JP2016191745A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition capable of maintaining high yield and providing a high-definition color filter with preferable luminosity.SOLUTION: There is provided a colored photosensitive resin composition comprising: a coloring agent (A); a resin (B); a polymerizable compound (C); and a polymerization initiator (D), in which the coloring agent (A) is a polyhalogenated zinc phthalocyanine (a1) which comprises less than 13 pieces of bromine in average in one molecule, and comprises a wavelength of 500-520 nm at which transmittance of a spectral transmittance spectrum in 380-780 nm becomes maximum, and the polymerization initiator (D) is an O-acyloxime compound.SELECTED DRAWING: None

Description

  The present invention relates to a green colored photosensitive resin composition, and in particular, may be referred to as polyhalogenated zinc phthalocyanine (hereinafter referred to as polyhalogenated zinc phthalocyanine (a1)) having a specific configuration as a colorant (A). And a colored photosensitive resin composition containing an O-acyl oxime compound as a polymerization initiator (D).

  In recent years, display displays have been developed to widen the color gamut that can be displayed, and as part of this, color filters having a darker color are required. In order to satisfy the requirement, there is a method of increasing the color material concentration in the color filter. However, when the color material concentration increases, the performance as a colored photosensitive resin composition deteriorates, such as the deterioration of the pattern shape. It is not preferable. In addition, in order to have the desired color characteristics, it is necessary to produce a color filter with a thick film. However, when applied to a liquid crystal display device, a color mixture of light with adjacent pixels occurs. Membrane formation is also not preferable.

  In Patent Document 1, C.I. I. Pigment Green G58 and C.I. I. Pigment blue 15: 3 and C.I. I. A green photosensitive resin composition containing a colorant containing CI Pigment Yellow 150, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent is described.

JP 2012-247539 A

  As a result of studies by the present inventors, in the step of developing a color resist pattern substrate by immersing the substrate in a developing solution and developing it, the colored photosensitive resin composition of the unexposed portion applied to the substrate is glass. The problem of peeling from the substrate and adhesion of the peeled pieces to other pixels was recognized. If the peeled piece adheres to other pixels, a normal color filter cannot be obtained, and the yield is extremely reduced, which is a problem. Also in the exposed area, the exposed area is peeled off or dissolved in the development process, causing a problem that the pattern shape does not remain.

  Therefore, the present invention has been made as an object to provide a colored photosensitive resin composition capable of providing a high-definition color filter having good brightness while maintaining a high yield.

  As a result of intensive studies to solve the above problems, the present inventors solved the above problems by combining a polyhalogenated zinc phthalocyanine (a1) and an O-acyloxime compound in a colored photosensitive resin composition. The present inventors have found that a possible colored photosensitive resin composition can be obtained and completed the present invention.

That is, the colored photosensitive resin composition according to the present invention has a gist in the following points.
[1] Including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As the colorant (A), a polyhalogenated zinc phthalocyanine containing less than 13 bromine on average in one molecule and having a wavelength of 500 to 520 nm at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum. Including (a1),
A colored photosensitive resin composition comprising an O-acyloxime compound as the polymerization initiator (D).
[2] The colored photosensitive resin composition according to [1], further including a pigment and / or a dye as the second colorant.
[3] The colored photosensitive composition according to [2], comprising at least one selected from the group consisting of a green pigment, a yellow pigment, and a blue pigment other than the polyhalogenated zinc phthalocyanine (a1) as a second colorant. Resin composition.
[4] Any one of [1] to [3], which includes at least one selected from the group consisting of the following formulas (d1), (d2), and (d3) as the O-acyloxime compound. The colored photosensitive resin composition described in 1.

[In the formulas (d1) to (d3),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which may have a substituent; The contained methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms; The methylene group (—CH ₂ —) contained in the aromatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—. ]
[5] Any one of [1] to [4], further including at least one selected from the group consisting of alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, and thiol compounds (T). The colored photosensitive resin composition described in 1.
[6] Any one of [1] to [5], further comprising at least one leveling agent (F) selected from silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. 2. The colored photosensitive resin composition according to item 1.
[7] A coating film formed using the colored photosensitive resin composition according to any one of [1] to [6].
[8] A color filter formed using the colored photosensitive resin composition according to any one of [1] to [6].
[9] A display device including the color filter according to [8].

  According to the present invention, a high-definition color having good brightness while maintaining a high yield by using a combination of a polyhalogenated zinc phthalocyanine (a1) and an oxime compound in a colored photosensitive resin composition. A colored photosensitive resin composition capable of providing a filter is obtained.

The colored photosensitive resin composition according to the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is a polyhalogenated compound. It contains zinc phthalocyanine (a1) and contains an O-acyloxime compound as the polymerization initiator (D).
The colored photosensitive resin composition according to the present invention preferably further contains a solvent (E).
The colored photosensitive resin composition according to the present invention preferably further contains a thiol compound (T).
Moreover, it is preferable that the colored photosensitive resin composition which concerns on this invention contains a leveling agent (F) further.
In addition, unless otherwise indicated, the compound illustrated as each component in this specification can be used individually or in combination of multiple types.

<Colorant (A)>
The colored photosensitive resin composition according to the present invention contains, as a colorant (A), an average of less than 13 bromine atoms in one molecule and a wavelength at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximized. The polyhalogenated zinc phthalocyanine (a1) having a thickness of 500 to 520 nm is contained as an essential component. The polyhalogenated zinc phthalocyanine (a1) is a known C.I. I. It can be produced by changing the number of bromine added to CI Pigment Green 58, for example, by the method described in Japanese Patent No. 4368157.

  Polyhalogenated zinc phthalocyanine (a1) is a known C.I. I. Pigment green 7, C.I. I. It can be distinguished from the pigment green 58 in terms of the number of bromine in the molecule and the wavelength at which the transmittance is maximum. C. I. Pigment Green 7 is chlorinated copper phthalocyanine, does not have bromine in the molecule, and C.I. I. Pigment Green 58 molecule contains an average of 14 bromines. When a coating film having a maximum transmittance spectrum of 90% was prepared, C.I. I. Pigment Green 58 exhibits the maximum transmittance in the range of more than 520 nm to 530 nm and the transmittance of 50% in the range of 570 to 575 nm. On the other hand, the polyhalogenated zinc phthalocyanine (a1) essential in the present invention exhibits the maximum transmittance in the range of 500 to 520 nm and the transmittance of 50% in the range of 560 to 565 nm.

  The number of bromine contained in one molecule of the polyhalogenated zinc phthalocyanine (a1) is preferably 12 or less on average, and more preferably 11 or less. Although a minimum is not limited, it is 1 or more, 3 or more are preferable, 6 or more are more preferable, and 8 or more are still more preferable.

  In the present specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored photosensitive resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

  If necessary, the polyhalogenated zinc phthalocyanine (a1) can be prepared by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid, etc. An atomization process by an atomization method or the like, a cleaning process with an organic solvent or water for removing impurities, a removal process by an ion exchange method of an ionic impurity, or the like may be performed.

  The polyhalogenated zinc phthalocyanine (a1) is preferably used in the form of a dispersion uniformly dispersed in a solvent, and the dispersion is prepared by mixing the polyhalogenated zinc phthalocyanine (a1) in the solvent. Can be obtained. You may mix a dispersing agent as needed.

The dispersant may be any of cationic, anionic, nonionic, and amphoteric dispersants, and examples thereof include polyester-based, polyamine-based, and acrylic-based dispersants.
These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF Corp.), Ajispur (Ajinomoto Fine Techno) (Manufactured by Co., Ltd.), Disperbyk (manufactured by Big Chemie) and the like.
When the dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in which the pigment is uniformly dispersed in the solvent tends to be obtained.

It does not specifically limit as a solvent, The solvent similar to the solvent (E) in the colored photosensitive resin composition of this invention is mentioned. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, More preferred are 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.
Although the usage-amount of a solvent is not specifically limited, It is good to use a solvent so that solid content concentration in a pigment dispersion liquid can be adjusted to 3-20 mass%, More preferably, it can be adjusted to 5-18 mass%.

  In addition, as a coloring agent (A), you may contain the pigment and / or dye which are 2nd coloring agents other than a polyhalogenated zinc phthalocyanine (a1).

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Examples of organic pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments other than polyhalogenated zinc phthalocyanine (a1) such as CI Pigment Green 7, 36, 58;
Is mentioned.

Among them, the pigment preferably contains at least one selected from the group consisting of a green pigment other than polyhalogenated zinc phthalocyanine (a1), a yellow pigment, and a blue pigment, and the blue pigment is included together with the yellow pigment. preferable.
Green pigments, yellow pigments and blue pigments other than polyhalogenated zinc phthalocyanine (a1) are C.I. I. Pigment yellow 138, 139, 150, 185, C.I. I. Pigment blue 15: 3, 15: 6, C.I. I. Pigment Green 7, 36, and 58 are preferable. Two or more of these pigments may be used.

  Pigments other than the polyhalogenated zinc phthalocyanine (a1) may be a rosin treatment, a surface treatment using a pigment derivative or a pigment dispersant into which an acidic group or a basic group is introduced, a pigment by a polymer compound, etc. Even if surface grafting, atomization by sulfuric acid atomization, etc., washing with organic solvent or water to remove impurities, removal by ionic impurity ion exchange, etc. Good. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  As the pigment dispersant, commercially available surfactants can be used, and silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surface activities. Agents and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan K.K.), Ajisper (registered trademark) (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (Bic Chemie Co., Ltd.) and the like. These can be used alone or in combination of two or more.

  When a pigment dispersant is used, the amount used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  The dye is not particularly limited, and a known dye can be used. Examples thereof include a solvent dye, an acid dye, a direct dye, and a mordant dye. Examples of the dye include compounds classified as those having a hue other than pigment in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). It is done. Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye And dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The amount of the polyhalogenated zinc phthalocyanine (a1) used is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more in 100% by mass of the colorant (A). is there. The amount of polyhalogenated zinc phthalocyanine (a1) used may be 100% by mass, 90% by mass or less, 50% by mass or less, or 30% by mass or less in 100% by mass of the colorant (A). .
When a green pigment other than the polyhalogenated zinc phthalocyanine (a1) is contained, the amount of the green pigment other than the polyhalogenated zinc phthalocyanine (a1) is 0. 1 mass part or more is preferable, More preferably, it is 1 mass part or more, More preferably, it is 10 mass parts or more, 2000 mass parts or less are preferable, 300 mass parts or less are more preferable, 100 mass parts or less are still more preferable.

The amount of all yellow pigment used is preferably 1 to 1000 parts by weight, more preferably 10 to 100 parts by weight, and still more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the polyhalogenated zinc phthalocyanine (a1).
The amount of all blue pigment used is preferably 0.001 to 300 parts by mass, more preferably 0.1 to 100 parts by mass, and further 1 to 20 parts by mass with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1). 1-10 mass parts is especially preferable.

  The total amount of the colorant (A) is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, and further preferably 35 to 50% by mass in 100% by mass of the solid content of the colored photosensitive resin composition. %.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) (hereinafter sometimes referred to as “(b)”) having an ethylenically unsaturated bond.
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases).
Resin [K3] Copolymer of (a) and (c).
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

As (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(B) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. A compound is preferred, and (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group. When (b) is a polymerizable compound having an oxy ring (oxiranyl group) and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), the resin (B) is a cyclic group having 2 to 4 carbon atoms. It becomes an ether structure-containing component.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic hydrocarbon And a monomer (b1-2) having a converted structure (hereinafter may be referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ¹ and X ² are each independently a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or * represents a -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decan-8-yl (meth) acrylate (in this technical field, it is said to be “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”) ), Tricyclo [ .2.1.0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic esters;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2. 2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

  Resin [K1] is described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be produced with reference to the cited references.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). Any solvent may be used as long as it dissolves each monomer, and a solvent (E) described later can be used as a solvent for the colored photosensitive resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Resin [K4] can be obtained by placing dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (such as hydroquinone) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) Resin such as acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) Resin with glycidyl (meth) acrylate added to acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, resin such as resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer [K4]; tricyclodecyl (meth) acrylate / (Meth) acrylic acid is reacted with glycidyl (meth) acrylate copolymer Resin [K5] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid; tricyclodecyl (meth) acrylate / glycidyl ( Examples include resins [K6] such as resins obtained by further reacting a copolymer of (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride, among which resin [K1] is preferable. .
These resins may be used alone or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the solubility of the unexposed part in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and still more preferably 12 to 50 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% in the solid content of 100% by mass of the colored photosensitive resin composition. % By mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

<Polymerizable compound (C)>
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) when irradiated with light, and has a polymerizable ethylenically unsaturated bond. And the like. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

  Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol. Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate , Tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol te La (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be given.

  The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, more preferably 80 to 120 parts by mass with respect to 100 parts by mass of the resin (B) in the colored photosensitive resin composition. .

<Polymerization initiator (D)>
The polymerization initiator (D) is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and initiating polymerization. The colored photosensitive resin composition according to the present invention contains an O-acyloxime compound as the polymerization initiator (D).

  The O-acyl oxime compound is a compound having a structure represented by the formula (d). Hereinafter, * represents a bond.

  Examples of the O-acyloxime compound include a compound represented by the following formula (d1) (hereinafter sometimes referred to as compound (d1)) and a compound represented by the formula (d2) (hereinafter referred to as compound (d2). And at least one selected from the group consisting of compounds represented by formula (d3) (hereinafter sometimes referred to as compound (d3)) is preferred.

[In the formulas (d1) to (d3),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which may have a substituent; The contained methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms; The methylene group (—CH ₂ —) contained in the aromatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—. ]

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position. Examples of the substituent include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group An alkyl group having 1 to 15 carbon atoms such as a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom;
The alkyl group as the substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a group that combines a linear group and a cyclic group. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be replaced with —O— or —S—. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.

Examples of the alkyl group as a substituent for the aromatic hydrocarbon group represented by R ^d1 include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include a group represented by the following formula. In the formula, * represents a bond.

As the aromatic hydrocarbon group which may have a substituent represented by R ^d1 , a group represented by the following formula is preferable.

[Wherein R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and a hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer of 1 to 5. ]

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 . R ^d6 has preferably 2 to 7 carbon atoms, more preferably 2 to 5 carbon atoms. The alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably linear.
Examples of the halogen atom that may substitute the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and fluorine is particularly preferable. In addition, 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are preferably substituted with halogen atoms, and 3 or more and 6 or less are preferably substituted with halogen atoms. The substitution position of the R ^d6 O— group is preferably the ortho position or the para position, and particularly preferably the para position.
M2 is preferably 1 to 2, particularly preferably 1.

The number of carbon atoms in the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The heterocyclic group represented by R ^d1 may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the alkyl group represented by R ^d1 is preferably 1-12. ^Examples of the alkyl group represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, A tetradecyl group, a pentadecyl group, etc. are mentioned. These alkyl groups may be linear, branched, or cyclic, and may be a group in which a linear group and a cyclic group are combined. In the alkyl group represented by R ^d1 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —, The hydrogen atom may be substituted with an OH group or an SH group.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched) or cyclic, and may be linear, branched, or cyclic. And a group in which a cyclic group is combined. In the alkyl group for R ^d5 , the methylene group (—CH ₂ —) may be replaced by —O— or —CO—.

Specific examples of the alkyl group which may have a substituent represented by R ^d1 include groups represented by the following formulas. * Represents a bond.

Further, as represented by R ^d1, the number of carbon atoms of the group formed by combining an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R ^d1 is preferably 7-33, more Preferably it is 7-18, More preferably, it is 7-12. The combined group may have one or more substituents, and the substituent is the same as the group exemplified as the substituent that the aromatic hydrocarbon group or the alkyl group may have. The group of is mentioned. Represented by the R ^d1, as the group which is a combination of an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R ^d1, an aralkyl group, specifically, the following formula The group represented by these can be mentioned. In the formula, * represents a bond.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent. Is more preferable.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.
The number of carbon atoms of the heterocyclic group represented by R ^d2 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The number of carbon atoms in the alkyl group represented by R ^d2 is preferably from 1 to 7, more preferably from 1 to 5, more preferably from 1 to 3. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. The alkyl group may be linear, branched, or cyclic, or may be a group that combines a chain group and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and a methyl group. Particularly preferred.

The aromatic hydrocarbon group represented by R ^d3 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.
The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. An alkyl group having 1 to 15 carbon atoms such as a group and a decyl group; an alkenyl group having 1 to 15 carbon atoms such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a decenyl group; Is mentioned.
The aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d3 may have more preferably 1 to 7 carbon atoms, and the aliphatic hydrocarbon group is linear or branched Either a chain or a ring may be used, or a group obtained by combining a chain group and a cyclic group may be used. The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced with —O—, —CO— or —S—, and the methine group (—CH <) is represented by —N— <May be replaced.

Examples of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by R ^d3 may have include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d3 include groups represented by the following formulae. In the formula, * represents a bond.

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
Further, the heterocyclic group represented by R ^d3 may have one or more substituents, and the substituent includes an aromatic hydrocarbon group represented by R ^d1. Examples thereof include the same groups as those exemplified as the good substituent.

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of groups is preferably 2 or more and 5 or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is more preferable.
Moreover, the aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, more preferably from 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Alkyl groups such as tridecyl, tetradecyl and pentadecyl; ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, butadecenyl Groups, and alkenyl groups such as a pentadecenyl group. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group for R ^d4 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO— or —S—, and the methine group (—CH <) is represented by — PO ₃ <may be substituted, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include groups represented by the following formulas. In the formula, * represents a bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain having no substituent. It is a chain alkyl group.

  Examples of the compound (d1) include a compound represented by the formula (d1), specifically, a compound represented by the formula (d1-1) to a compound represented by the formula (d1-67). In Tables 1 to 7, * represents a bond.

Among them, the compound represented by formula (d1-3) to the compound represented by formula (d1-6), the compound represented by formula (d1-18) to the compound represented by formula (d1-52), A compound represented by the formula (d1-55), a compound represented by the formula (d1-56), a compound represented by the formula (d1-60), and a compound represented by the formula (d1-61) are preferable.
More preferably, a compound represented by formula (d1-3) to a compound represented by formula (d1-6), a compound represented by formula (d1-18) to a compound represented by formula (d1-41) And more preferably a compound represented by the formula (d1-24), a compound represented by the formula (d1-36) to a compound represented by the formula (d1-40), particularly preferably the formula (d1 -24).

  Compound (d1) can be produced by the production method described in JP-T-2014-500852.

Compound (d2) is
R ^d1 may have a substituent, an alkyl group having 1 to 15 carbon atoms,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
An aromatic hydrocarbon group having 6 to 18 carbon atoms in which R ^d3 may have a substituent,
A compound in which R ^d4 is an ^optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferred,
More preferably, R ^d1 represents a methyl group, an ethyl group or a propyl group,
R ^d2 represents a methyl group, an ethyl group or a propyl group;
R ^d3 represents a phenyl group substituted with a methyl group;
A compound in which R ^d4 is a methyl group, an ethyl group or a propyl group;
More preferably, R ^d1 and R ^d2 are methyl groups, R ^d3 is an o-tolyl group, and R ^d4 is an ethyl group.

The compound (d3) is preferably a compound in which R ^d1 is an optionally substituted alkyl group having 1 to 15 carbon atoms and R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms.
More preferably, R ^d1 is a hexyl group and R ^d2 is a phenyl group.

  Examples of such O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [ -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02, OXE03 (manufactured by BASF) and N-1919 (ADEKA) may be used. When these O-acyloxime compounds are used, a color filter excellent in litho performance tends to be obtained.

  The amount of the O-oxime compound used is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1). In particular, it is 5 parts by mass or more and may be 800 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 80 parts by mass or less. Further preferred.

  The colored photosensitive resin composition according to the present invention may further contain at least one selected from the group consisting of alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

  The alkylphenone compound is a compound having a partial structure represented by the formula (d4) or a partial structure represented by the formula (d5). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxypheny ) Biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) etheni ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part, More preferably, it is 10-20 mass parts. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

  The amount of the O-oxime compound used is preferably 5% by mass or more, more preferably 10% by mass or more in 100% by mass of the polymerization initiator (D), and the upper limit is not particularly limited, but is 100% by mass or less. It may be 70 mass% or less.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more polymerization initiation assistants (D1) may be contained.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiation assistant (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Thiol compound (T)>
The colored photosensitive resin composition of the present invention may contain a thiol compound (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an O-acyl oxime compound and / or a biimidazole compound. The thiol compound (T) is a compound having a sulfanyl group (—SH) in the molecule.

  The compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanyl. Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamidine -6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6 -Propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2- Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2- Methyl-4H-1,2,4-triazo Lu-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2- Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro Ro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, etc. Is mentioned.

  Compounds having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl) Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris Mud carboxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate) and 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

As the thiol compound (T), a compound having one sulfanyl group in the molecule is preferable.
The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 40 parts per 100 parts by mass of the polymerization initiator (D). Part by mass. When the content of the thiol compound (T) is within this range, sensitivity tends to be high and developability tends to be good.

<Solvent (E)>
The colored photosensitive resin composition of the present invention preferably contains a solvent (E). As the solvent (E), ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), Examples include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate and the like.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Two or more solvents (E) may be used in combination.
An organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3 More preferred are -methoxy-1-butanol and ethyl 3-ethoxypropionate.

  The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, and preferably from 0.002% by mass to 0.1%, based on the total amount of the colored photosensitive resin composition. It is not more than mass%, more preferably not less than 0.005 mass% and not more than 0.05 mass%. This content does not include the content of the pigment dispersant.

<Antioxidant (J)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to contain an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used. Two or more antioxidants may be used.
Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corp.), Irganox 1076. (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corp.), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5 , 5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corporation), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation), Irganox 3790: 1,3,5-tris ((4-t-butyl) -3-Hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by BASF Corp.), Irganox 1035 : Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation, Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis ( 1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Corp.), Irganox 1520 (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Corp.), Irganox 3125 (Irganox 3125, manufactured by BASF Corp.), Irganox 565 (Irganox 565: 2, 4 -Bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-t-butylanilino) -1,3,5-triazine, manufactured by BASF Corp.), ADK STAB AO-80 (ADK STAB AO- 80: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetra Oxaspiro (5,5) undecane (manufactured by ADEKA), Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.) , Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.) and Vitamin E (Eisai) Etc.).
Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Corp.), Irgafos 12 (Irgafos 12: Tris [2-[[2 , 4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corporation), Irgaphos 38 ( Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation), Adeka Stub 329K (manufactured by ADEKA Corporation), Adeka Stub PEP36 ( (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (Clarian) ), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilyzer GP (Sumizer GP: 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] dioxaphosphine (Manufactured by Sumitomo Chemical Co., Ltd.).
Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Is mentioned.

  Moreover, it is preferable that the colored photosensitive resin composition which concerns on this invention contains a C2-C4 cyclic ether structure containing component. The C2-C4 cyclic ether structure-containing component is not particularly limited as long as it is a compound having a C2-C4 cyclic ether structure (for example, an oxirane ring, an oxetane ring, a tetrahydrofuran ring, etc.). It may be a monomer having a cyclic ether structure of ˜4, or a copolymer having a cyclic ether structure of 2 to 4 carbon atoms. Further, for example, the resin (B) may also serve as a C2-C4 cyclic ether structure-containing component.

<Other ingredients>
In the colored photosensitive resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amine compound, curing An additive such as an agent can also be used in combination.

  Examples of the filler include glass, silica, and alumina.

  Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Note that 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is an example of a component having a cyclic ether structure having 2 to 4 carbon atoms.

  Examples of ultraviolet absorbers include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone Compound; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-hexyloxyphenol and other triazine compounds;

  Examples of the aggregation inhibitor include sodium polyacrylate.

Organic acids are used to adjust developability. Specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

As an organic amine compound,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol ;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkane diols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, aminobenzoic acid such as p-diethylaminobenzoic acid; and the like.

  Examples of the curing agent include a compound that can react with the carboxy group in the resin (B) when heated to crosslink the resin (B), a compound that can be polymerized alone to cure the colored pattern, and the like. , Epoxy compounds, oxetane compounds and the like. These correspond to a cyclic ether structure-containing component having 2 to 4 carbon atoms.

Here, as the epoxy compound, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic type epoxy resin, fat Aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, fats other than epoxy resins and their brominated derivatives Epoxy compounds of aliphatic, alicyclic or aromatic, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylates and triglycidyl isocyanurates Etc.
Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored photosensitive resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As polyvalent carboxylic acid,
Phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetra Aromatic polycarboxylic acids such as carboxylic acids;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As polyvalent carboxylic acid anhydride,
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As the epoxy resin curing agent, trade name “Adeka Hardener (registered trademark) EH-700” (manufactured by ADEKA), trade name “Rikacid (registered trademark) HH” (manufactured by Shin Nippon Rika Co., Ltd.), trade name “MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) and the like.
Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate Examples include rates.

  Two or more curing agents may be used in combination.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and, if necessary, a solvent (E), It can be prepared by mixing the thiol compound (T), the leveling agent (F), the polymerization initiation assistant (D1), the antioxidant (J), and other components.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

  As a substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate Further, aluminum, silver, a silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored photosensitive resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. Further, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.
A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  Since the film thickness of the obtained coating film affects adjacent pixels, the coating film is preferably as thin as possible. In particular, when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured. May be lost. The coating film after post-baking is preferably, for example, 3 μm or less, more preferably 2.8 μm or less. Although the minimum of a coating film is not specifically limited, Usually, 1 micrometer or more may be 1.5 micrometers or more.

  Moreover, the lightness of a coating film is so preferable that it is high, 38.5 or more are preferable, More preferably, it is 39 or more, Although an upper limit is not specifically limited, Usually, it is 70 or less.

  By using the colored photosensitive resin composition of the present invention, a color filter with particularly high brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Synthesis example 1
An appropriate amount of nitrogen was passed through a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 280 parts by mass of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts by mass of acrylic acid, 289 parts by mass of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, 125 parts of propylene glycol monomethyl ether acetate Part of the mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution in which 33 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23 ° C.) of 125 mPas, a solid content of 37.0% by mass and a solution acid value of 27 mg-KOH / g (Hereinafter, it may be referred to as a resin solution (B1).) The produced copolymer had a weight average molecular weight Mw of 9,200 and a dispersity of 2.08. The obtained copolymer showed almost no absorption at 500 to 600 nm.

About the measurement of polystyrene conversion weight average molecular weight Mw and number average molecular weight Mn of resin obtained by said synthesis example, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

[Preparation of pigment dispersion 1]
Polyhalogenated zinc phthalocyanine (a1) 14.0 parts Acrylic pigment dispersant 1.9 parts Propylene glycol monomethyl ether acetate 84.1 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. (A-1) was obtained.
Here, as the polyhalogenated zinc phthalocyanine (a1), it was synthesized by the method described in Japanese Patent No. 4368157, and the obtained polyhalogenated zinc phthalocyanine (a1) was analyzed in one molecule from the halogen content analysis by mass spectrometry. Contained an average of 10 bromines. A composition prepared by mixing the pigment dispersion 1 and the resin solution (B1) and adjusting the concentration of the polyhalogenated zinc phthalocyanine (a1) in the solid content to 30% is a 2-inch square glass substrate (Eagle XG; After being applied by spin coating, it was pre-baked at 100 ° C. for 3 minutes. After cooling and further baking in an oven at 230 ° C. for 30 minutes, the color of the coating film obtained was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), maximum transmission The wavelength of the rate was 515 nm. The acrylic pigment dispersant, the resin solution (B1), and propylene glycol monomethyl ether acetate had almost no effect on the transmittance.

[Preparation of pigment dispersion 2]
C. I. Pigment Green 58 13.0 parts Acrylic pigment dispersant 2.0 parts Propylene glycol monomethyl ether acetate 85.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-2) Got.
C. I. Pigment Green 58 contained an average of 14 bromine atoms in one molecule based on a halogen content analysis by mass spectrometry. As in the case of pigment dispersion 1, colorimetry was performed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the maximum transmittance wavelength was 525 nm. The acrylic pigment dispersant, the resin solution (B1), and propylene glycol monomethyl ether acetate had almost no effect on the transmittance.

[Preparation of pigment dispersion 3]
C. I. Pigment Green 7 11.0 parts Acrylic pigment dispersant 3.3 parts Propylene glycol monomethyl ether acetate 85.7 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-3) Got.

[Preparation of pigment dispersion 4]
C. I. Pigment Blue 15: 3 12.0 parts Acrylic pigment dispersant 4.0 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed, and the pigment dispersion (A- 4) was obtained.

[Preparation of pigment dispersion 5]
C. I. Pigment Yellow 185 5.0 parts Acrylic pigment dispersant 3.5 parts Propylene glycol monomethyl ether acetate 91.5 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-5) Got.

[Preparation of pigment dispersion 6]
C. I. Pigment Yellow 138 15.0 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 80.5 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-6) Got.

Examples 1-9 and Comparative Examples 1-3
[Preparation of colored photosensitive resin composition]
The components shown in Table 8 were mixed to obtain a colored photosensitive resin composition. In addition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition was “solid content (%)” in Table 8.

In Table 8, each component is as follows.
Colored dispersant (A1); Pigment dispersion (A-1) obtained above
Colored dispersant (A2); Pigment dispersion (A-2) obtained above
Colored dispersant (A3); Pigment dispersion (A-3) obtained above
Colored dispersant (A4); Pigment dispersion (A-4) obtained above
Colored dispersant (A5); Pigment dispersion obtained above (A-5)
Colored dispersant (A6); Pigment dispersion (A-6) obtained above
Resin solution (B1); copolymer solution obtained in Synthesis Example 1 polymerizable compound (C1); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF; O-acyloxime compound)
Polymerization initiator (D2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF; alkylphenone compound)
Leveling agent (F1); polyether-modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of pattern]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm). As a photomask, a mask on which a 50 μm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and 230 ° C. in an oven. And post-baked for 30 minutes to obtain a pattern.

[Film thickness measurement]
About the obtained pattern, film thickness FT (micrometer) was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 9. In the table, the case where the film thickness is 3 μm or less is “◯”, and the case where the film thickness is more than 3 μm is “x”.

[Chromaticity evaluation]
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE (Characteristic function of C light source) x, y) and brightness Y were measured. The results are shown in Table 9. In the table, the case where the brightness is 38.5 or more is “◯”, and the case where the brightness is less than 38.5 is “x”.

[Pattern shape]
The obtained pattern was observed with the shape of an optical microscope. When the pattern edge was a straight line, it was evaluated as “◯”, and when it was notched due to chipping or the like, it was evaluated as “x”. The results are shown in Table 9.

  A high-definition color filter having good lightness can be produced from the colored photosensitive resin composition of the present invention. Moreover, a pattern with a favorable pattern shape can be produced from the colored photosensitive resin composition of the present invention, and chipping derived from the colored photosensitive resin composition is unlikely to occur during pattern production.

Claims (9)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
As the colorant (A), a polyhalogenated zinc phthalocyanine containing less than 13 bromine on average in one molecule and having a wavelength of 500 to 520 nm at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum. Including (a1),
A colored photosensitive resin composition comprising an O-acyloxime compound as the polymerization initiator (D).   The colored photosensitive resin composition according to claim 1, further comprising a pigment and / or a dye as the second colorant.   The colored photosensitive resin composition according to claim 2, comprising at least one selected from the group consisting of a green pigment, a yellow pigment, and a blue pigment other than the polyhalogenated zinc phthalocyanine (a1) as the second colorant. object. The colored photosensitive composition according to any one of claims 1 to 3, comprising at least one selected from the group consisting of the following formulas (d1), (d2), and (d3) as the O-acyloxime compound. Resin composition.
[In the formulas (d1) to (d3),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which may have a substituent; The contained methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms; The methylene group (—CH ₂ —) contained in the aromatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—. ]   Furthermore, at least 1 sort (s) or more chosen from the group which consists of an alkylphenone compound, a biimidazole compound, a triazine compound, an acyl phosphine oxide compound, and a thiol compound (T) is contained, The colored photosensitivity of any one of Claims 1-4. Resin composition.   Furthermore, at least 1 type of leveling agent (F) chosen from the silicone type surfactant, a fluorine type surfactant, and the silicone type surfactant which has a fluorine atom is contained in any one of Claims 1-5. Colored photosensitive resin composition.   The coating film formed using the colored photosensitive resin composition of any one of Claims 1-6.   The color filter formed using the colored photosensitive resin composition of any one of Claims 1-6.   A display device comprising the color filter according to claim 8.