.

[3] Manufacture of color filter substrate

Next, a color filter according to the present invention will be described.

The color filter which concerns on this invention has the pixel formed using the colored resin composition of this invention. It is preferable that the colored resin composition of this invention is a colored resin composition for pixel formation of a color filter.

[3-1] Transparent substrate (support)

As a transparent substrate of a color filter, if it is transparent and has moderate intensity|strength, the material will not be specifically limited. Examples of the material include a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate, and polysulfone, an epoxy resin, and an unsaturated poly A thermosetting resin sheet, such as an ester resin and poly(meth)acrylic-type resin, or various glass, etc. are mentioned. Among these, from a heat resistant viewpoint, glass or heat resistant resin is preferable.

The transparent substrate and the black matrix formation substrate may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. as necessary for improvement of surface properties such as adhesion. do. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, Moreover, it is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

[3-2] Black Matrix

The color filter which concerns on this invention can be manufactured by forming a black matrix on the transparent substrate mentioned above, and also forming normally red, green, and blue pixel image further. It is preferable to use the said colored resin composition as a coating liquid (Hereinafter, it may abbreviate as "green resist") for green pixel (resist pattern) formation among red, green, and blue pixels. Application, heat drying, image exposure, image development, and heat on the resin black matrix formation surface formed on a transparent substrate using green resist, or on the metal black matrix formation surface formed using a chromium compound or other light-shielding metal material Each process of curing is performed to form a pixel image.

A black matrix is formed on a transparent substrate using a light-shielding metal thin film or the colored resin composition for black matrices. As a light-shielding metal material, chromium compounds, such as metallic chromium, chromium oxide, and chromium nitride, nickel, a tungsten alloy, etc. are used, and what laminated|stacked these in multiple layers may be sufficient.

These metal light-shielding films are generally formed by sputtering, and after a desired pattern is formed on a film with a positive photoresist, for chromium, an etching solution in which cerium ammonium nitrate, perchloric acid and/or nitric acid is mixed is used. And, about other materials, it is etched using the etching solution according to the material, and finally, a black matrix can be formed by peeling a positive photoresist with a special release agent.

In this case, first, a thin film of these metals or metal/metal oxide is formed on a transparent substrate by vapor deposition or sputtering method or the like. Next, after forming a coating film of a colored resin composition on this thin film, using the photomask which has repeating patterns, such as stripe, mosaic, and a triangle, the coating film is exposed and developed, and a resist image is formed. Then, an etching process can be given to this coating film, and a black matrix can be formed.

When using the photosensitive colored resin composition for black matrices, a black matrix is formed using the colored resin composition containing a black coloring agent. For example, by mixing single or multiple black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed by carrying out similarly to the method of forming the following red, green, and blue pixel images using the colored resin composition containing a black coloring agent.

[3-3] Formation of pixels

On the transparent substrate on which the black matrix was formed, the colored resin composition of one color among red, green, and blue is apply|coated, and after drying, a photomask is superposed|stacked on the coating film, and image exposure and development are passed through this photomask. , to form a pixel image by thermosetting or photocuring, if necessary. A color filter image can be formed by performing this operation with respect to the colored resin composition of three colors of red, green, and blue, respectively.

Application|coating of the colored resin composition for color filters can be performed by the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, the spray coat method, etc. Among them, according to the die coating method, the amount of the coating liquid used is significantly reduced, and there is no effect of mist adhering when the spin coating method is used, and furthermore, it is preferable from a general viewpoint, such as suppressing the generation of foreign substances. .

When the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell-forming process may become difficult, while when it is too small, it becomes difficult to raise the pigment concentration, and desired color expression becomes impossible. have. The thickness of the coating film is a 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 is in the range of 5 μm or less.

[3-4] Drying of the coating film

It is preferable that drying of the coating film after apply|coating a colored resin composition to a board|substrate is based on the drying method using a hotplate, IR oven, and a convection oven. Usually, it is dried by heating again after preliminary drying. The conditions of preliminary drying can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, etc. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer to be used, and the like. Specifically, the drying temperature is usually 40° C. or higher, preferably 50° C. or higher, and usually 80° C. or lower, It is preferably in the range of 70°C or less, and the drying time is usually in the range of 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 predrying temperature, specifically, usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, particularly Preferably, it is in the range of 130 degrees C or less. Moreover, although drying time changes with heating temperature, it is normally 10 second or more, especially 15 second or more, Moreover, it is usually 10 minutes or less, It is preferable to set it as the range of 5 minutes especially. Although the adhesiveness to a transparent substrate improves so that a drying temperature is high, when too high, alkali-soluble resin may decompose|disassemble, induce thermal polymerization, and generate|occur|produce poor image development. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a pressure reduction chamber without raising temperature.

[3-5] Exposure process

Image exposure superimposes a negative matrix pattern on the coating film of a colored resin composition, and irradiates and performs the light source of an ultraviolet-ray or visible light through this mask pattern. At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer by oxygen, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer. The light source used for the said image exposure is not specifically limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers. and laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

[3-6] Development process

After performing image exposure with the said light source with respect to the coating film using the colored resin composition which concerns on this invention, the color filter which concerns on this invention develops using the aqueous solution containing an organic solvent or surfactant and an alkaline compound By carrying out, an image can be formed on the substrate and manufactured. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate. Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or organic alkaline compounds such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. A mixture of 2 or more types may be sufficient as these alkaline compounds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; and anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. An organic solvent can be used together with aqueous solution.

Although there is no restriction|limiting in particular in the conditions of a developing process, The developing temperature is normally 10 degreeC or more, especially 15 degreeC or more, further 20 degreeC or more, and, and also usually 50 degrees C or less, especially 45 degrees C or less, further 40 degrees C or less range is preferred. The developing method can be based on any method, such as the immersion developing method, the spray developing method, the brush developing method, and the ultrasonic developing method.

[3-7] Heat curing treatment

A thermosetting process is given to the color filter after image development. At this time, the thermosetting treatment conditions are selected from the range where the temperature is usually 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 250°C or lower, and the time is 5 minutes or longer, It is selected from the range of 60 minutes or less. Through these series of steps, the formation of a patterned image of one color is finished. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. In addition, the order of the patterning of four colors is not limited to the above-mentioned order.

[3-8] Formation of transparent electrode

The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of parts such as a color display and liquid crystal display device. In order to improve surface smoothness and durability, if necessary , a top coat layer such as polyamide or polyimide may be formed on the image. Moreover, in some uses, such as a planar alignment type drive system (IPS mode), a transparent electrode may not be formed.

[4] Image display device (panel)

Next, the image display apparatus of this invention is demonstrated. The image display apparatus of this invention has the above-mentioned color filter. Hereinafter, as an image display apparatus, a liquid crystal display device and an organic electroluminescent display are demonstrated in detail.

[4-1] Liquid crystal display device

The manufacturing method of the liquid crystal display device which concerns on this invention is demonstrated. The liquid crystal display device according to the present invention generally forms an alignment film on the color filter according to the present invention, disperses a spacer on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, and to the formed liquid crystal cell Liquid crystal is injected, and the connection to the counter electrode is completed. The alignment film is preferably a resin film such as polyimide. A gravure printing method and/or a flexographic printing method are normally employ|adopted for formation of an alignment film, and the thickness of an alignment film is set to several 10 nm. After hardening of an alignment film by thermal baking, it surface-treats by irradiation of an ultraviolet-ray or treatment with a rubbing cloth, and is processed to the surface state which can adjust the inclination of a liquid crystal.

As the spacer, a spacer having a size corresponding to the gap (gap) with the opposing substrate is used, and the spacer is preferably 2 to 8 µm. On the color filter substrate, a photo-spacer PS of a transparent resin film may be formed by a photolithography method, and this may be utilized instead of a spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

Although the gap of bonding with a counter board|substrate changes with the use of a liquid crystal display device, it is normally selected from the range of 2 micrometers or more and 8 micrometers or less. After bonding with a counter board|substrate, parts other than a liquid crystal injection port are sealed with sealing materials, such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.

After the liquid crystal cell in which the periphery was sealed is cut|disconnected by panel unit, it is made into pressure reduction in a vacuum chamber, and after immersing the said liquid crystal injection port in a liquid crystal, the inside of a chamber is leaked, and a liquid crystal is inject|poured into a liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1 × 10 ^-2 Pa or more, preferably 1 × 10 ^-3 Pa or more, and usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa or less is the range of Moreover, it is preferable to warm a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30 degreeC or more normally, Preferably it is 50 degreeC or more, and also usually 100 degrees C or less, Preferably it is the range of 90 degrees C or less.

The heating and maintenance at the time of reduced pressure is normally in the range of 10 minutes or more and 60 minutes or less, and is immersed in the liquid crystal after that. A liquid crystal display device (panel) is completed by the liquid crystal cell which inject|poured liquid crystal hardening and sealing a liquid crystal injection port UV hardening resin.

There is no restriction|limiting in particular in the kind of liquid crystal, As a conventionally known liquid crystal, such as an aromatic type, an aliphatic type, and a polycyclic compound, any of a lyotropic liquid crystal, a thermotropic liquid crystal, etc. may be sufficient. As a thermotropic liquid crystal, although a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, etc. are known, any may be sufficient.

[4-2] Organic EL display device

When manufacturing the organic electroluminescent display apparatus which has a color filter of this invention, as shown, for example in FIG. 1, the blue color in which the pixel 20 was formed with the colored resin composition of this invention on the transparent support substrate 10. A multicolor organic EL element is manufactured by laminating|stacking the organic light emitting body 500 with the organic protective layer 30 and the inorganic oxide film 40 interposed on a filter.

As a lamination method of the organic light emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter. ), a method of sequentially forming the organic light emitting body 500 formed on a separate substrate on the inorganic oxide film 40, and the like. The organic EL element 100 manufactured in this way is applicable to both an organic EL display device of a passive drive system and an organic EL display device of an active drive system.

Example

Next, although an Example and comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following example, unless the summary is exceeded.

<Phthalocyanine compound A>

The phthalocyanine compound A synthesized based on Example 30 of Unexamined-Japanese-Patent No. 05-345861 and having the following chemical structures was used.

[Formula 30]

Et in the formula represents ethyl.

<Phthalocyanine compound B>

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 are mixed and heated to 70°C It was heated and stirred as it was for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was filtered and concentrated. The obtained residue was recrystallized from acetonitrile to obtain 4.70 g of a mixture of the intermediate A and the intermediate B (yield 59%, purity 77.9%, intermediate A/intermediate B = 73/23). In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 31]

3.00 g (7.15 mmol) of a mixture of the intermediate A and the intermediate B, 0.69 g (2.14 mmol) of zinc iodide, and 7.2 g of benzonitrile were mixed, and reacted at 170°C for 6.5 hours. After completion of the reaction, the reaction solution was cooled and poured into 20 ml of methanol. After filtering the produced|generated solid content, the phthalocyanine compound B of 2.62 g (yield 84%) was obtained by washing|cleaning with methanol and water and drying under reduced pressure at 50 degreeC.

[Formula 32]

1 mg of phthalocyanine compound B was dissolved in 100 ml of DMSO (dimethyl sulfoxide), and the visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a quartz cell having a width of 1 cm. As a result of the measurement, the maximum absorption wavelength was 651.0 nm, and the molar extinction coefficient (ε) was 4.08 × 10 ⁵ .

<Phthalocyanine compound C>

4.00 g (20 mmol) of tetrafluorophthalonitrile, 2.90 g (5.0 mmol) of potassium fluoride, and 10 ml of acetone were mixed and cooled on ice, followed by 6.65 g (40 mmol) of ethyl p-hydroxybenzoate in acetone ( 30 ml) solution was added, and the mixture was stirred as it was for 5 hours. The reaction liquid was filtered and concentrated after completion|finish of reaction, and the 6.20g (yield 63%, purity 97.6%) intermediate C was obtained by adding ethanol 60ml, and filtering and drying the precipitate which precipitated. In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 33]

Et in the formula represents ethyl.

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 were mixed, and it was made to react at 160 degreeC for 7 hours. After completion of the reaction, the reaction solution was cooled and poured into 40 ml of methanol. After filtration of the produced|generated solid content, it wash|cleaned with methanol and dried under reduced pressure at 50 degreeC. 1.13 g (yield 40%) of phthalocyanine compound C was obtained by purifying the obtained solid by medium-pressure separation-collection liquid chromatography (the developing solvent is a mixed solvent of chloroform and methanol, the gradient of 100:0-92:8 (volume ratio)).

[Formula 34]

Et in the formula represents ethyl.

1 mg of phthalocyanine compound C was dissolved in 100 ml of THF (tetrahydrofuran), and the visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Co., Ltd.) using a quartz cell having a width of 1 cm. As a result of the measurement, the maximum absorption wavelength was 695.0 nm, and the molar extinction coefficient (ε) was 1.11 × 10 ⁵ .

<Phthalocyanine compound D>

5.00 g (25.0 mmol) of tetrafluorophthalonitrile, 6.90 g (50.0 mmol) of potassium carbonate, and 50 ml of acetonitrile were mixed. At room temperature, a solution of 8.21 g (50.0 mmol) of 4-t-amylphenol in acetonitrile (30 ml) was added and stirred for 5 hours, followed by heating at 80° C. and further stirring for 2 hours. After cooling the reaction liquid, it filtered, acetonitrile was distilled off from the filtrate with a rotary evaporator, ethanol was added, and recrystallization was performed. The obtained solid was filtered and the intermediate body D of 7.20g (yield 59%, purity 91.4%) was obtained by vacuum-drying. In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 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)

4.95 g (10.5 mmol) of the intermediate D, 1.00 g (3.14 mmol) of zinc iodide, and 10 g of benzonitrile were mixed and reacted at 160°C for 6 hours. After completion of the reaction, the reaction solution was cooled and poured into 100 ml of methanol. After filtering the produced|generated solid content, the phthalocyanine compound D of 4.46 g (yield 84%) was obtained by washing|cleaning with methanol and water, and drying under reduced pressure at 50 degreeC.

[Formula 36]

1 mg of phthalocyanine compound D was dissolved in 100 ml of DMSO, and the visible absorption spectrum was measured with an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a quartz cell having a width of 1 cm. The absorption wavelength was 701.0 nm, and the molar extinction coefficient (ε) was 1.248×10 ⁵ .

<Phthalocyanine compound E>

Tetrafluorophthalonitrile 5.00 g (25.0 mmol), potassium carbonate 6.90 g (50.0 mmol), and acetone 85 ml were mixed and cooled on ice. A solution of 7.60 g (50.0 mmol) of methyl p-hydroxybenzoate in acetone (30 mL) was added at 2 to 4°C, and the mixture was stirred as it was for 6 hours. The reaction liquid was filtered, acetone was distilled off from the filtrate with a rotary evaporator, ethanol was added, and recrystallization was performed. The obtained solid was filtered and the intermediate body E of 7.20g (62% of yield, 91.5% of purity) was obtained by vacuum-drying. In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 37]

Me in the formula represents methyl.

¹ H-NMR (CDCl ₃ )

δ: 3.91 (s, 6H), 6.80 (d, 4H), 7.97 (d, 4H)

5.00 g (10.8 mmol) of the intermediate E, 1.03 g (3.23 mmol) of zinc iodide, and 12 ml of benzonitrile were mixed and reacted at 170°C for 9 hours. After completion of the reaction, the reaction solution was cooled and poured into 20 ml of methanol. After filtering the produced|generated solid content, the phthalocyanine compound E of 4.46 g (yield 85%) was obtained by washing|cleaning with methanol and water and drying under reduced pressure at 50 degreeC.

[Formula 38]

Me in the formula represents methyl.

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 absorption spectrum was measured with an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a quartz cell having a width of 1 cm. The absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.190×10 ⁵ .

<Phthalocyanine compound F>

3.02 g (15.0 mmol) of tetrafluorophthalonitrile, 4.14 g (30.0 mmol) of potassium carbonate, and 50 ml of acetone were mixed and ice-cooled. A solution of 5.40 g (30.0 mmol) of p-hydroxybenzoic acid n-propyl in acetone (30 ml) was added at 2 to 4°C, and the mixture was stirred as it was for 5 hours. The reaction liquid was filtered, acetone was distilled off from the filtrate with a rotary evaporator, ethanol was added, and recrystallization was performed. The obtained solid was filtered and the intermediate body F of 4.0g (51% of yield, 95.9% of purity) was obtained by vacuum-drying. In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 39]

n-Pr in the formula represents n-propyl.

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)

1.00 g (2.15 mmol) of the intermediate F, 0.21 g (0.65 mmol) of zinc iodide, and 2.4 ml of benzonitrile were mixed, and it was made to react at 170 degreeC for 13 hours. After completion of the reaction, the reaction solution was cooled and poured into 20 ml of methanol. After filtering the produced|generated solid content, the phthalocyanine compound F of 0.33 g (yield 29%) was obtained by washing|cleaning with methanol and water and drying under reduced pressure at 50 degreeC.

[Formula 40]

n-Pr in the formula represents n-propyl.

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 (dimethyl sulfoxide), and the visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), using a quartz cell having a width of 1 cm. As a result of the measurement, the maximum absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.202 × 10 ⁵ .

<Phthalocyanine compound G>

After mixing 2.00 g (10 mmol) of tetrafluorophthalonitrile, 1.45 g (2.5 mmol) of potassium fluoride, and 5 ml of acetone, and cooling on ice, 3.78 g (21) of methyl 3-(4-hydroxyphenyl)propanoate mmol) in acetone (5 ml) was added, and the mixture was stirred as it was for 5 hours. After completion of the reaction, the reaction solution was extracted with chloroform-water, the organic layer was extracted with saturated brine, and the concentrated product was separated by medium pressure liquid chromatography (the developing solvent is a mixed solvent of hexane and ethyl acetate, 94: 6 to 73: 27 (volume ratio) ) to obtain an intermediate G of 3.00 g (yield 58%, purity 97.8%). In addition, this purity is the value of the area% computed from the result of high performance liquid chromatography analysis.

[Formula 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)

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

[Formula 42]

1 mg of phthalocyanine compound G was dissolved in 100 ml of DMSO, and the visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a quartz cell having a width of 1 cm. The absorption wavelength was 700.0 nm, and the molar extinction coefficient (ε) was 2.278 × 10 ⁵ .

<Dispersant A: Dispersant "BYK-LPN6919" manufactured by Bikchemi>

A methacrylic acid-based AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. It has repeating units of the following formulas (2a) and (3a), and does not have a repeating unit of the following formulas (1a). The amine value is 120 mgKOH/g and the acid value is 1 mgKOH/g or less.

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

[Formula 43]

<Preparation of green pigment dispersion liquid 1>

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

<Preparation of green pigment dispersion 2>

C.I. 11.0 parts by mass of Pigment Green 59, 1.6 parts by mass of dispersant A in terms of solid content, 3.3 parts by mass of alkali-soluble resin A described later in terms of solid content, and 84.1 parts by mass of propylene glycol monomethyl ether acetate as a solvent (derived from dispersant A) The solvent and the solvent derived from alkali-soluble resin A are also included), 225 mass parts of zirconia beads with a diameter of 0.5 mm were filled in a stainless steel container, and it disperse|distributed with a paint shaker for 6 hours. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare a green pigment dispersion 2 .

<Alkali-soluble resin A>

It stirred while purging with nitrogen 145 mass parts of propylene glycol monomethyl ether acetate, and it heated up at 120 degreeC. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are added dropwise thereto, and further, at 120°C for 2 hours. Stirring was continued. Next, the inside of the reaction container was changed to air substitution, 0.7 mass parts of trisdimethylaminomethylphenol and 0.12 mass parts of hydroquinone were thrown into 27 mass parts of acrylic acid, and reaction was continued at 120 degreeC for 6 hours. Then, 52 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass parts of triethylamine were added, and it was made to react at 120 degreeC for 3.5 hours. It cooled to room temperature, and the weight average molecular weight Mw of polystyrene conversion measured by GPC obtained 8000, and alkali-soluble resin A whose acid value is 80 mgKOH/g.

<Photopolymerizable monomer A>

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

<Photopolymerizable monomer B>

Modified succinic anhydride of a reaction product of dipentaerythritol and acrylic acid

<Photoinitiator A>

Oxime ester compound having the following chemical structure

(4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate methyl)

[Formula 44]

Me in the formula represents methyl.

<Surfactant A>

Megapac (registered trademark) F-559 (manufactured by DIC)

<Preparation of colored resin composition>

Each component was mixed so that it might become the ratio in the solid content of Table 1 and 2, and the ratio in a solvent, and each colored resin composition whose content rate of total solid is 15 mass % was prepared. The "ratio in solid content" means the ratio (mass %) in the total solid of the solid content of various components. In addition, the "ratio in a solvent" means the ratio (mass %) of various solvents in the total solvent, and the solvent derived from alkali-soluble resin and a pigment dispersion liquid is also contained in the quantity of various solvents.

In addition, in Comparative Examples 7 and 8, C.I. Pigment Green 58 and C.I. The content rate of pigment green 59 was made to be 40.0 mass % in total solid.

In addition, the detail of the various solvents of Table 1 and Table 2 is as having described in Table 3. The boiling point (degreeC) in a table|surface is a value in 1013.25 hPa.

<Evaluation of alkali development time and residue on a glass substrate>

On a glass substrate (manufactured by AGC, AN100) having a width of 50 mm and a thickness of 0.7 mm, the colored resin composition was applied with a spin coater so that the film thickness after drying was 2.3 μm, followed by drying at 80° C. for 3 minutes An evaluation board was obtained. With respect to the evaluation board|substrate, it developed using 23 degreeC 0.4 mass % potassium hydroxide aqueous solution, and time (dissolution time) until a coating film melt|dissolved and a board|substrate surface was exposed was measured.

Then, with respect to the evaluation substrate obtained by the same procedure, using a 23 degreeC 0.4 mass % potassium hydroxide aqueous solution, developing treatment was performed for twice the dissolution time, and spray water washing treatment at a water pressure of 1 kg/cm 2 for 10 seconds was carried out to prepare a residue evaluation substrate 1 . Moreover, the residue evaluation board|substrate 2 was manufactured by the same procedure except having changed the time of the developing process to 60 second.

About the residue evaluation board|substrate 1, visual observation is performed, and the area (A) of a part in which a residue is not visible and the area (B) of a part in which a residue is visible on a 50 mm horizontal and vertical glass substrate are measured, and residual Water generation area ratio (%)=(B)/{(A)+(B)}x100 evaluated. A result is shown in Table 4.

Next, also about the residue evaluation board|substrate 2, visual observation was performed, it carried out similarly to the residue evaluation board|substrate 1, and evaluated the residue generation area ratio (%), As a result, Example 1 was 1%, Example 2 0%, Example 3 1%, Example 4 0%, Example 5 0%, Example 6 0%, Example 7 0%, Example 8 0%, Example 9 0%, Example 10 0%, Example 11 1%, Example 12 0%, Example 13 0%, Example 14 0%, Example 15 1%, Example 16 1% was %.

<Evaluation of color characteristics>

Example 1, Example 4, Example 8, Example 13, Example 14, Example 15, Example 16, Comparison on a glass substrate of 50 mm in width and 0.7 mm in thickness (manufactured by AGC, AN100) After apply|coating the colored resin composition of Example 5, Comparative Example 6, Comparative Example 7, and Comparative Example 8 with a spin coater, it was dried at 80 degreeC for 3 minutes. Then, the whole surface exposure process was implemented with the exposure amount of 40 mJ/cm<2> with a 2 kW high-pressure mercury-vapor lamp. Then, it developed using 23 degreeC 0.4 mass % potassium hydroxide aqueous solution. Then, the spray water washing process was performed for 10 second by the water pressure of 3 kg/cm<2>, and the colored resin composition application board|substrate was manufactured. Then, the thermosetting process for 30 minutes was performed at 230 degreeC, and the colored board|substrate whose film thickness is 2.0 micrometers was manufactured. About the obtained colored board|substrate, the C light source measured the transmission spectrum with the spectrophotometer U-3310 by Hitachi Corporation, and the chromaticity (sx, sy) and the brightness|luminance were computed. Example 1 has chromaticity sx=0.220, sy=0.460, luminance LY 58.7, Example 4 has chromaticity sx=0.220, sy=0.460, luminance LY 58.8, Example 8 has chromaticity sx = 0.220, sy = 0.460, and luminance LY was 58.7. In Example 13, chromaticity is sx=0.249, sy=0.355, luminance LY is 65.4, Example 14 has chromaticity sx=0.266, sy=0.341, luminance LY is 79.9, and Example 15 has chromaticity sx = 0.224, sy = 0.459, luminance LY was 58.3, and in Example 16, chromaticity was sx = 0.228, sy = 0.466, and luminance LY was 57.3. Comparative Example 5 had chromaticity sx=0.219 and sy=0.425, luminance LY was 50.0, Comparative Example 6 had chromaticity sx=0.297, sy=0.428, luminance LY was 47.3, and Comparative Example 7 had chromaticity sx=0.238, sy=0.556, and luminance LY of 51.6. In Comparative Example 8, chromaticity was sx=0.172, sy=0.483, and luminance LY was 38.5.

Moreover, when the surface of the colored substrates of Examples 1-12 manufactured by the same procedure was visually observed, a foreign material was not observed.

As is clear from Table 4, the colored resin composition containing the phthalocyanine compound (1) WHEREIN: When the high boiling point solvent of 160 degreeC or more boiling point is not contained like Comparative Examples 1-4, a large amount of residues on a glass substrate This occurred.

Since the phthalocyanine compound (1) has high solubility in a solvent and does not require a dispersion treatment step, there are hardly any dispersants or alkali-soluble resins around the phthalocyanine compound (1). In the colored resin composition, the phthalocyanine compound ( It is thought that the affinity of 1) and alkali-soluble resin is weak. In particular, in the phthalocyanine compound (1), molecules easily associate with each other by π-π interaction between phthalocyanine rings and π-π interaction between groups represented by the formula (2), and a fluorine atom with a small atomic radius By having , the packing of molecules becomes denser, the affinity with the alkali-soluble resin is weak, and the alkali developer becomes difficult to permeate into the phthalocyanine compound (1) during alkali development, so the alkali solubility decreases and remains on the glass substrate It is thought that water became easy to remain|survive.

On the other hand, like Examples 1-16, the colored resin composition containing a phthalocyanine compound (1) WHEREIN: When a high boiling point solvent of 160 degreeC or more of boiling points is contained, a residue hardly generate|occur|produces on a glass substrate, especially Like Examples 6, 8, 9 and 10, when the boiling point of a solvent was high, or when the content rate of the solvent of 160 degreeC or more of boiling points was high, the residue on a glass substrate did not generate|occur|produce at all.

By containing a high-boiling solvent with a boiling point of 160 ° C. or higher, drying of the coating film during the alkali developing step is suppressed, resulting in a sufficiently wet state, the alkali developer penetrates sufficiently into the coating film, and the neutralization reaction is accelerated, and the phthalocyanine compound ( 1) It is also fully melt|dissolved in alkali developing solution, and it is thought that the residue derived from a colored resin composition became difficult to generate|occur|produce on a glass substrate.

On the other hand, from the comparison of Comparative Example 1 and Comparative Examples 5 and 6 in Table 4, the phthalocyanine compounds B and C which do not satisfy the above formula (1) have a larger value of the residue area than the phthalocyanine compound (1). The phthalocyanine compound B has a chlorine atom instead of a fluorine atom, and by it the polarity of a phthalocyanine compound becomes low, it is thought that it is because the solubility with respect to a highly polar developing solution (aqueous alkali aqueous solution) became low. Moreover, as for the phthalocyanine compound C, the central metal is copper, the ionization tendency of a phthalocyanine compound becomes low by it, and it is thought that it is because the solubility with respect to a developing solution (aqueous alkali solution) became low.

Moreover, as mentioned above, compared with Comparative Example 5 and Comparative Example 6, the brightness|luminance in Example 1 is high. This is because the phthalocyanine compound (1) contained in Example 1 has a fluorine atom, so that the polarity of the phthalocyanine compound increases, so that solubility in a solvent in the colored resin composition increases, and aggregation of phthalocyanine compounds is suppressed. It is thought that this is because the crystal form is optimized because the central metal is zinc.

In addition, as in Comparative Examples 7 and 8, in the colored resin composition containing a green pigment instead of the phthalocyanine compound (1), there are many dispersing resins and dispersing agents in the vicinity of the green pigment in the colored resin composition, It is thought that the affinity becomes strong, and the alkali solubility of a green pigment is high by it, and it became difficult for a residue to remain|survive on a glass substrate in spite of not containing the high boiling point solvent of 160 degreeC or more boiling point.

10: transparent support substrate
20: pixel
30: organic protective layer
40: inorganic oxide film
50: transparent anode
51: hole injection layer
52: hole transport layer
53: light emitting layer
54: electron injection layer
55: cathode
100: organic EL device
500: organic light emitting material

Claims (7)

A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
Said (A) coloring agent contains the phthalocyanine compound which has a chemical structure represented by following General formula (1),
Said (B) solvent contains the high boiling point solvent whose boiling point in 1013.25 hPa is 160 degreeC or more, The colored resin composition characterized by the above-mentioned.

(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). However, ^{at least one of A 1} to A ¹⁶ represents a fluorine atom. and, ^{at least one 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) may have an arbitrary substituent. * represents a bond.) The method of claim 1,
The colored resin composition whose content rate of the said (B) solvent in a colored resin composition is 50 mass % or more. 3. The method according to claim 1 or 2,
The colored resin composition in which the content rate of the said high boiling point solvent in the said (B) solvent is 0.5 mass % or more. 4. The method according to any one of claims 1 to 3,
The colored resin composition whose content rate of the said phthalocyanine compound is 5 mass % or more in total solid. 5. The method according to any one of claims 1 to 4,
The colored resin composition in which the said (D) photoinitiator contains an oxime ester type photoinitiator. The color filter which has the pixel manufactured using the colored resin composition in any one of Claims 1-5. The image display apparatus which has the color filter of Claim 6.

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