JP6707380B2 - Colored photosensitive resin composition - Google Patents

Description

The present invention relates to a colored photosensitive resin composition.

In recent years, display displays have been under development for expanding the color reproduction range that can be displayed, and as a part thereof, color filters with deeper colors are required. In order to meet the demand, 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. Not preferable. Further, in order to have the desired color characteristics, it is necessary to fabricate the color filter with a thick film, but when applied to a liquid crystal display device, color mixing of light with adjacent pixels occurs, Film formation is also not preferable.

In order to design a dark green color filter, Patent Document 1 discloses C.I. I. Pigment Green 58 and C.I. I. Pigment Blue 15:3 and C.I. I. Pigment Yellow 150 and the like, a green photosensitive resin composition containing a colorant, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent are described.

JP2012-247539A

Therefore, the present invention has an object to provide a colored photosensitive resin composition capable of producing a thin film, a color filter having a good pattern shape and high brightness.

That is, the colored photosensitive resin composition according to the present invention has the following points.
[1] contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As the colorant (A), a polyhalogenated zinc phthalocyanine containing an average of less than 13 bromine atoms in one molecule and having a maximum transmittance of 500 to 520 nm in a spectral transmittance spectrum at 380 to 780 nm. A colored photosensitive resin composition comprising (a1) and a blue dye.
[2] The colored photosensitive resin composition according to [1] or [2], which further contains a green pigment other than the polyhalogenated zinc phthalocyanine (a1) as the colorant (A).
[3] As the colorant (A), C.I. I. The colored photosensitive resin composition according to [1] or [2], which contains Pigment Green 58.
[4] The blue dye is C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6 and at least one selected from 60 or more, the colored photosensitive resin composition according to any one of [1] to [3].
[5] The blue dye is C.I. I. Pigment Blue 15:3 and 15:4, which is at least one kind or more, and the colored photosensitive resin composition according to any one of [1] to [4].
[6] A coating film formed from the colored photosensitive resin composition according to any one of [1] to [5].
[7] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [5].
[8] A display device including the color filter according to [7].

According to the colored photosensitive resin composition of the present invention, it is possible to provide a color filter which is a thin film and has a good pattern shape and high brightness.

The colored photosensitive resin composition according to the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and as the colorant (A), a polyhalogenated compound is used. It is characterized by containing zinc phthalocyanine (a1) and a blue dye. The color filter formed from the colored photosensitive resin composition of the present invention can have a good pattern shape after exposure and development, and can exhibit high brightness even in a thin film.
The compounds exemplified as each component in the present specification can be used alone or in combination of two or more kinds unless otherwise specified.

<Colorant (A)>
The colored photosensitive resin composition according to the present invention contains polyhalogenated zinc phthalocyanine (a1) and a blue dye as essential components as a colorant (A).
The polyhalogenated zinc phthalocyanine (a1) contains an average of less than 13 bromine atoms in one molecule, and has a wavelength at which the maximum transmittance is 500 to 520 nm in the spectral transmittance spectrum at 380 to 780 nm. The bromine number can be quantified by halogen content analysis by mass spectrometry.
The above spectral transmittance spectrum is obtained from the polyhalogenated zinc phthalocyanine (a1) from the light transmittance (T1) measured by a colorimeter for a coating film (thickness 2 μm) of the polyhalogenated zinc phthalocyanine (a1) prepared by the following procedure. Is a spectrum showing a value (=T1-T2) obtained by subtracting the transmittance value (T2) measured in the same manner for a coating film prepared by the same procedure as the above-mentioned coating film except that () is not included.
Examples of the colorimeter include OSP-SP-200 (manufactured by Olympus Corporation). The measurement is typically performed using a halogen lamp as a light source and a pinhole diameter of about 50 μm.
[Coating method]
By mixing the polyhalogenated zinc phthalocyanine (a1) with an epoxy resin solution [resin concentration: about 30 to 40% by mass, solvent: ether ester solvent (propylene glycol monomethyl ether acetate, etc.)], the total amount of resin and pigment A composition with a pigment content of 30% by weight is prepared. Further, the composition was applied onto a 2-inch square glass substrate, the obtained coating film was pre-baked at 100° C. for 3 minutes, once cooled to room temperature, and then post-baked at 230° C. for 30 minutes. To do.

The polyhalogenated zinc phthalocyanine (a1) is a C.I. I. Pigment Green 58 can be produced by changing the number of bromine added, and can be produced by the method described in Japanese Patent No. 4368157 or the like.

The polyhalogenated zinc phthalocyanine (a1) is a C.I. I. Pigment Green 7, C.I. I. Pigment Green 58 can be distinguished from the number of bromine in the molecule and the wavelength at which the transmittance is maximum.
C. I. Pigment Green 7 is a chlorinated copper phthalocyanine, has no bromine in the molecule, and is C.I. I. Pigment Green 58 molecule contains 14 bromine on average. When a coating film having a maximum transmittance spectrum of 90% is prepared, C.I. I. Pigment Green 58 has a maximum transmittance in the range of more than 520 nm to 530 nm and a transmittance of 50% in the range of 570 to 575 nm. On the other hand, the polyhalogenated zinc phthalocyanine (a1) shows 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 average number of bromine contained in one molecule of the polyhalogenated zinc phthalocyanine (a1) is preferably 12 or less, more preferably 11 or less. Although the lower limit is not limited, it is 1 or more, preferably 3 or more, more preferably 6 or more, still more preferably 8 or more.

In the present specification, the "total amount of solids" refers to the total amount of components excluding the solvent (E) from the colored photosensitive resin composition of the present invention. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

The polyhalogenated zinc phthalocyanine (a1) is preferably used in the state of a dispersion liquid (pigment dispersion liquid) uniformly dispersed in a solvent, and the dispersion liquid (pigment dispersion liquid) is a polyhalogenated zinc phthalocyanine (a1). It can be obtained by mixing a1) in a solvent. 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, polyamine, and acrylic dispersants.
These dispersants may be used alone or in combination of two or more kinds. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), and Azisper (Ajinomoto Fine Techno Co., Ltd.) are trade names. Co., Ltd.), Disperbyk (manufactured by Big Chemie), and the like.
When the pigment dispersion liquid contains a dispersant, the content thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the pigment in the pigment dispersion liquid. Is. When the content of the pigment dispersant is within the above range, a pigment dispersion liquid in which the polyhalogenated zinc phthalocyanine (a1) is uniformly dispersed in the solvent tends to be obtained.

Examples of the solvent include the same solvents as the solvent (E) in the colored photosensitive resin composition of the present invention. 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 are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like are more preferable.
The solvent is preferably used so that the solid content concentration in the pigment dispersion can be adjusted to 3 to 20% by mass, more preferably 5 to 18% by mass.

Blue pigments include blue pigments and blue dyes.
Examples of blue pigments include C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and the like.
As the blue dye, C.I. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, C. 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139 and the like. I. Solvent blue dye;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340 and the like. I. Acid blue dye;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, C. 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, and the like. I. Direct blue dye;
C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like. I. Disperse blue dye; C.I. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89 and the like. I. Basic blue dye;
C. I. Modant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84C. I. And the like: modant blue dye;
Among them, the blue pigment is preferably a blue pigment, more preferably C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6 and 60 or more, and more preferably C.I. I. Pigment Blue 15:3 and at least one selected from 15:4.

As the coloring agent (A), a coloring agent other than polyhalogenated zinc phthalocyanine (a1) and a blue dye (may be referred to as “second coloring agent”), a pigment (may be referred to as “second pigment”) A) and/or a dye (sometimes referred to as a “second dye”).

Examples of the second pigment include polyhalogenated zinc phthalocyanine (a1) and organic pigments and inorganic pigments other than the blue dye, which are classified as pigments by the Color Index (published by The Society of Dyers and Colorists). Is mentioned.
Examples of the organic pigment 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. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments other than polyhalogenated zinc phthalocyanine (a1);
Etc.

As the second pigment, green pigments other than polyhalogenated zinc phthalocyanine (a1) are preferable, and C.I. I. Pigment Green 7, 36 and 58 are more preferable, and C.I. I. Pigment Green 58 is more preferable.
Further, it is preferable that a yellow pigment is included as the second pigment. Examples of the yellow pigment include C.I. I. Pigment Yellow 138, 139, 150 and 185, and more preferably at least one selected from C.I. I. Pigment Yellow 138 or 185 is more preferable, and C.I. I. Pigment Yellow 185.
You may use 2 or more types of 2nd pigments.

The pigment is, if necessary, rosin treatment, surface treatment using a pigment derivative or a pigment dispersant having an acidic group or a basic group introduced therein, graft treatment on a pigment surface with a polymer compound, sulfuric acid atomization. Atomization treatment by a method or the like, cleaning treatment by an organic solvent or water for removing impurities, removal treatment by an ion exchange method for ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by incorporating the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

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

When the pigment dispersion contains a pigment dispersant, the content thereof is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment. When the content of the pigment dispersant is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.

As the second dye, known dyes other than the blue dye can be used, and examples thereof include solvent dyes (organic solvent-soluble dyes), acid dyes, direct dyes, and mordant dyes. As the dyes, among the compounds classified by the Color Index (published by The Society of Dyers and Colorists) as those having a hue other than pigment, and among the known dyes described in Dyeing Note (Shikisosha), blue Dyes other than dyes may be mentioned. Further, according to the 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. Examples thereof include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The content of the polyhalogenated zinc phthalocyanine (a1) in 100% by mass of the colorant (A) is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. Yes, and more preferably 20% by mass or more. Further, the content of the polyhalogenated zinc phthalocyanine (a1) in 100% by mass of the colorant (A) may be 100% by mass, 90% by mass or less, 50% by mass or less, and 30% by mass or less. ..
When a green pigment other than the polyhalogenated zinc phthalocyanine (a1) is contained, the content of the green pigment other than the polyhalogenated zinc phthalocyanine (a1) is 1 part by mass relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1). It is preferably not less than 10 parts by mass, more preferably not less than 10 parts by mass, still more preferably not less than 50 parts by mass, further preferably not less than 80 parts by mass, preferably not more than 4000 parts by mass, 2000 The amount is preferably not more than 100 parts by mass, more preferably not more than 1000 parts by mass, even more preferably not more than 300 parts by mass, and even preferably not more than 100 parts by mass.

The content of the blue colorant (the total of the blue pigment and the blue dye, preferably the blue pigment) is preferably 0.001 to 300 parts by mass with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1), and a content of 0. The amount is more preferably 05 to 100 parts by mass, further preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 20 parts by mass.
The total content of the yellow pigment is preferably 1 to 1000 parts by mass, more preferably 10 to 100 parts by mass, and 10 to 80 parts by mass with respect to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1). More preferably, the amount is 10 to 40 parts by mass.

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

When the colored photosensitive resin composition contains a dye, the content of the dye in the colorant (A) is less than 90% by mass, preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably Is 10% by mass or less.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin and is derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as “(a)”). It is preferably a polymer having a structural unit.
The copolymer having a structural unit derived from (a) is a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, referred to as “(b)” in some cases. It is preferably a copolymer having at least one selected from the group consisting of structural units derived from (i) and structural units having an ethylenically unsaturated bond. The copolymer may further have other structural units. As the other structural unit, a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b), and may be referred to as “(c)” hereinafter) Is mentioned.
Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] A copolymer having a structural unit derived from (a) and a structural unit derived from (b).
Resin [K2] A copolymer having a structural unit derived from (a), a structural unit derived from (b) and a structural unit derived from (c).
Resin [K3] A copolymer having a structural unit derived from (a) and a structural unit derived from (c).
A polymer having a structural unit obtained by reacting (preferably adding) (b) with a structural unit derived from a resin [K4] (a).
A polymer having a structural unit obtained by reacting (preferably adding) (a) with a structural unit derived from a resin [K5] (b).
Structural unit derived from resin (K6) (b) and structural unit derived from (c) by reacting (preferably adding) (a) and further reacting (preferably adding) carboxylic anhydride. A copolymer having and.

As (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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, 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 Bicyclo unsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene and 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 divalent or higher valent polycarboxylic 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 alkaline aqueous 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, preferably (b), is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In addition, in this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.

As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond (B2) (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), and the like. ..

(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 is epoxy A monomer (b1-2) having a modified structure (hereinafter sometimes referred to as “(b1-2)”) is included.

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and 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-tris (Glycidyloxymethyl) styrene etc. are mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, cyclo. Mar A400; manufactured by Daicel Co., Ltd., 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by Formula (I) and Formula (II). The compound etc. which are represented are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b 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 replaced with.
X ¹ and X ² are each independently a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Examples of the alkyl group having a hydrogen atom substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group and a 1-hydroxy group. Examples thereof 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 or a 2-hydroxyethyl group, and more preferably a hydrogen atom or 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- 1,6-diyl group and the like can be mentioned.
As X ¹ and X ² , a single bond, a methylene group, an ethylene group, a *—CH ₂ —O— (* represents a bond with O) group, and a *—CH ₂ CH ₂ —O— group are preferable. Among them, more preferably a single bond, * - include CH ₂ CH ₂ -O- group.

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (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 preferred are formula (I-1), formula (I-7), formula (I-9) and formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (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, the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) can be mentioned.

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Also, they can be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably in the formula (I): formula (II), 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80. ~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. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane. , 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.), and tetrahydrofurfuryl methacrylate.

Examples of (c) include 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 the technical field, it is referred to as “dicyclopentanyl(meth)acrylate” as a trivial name, and may be referred to as “tricyclodecyl(meth)acrylate”. ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (known in the art as the trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates;
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, and itaconic acid diethyl;
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(cyclohexyl) Bicyclo unsaturated compounds such as oxycarbonyl)bicyclo[2.2.1]hept-2-ene;
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 and 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.
Among 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. Further, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable because they are excellent in developability during pattern formation.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range in 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), particularly structural unit derived from (b1); 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, the developability, and the solvent resistance of the obtained pattern tend to be excellent.

The resin [K1] is described in the literature “Experimental method for polymer synthesis” (Takayuki Otsu, Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited references.

Specifically, a method of charging a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent and the like into a reaction vessel, and stirring, heating and keeping the temperature in a deoxygenated atmosphere is a method. Can be mentioned. The polymerization initiator, solvent and the like used here are not particularly limited, and any of those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent capable of dissolving each monomer may be used, and the solvent (E) described later or the like can be used as the solvent of the colored photosensitive resin composition.

The obtained copolymer may be used as the solution after the reaction as it is, or may be used as a concentrated or diluted solution, or taken out as a solid (powder) by a method such as reprecipitation. You may use the thing. In particular, when the solvent (E) described below is used as a solvent in this 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 in the following range in 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), particularly structural unit derived from (b1); 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 within the above range, storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent.

The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1].
Specifically, the reaction vessel is charged with a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. There is a method of doing. The obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-55 mol%, more preferably 10-50 mol%
Structural unit derived from (c); 45 to 98 mol%, more preferably 50 to 90 mol%
The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].

In the resin [K4], a copolymer of (a) and (c) is obtained, and (a) has a cyclic ether having 2 to 4 carbon atoms, which is contained in (b), and particularly has an oxirane ring contained in (b1). It can be produced by addition to a carboxylic acid and/or a carboxylic anhydride.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range in all structural units constituting the copolymer of (a) and (c).
Structural unit derived from (a); 5 to 50 mol%, more preferably 10 to 45 mol%
Structural unit derived from (c); 50 to 95 mol%, more preferably 55 to 90 mol%

Next, in part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above copolymer, the cyclic ether having 2 to 4 carbon atoms contained in (b), particularly the oxirane contained in (b1). React the rings.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b) (particularly (b1)), carboxylic acid or carboxylic anhydride and cyclic ether The reaction catalyst (for example, tris(dimethylaminomethyl)phenol, etc.), the polymerization inhibitor (for example, hydroquinone, etc.) and the like are put in a flask and reacted at 60 to 130° C. for 1 to 10 hours to give a resin [K4]. Obtainable.
The amount of (b) used, particularly the amount of (b1) used, is preferably 5 to 80 mol, and more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be well balanced. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as the (b) used in the resin [K4], and further (b1-1) is preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c).
Reaction conditions such as a charging method, a reaction temperature and a time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

As the resin [K5], in the first step, a copolymer of (b) (particularly (b1)) and (c) is obtained in the same manner as in the above-mentioned method for producing the resin [K1]. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a 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) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b), particularly structural unit derived from (b1); 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], (a) is contained in the cyclic ether derived from (b) which the copolymer of (b) (particularly (b1)) and (c) has. The resin [K5] can be obtained by reacting a carboxylic acid or a carboxylic anhydride.
The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol per 100 mol of (b) (particularly (b1)). Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as the (b) used in the resin [K5], and further (b1-1) is preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or the carboxylic acid anhydride is reacted with the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride) and the like. Be done.
Of the resins [K1] to [K6], the preferred resin is [K1] or [K2].
These resins may be used alone or in combination of two or more kinds.

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 within the above range, the unexposed portion tends to have high solubility in a developing solution, and the residual film rate and hardness of the obtained 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 further 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, for example, by titration with 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 100% by mass of the solid content of the colored photosensitive resin composition. It is% by mass. When the content of the resin (B) is within the above range, the solubility of the unexposed area in the developing solution tends to be high.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond. 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, and 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 tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified Examples thereof include 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 them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like can be mentioned.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total solid content. The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 80 to 120 parts by mass, relative 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 to start the polymerization.

Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphine oxide compounds. As the polymerization initiator (D), only one type may be used, or two or more types may be used. The preferred polymerization initiator (D) is an O-acyl oxime compound.

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

As the O-acyl oxime compound, a compound represented by the formula (d1) (hereinafter sometimes referred to as compound (d1)) and a compound represented by the formula (d2) (hereinafter referred to as compound (d2)) And a compound represented by the formula (d3) (hereinafter sometimes referred to as the compound (d3)) are preferable.

[In formulas (d1) to (d3),
R ^d1 has an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, and a substituent group. Optionally represents an alkyl group having 1 to 15 carbon atoms or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, and a methylene group (—CH ₂ —) contained in the alkyl group or aralkyl group. is, -O -, - CO -, - S -, - SO 2 - or -NR ^d5 - may be replaced with.
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 aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, group a methylene group contained in the hydrocarbon group (-CH ₂ -) is, -O -, - may be replaced in the CO- or -S-, a methine group (-CH contained in the aliphatic hydrocarbon group < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced 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—. ]

When the colored photosensitive resin composition of the present invention contains the O-acyl oxime compound of formula (d1) to formula (d3), it is possible to form a coating film having high lightness and capable of forming a pattern excellent in shape. it can. From the viewpoint of improving the shape of the obtained pattern, the content of the O-acyl oxime compound of the formulas (d1) to (d3) is preferably 0.5% by mass or more, more preferably 100% by mass in the solid content of 100% by mass. Is 1% by mass or more, and more preferably 2% by mass or more. The content is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less in 100% by mass of solid content in order to increase the brightness of the obtained coating film.

The aromatic hydrocarbon group represented by R ^d1 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and further 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. 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, more preferably at the γ-position. As the substituent, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group. And the like, an alkyl group having 1 to 15 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom;
The alkyl group as the substituent has preferably 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 combination of a chain and a cyclic group. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be replaced with —O— or —S—. Further, 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 and a bromine atom, and is preferably substituted with a fluorine atom.

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

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

The aromatic hydrocarbon group ^optionally represented by R ^d1 is preferably a group represented by the following formula.

[In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom contained in the alkyl group 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 of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably 2 to 7, and more preferably 2 to 5. The alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably linear.
Examples of the halogen atom which may be substituted for 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. Further, it is preferable that 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and 3 or more and 6 or less of hydrogen atoms are substituted with halogen atoms. The substitution position of the R ^d6 O- group is preferably the ortho position and the para position, and particularly preferably the para position.
Further, m2 is preferably 1 to 2, and particularly preferably 1.

The heterocyclic group represented by R ^d1 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. 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 which the aromatic hydrocarbon group represented by R ^d1 may have.

The alkyl group represented by R ^d1 preferably has 1 to 12 carbon atoms. ^Examples of the alkyl group represented by R ^d1 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, Examples thereof include a tetradecyl group and a pentadecyl group. These alkyl groups may be linear, branched or cyclic, or may be a group in which a chain group and a cyclic group are combined. In the alkyl group represented by R ^d1 , the methylene group (—CH ₂ —) may be replaced with —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), cyclic, linear, branched, or cyclic, and is a linear group. It may be a group in which a cyclic group and a cyclic group are combined. Further, in the alkyl group of R ^d5 , the methylene group (—CH ₂ —) may be replaced with —O— or —CO—.

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

Further, aralkyl group which may have a substituent represented by R ^d1 is represented by R ^d1, and alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R ^d1 It is preferably a group in which The aralkyl group has preferably 7 to 33 carbon atoms, more preferably 7 to 18 carbon atoms, and further preferably 7 to 12 carbon atoms. The aralkyl group may have one or two or more substituents, and as the substituent, a substituent which the aromatic hydrocarbon group represented by R ^d1 and the alkyl group may have. The same groups as those exemplified above can be mentioned. Specific examples of the group represented by R ^d1 which is a combination of the aromatic hydrocarbon group and the alkanediyl group derived from the alkyl group represented by R ^d1 include groups represented by the following formulas: Can be mentioned. In the formula, * represents a bond.

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, and a phenyl group which may have a substituent is further preferable. As the substituents on the aromatic hydrocarbon group and the phenyl group, an alkoxy group having 4 to 9 carbon atoms, an alkoxy group having 4 to 9 carbon atoms having a halogen (preferably a fluorine atom), and 1 to 3 methylenes. An alkoxy group having 5 to 9 carbon atoms in which the group is substituted with an ether bond is preferable. All of these substituents preferably have a branched structure.

The aromatic hydrocarbon group represented by R ^d2 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 and even 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.
The heterocyclic group represented by R ^d2 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. 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 alkyl group represented by R ^d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. The alkyl group may be linear, branched or cyclic, or may be a combination of a chain and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, further 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 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, and a phenyl group and a naphthyl group are more preferable.
Moreover, 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 group. C1-15 alkyl groups such as groups and decyl groups; ethenyl groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, nonenyl groups, decenyl groups and other alkenyl groups having 1 to 15 carbon atoms; Is mentioned.
The aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d3 may have has preferably 1 to 7 carbon atoms, and the aliphatic hydrocarbon group is linear or branched. It may be either chain-shaped or cyclic, and may be a group in which a chain-shaped group and a cyclic group are combined. Further, a methylene group contained in the aliphatic hydrocarbon group (-CH ₂ -) is, -O -, - may be replaced in the CO- or -S-, the methine group (-CH <), -N It may be replaced by <.

Examples of the aliphatic hydrocarbon group which 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 heterocyclic group represented by R ^d3 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. 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 may be the aromatic hydrocarbon group represented by R ^d1. Examples of the substituent that may be mentioned include the same groups as those exemplified.

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 is preferably 2 or more and 5 or less.

The aromatic hydrocarbon group represented by R ^d4 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 and even 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. A phenyl group and a naphthyl group are more preferable, and a phenyl group is still more preferable.
The aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituents that the aromatic hydrocarbon group for R ^d1 may have.

The aliphatic hydrocarbon group represented by R ^d4 preferably has 1 to 13 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 4 to 9 carbon atoms. 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 group, tetradecyl group and pentadecyl group; ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadecenyl group And alkenyl groups such as pentadecenyl group; and the like. These aliphatic hydrocarbon groups may be linear (linear or branched), cyclic, or a combination of a linear group and a cyclic group. Further, in the aliphatic hydrocarbon group of R ^d4 , the methylene group (—CH ₂ —) may be replaced with —O—, —CO— or —S—, and the methine group (—CH<) is — PO ₃ <may be substituted, and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced 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 formula. 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, and further preferably a branched chain alkyl group.

Examples of the compound (d1) include the compounds (d1-1) to (d1-67) having the substituents shown in the table below. In Tables 1 to 7, * represents a bond.

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

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

The compound (d2) is
R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,
A compound in which R ^d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent is preferable,
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.

Such O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane. -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-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-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane- 1-on-2-imine, a compound represented by the following formula:

Commercially available products such as Irgacure OXE01, Irgacure OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. With these O-acyl oxime compounds, a color filter having excellent lithographic performance tends to be obtained.

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 the structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 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. Be done. Commercially available products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having the structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy). )Phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by 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(trialkoxyphenyl) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), imidazole in which the phenyl group at the 4,4′,5,5′-position is substituted with a carbalkoxy group. Examples thereof include compounds (see, for example, JP-A-7-10913). Among them, compounds represented by the following formula and mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine and the like can be mentioned. ..

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

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 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 and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the below-mentioned polymerization initiation aid (D1) (particularly amines).

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 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 that the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation aid (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When the polymerization initiator auxiliary agent (D1) is contained, 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 preferable. Two or more kinds of polymerization initiation aids (D1) may be contained.

As the amine compound, 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 called Michler's ketone), 4,4′-bis(diethylamino)benzophenone, 4,4′-bis( Examples thereof include ethylmethylamino)benzophenone, and among them, 4,4′-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

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. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

As the carboxylic acid compound, 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 can be mentioned.

The content of the polymerization initiation aid (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). It is a department. When the amount of the polymerization initiation aid (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.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid and 2-sulfanyl. Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridin-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-diamino-6 -Sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propyl Pyrimidine, 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-triazole-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-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine and 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine and the like. Is mentioned.

Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis(3-sulfanyl). Acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanyl propionate), trimethylol propane tris(3-sulfanyl propionate), tri Methylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanyl propionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanyl propionate), pentaerythritol tetrakis(3) -Sulfanyl butyrate) and 1,4-bis(3-sulfanylbutyloxy)butane.

The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.
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 by mass with respect to 100 parts by mass of the polymerization initiator (D). It is a mass part. When the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the 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 solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-), Ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be mentioned.

As the ester solvent, 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.

As the ether solvent, 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, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.

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, and 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent 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.

You may use together 2 or more types of solvent (E).
From the viewpoint of coating property and drying property, an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable. 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) in the colored photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 92% by mass. 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 in the colored photosensitive resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of application becomes good, and the color density does not become insufficient when a color filter is formed, so that the display characteristics tend to be good.

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

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: 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 (manufactured by Momentive Performance Materials Japan LLC) and the like. Can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florade (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543. R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

Examples of the silicone-based surfactant further include a silicone-based surfactant having a fluorine atom. Examples of the silicone-based surfactant having a fluorine atom include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass in the total amount of the colored photosensitive resin composition. Or less, more preferably 0.005 mass% or more and 0.05 mass% or less. The content of the pigment dispersant is not included in this content.

<Antioxidant (J)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like can be used. You may use 2 or more types of antioxidants.
As the phenolic antioxidant, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corp.), Irganox 1076. (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Ltd.), Irganox 1330 (Irganox 1330:3,3′,3″,5). , 5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corp., Irganox 3114. (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione , BASF Corporation, Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine. -2,4,6(1H,3H,5H)-trione, manufactured by BASF Ltd., Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxy). (Phenyl)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, BASF). Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Ltd.), Irganox 3125 (Irganox 3125, manufactured by BASF Ltd.), Irga Knox 565 (Irganox 565:2,4-bis(n-octylthio)-6-(4-hydroxy3′,5′-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation) Adekastab AO-80 (Adekastab AO-80:3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)- 2,4,8,10-Tetraoxaspiro(5,5)undecane, ADEKA Corporation ), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.) and the like.
Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Ltd.), Irgafos 12 (Irgafos 12: Tris[2-[[[2 , 4,8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Ltd., Irgafos 38 ( Irgafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Ltd., Adekastab 329K (manufactured by ADEKA), Adekastab PEP36 ( ADEKA Corporation, ADEKA STAB PEP-8 (made by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE). , Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10. -Tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.
Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkylmercaptopropionate ester compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. Is mentioned.

<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 anticoagulant, an organic acid, an organic amine compound, and a curing agent. It is also possible to use additives such as agents.

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

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

As the adhesion promoter, 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 thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. The 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is an example of a cyclic ether structure-containing component having 2 to 4 carbon atoms.

Examples of the ultraviolet absorber include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone. Compounds; 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; and the like.

Examples of the aggregation preventing agent include sodium polyacrylate and the like.

Organic acid is used for adjusting the developability, and specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid and other aliphatic dicarboxylic acids;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanoic acid and pyromellitic acid; and the like.

As the 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;
Dicycloalkylamine 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 and 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. ;
A monocycloalkanolamine such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
A dicycloalkanolamine such as di(4-cyclohexanol)amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine and 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 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanediols;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol and 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 and 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 alcohol 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 and p-diethylaminophenol;
Aminobenzoic acid such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid;

Examples of the curing agent include a compound capable of reacting with a carboxy group in the resin (B) to crosslink the resin (B) when heated, a compound capable of being polymerized alone to cure a colored pattern, and the like. , Epoxy compounds, oxetane compounds and the like.

Here, as the epoxy compound, a bisphenol A-based epoxy resin, a hydrogenated bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a hydrogenated bisphenol F-based epoxy resin, a novolac-type epoxy resin, another aromatic-based epoxy resin, an oil Epoxy resins such as cyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, brominated derivatives of these epoxy resins, epoxy resins and fats other than their brominated derivatives Group, alicyclic or aromatic epoxy compound, epoxide of (co)polymer of butadiene, epoxidized product of (co)polymer of isoprene, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate Etc.
Examples of commercially available epoxy resins include orthocresol novolac type epoxy resin, "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 cyclohexanedicarboxylic acid bisoxetane.

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. Examples of the compound include polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like.

As a polycarboxylic 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′-benzophenonetetra Aromatic polycarboxylic acid such as carboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and 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 polyvalent carboxylic acid such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As the polycarboxylic acid anhydride,
Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride, pyromellitic dianhydride, trimellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic acid 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 polyvalent carboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride and nadic acid anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bis trimellitate acid and glycerin tris trimellitate anhydride; and the like.

As the carboxylic acid anhydride, one commercially available as a curing agent for epoxy resin may be used. As a curing agent for epoxy resin, a trade name "ADEKA HARDNER (registered trademark) EH-700" (manufactured by ADEKA), a trade name "RIKACID (registered trademark) HH" (manufactured by Shin Nippon Rika Co., Ltd.), a commodity The name "MH-700" (manufactured by Shin Nippon Rika Co., Ltd.) and the like can be mentioned.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosyl Rate etc. are mentioned.
The curing agents may be used alone or in combination of two or more.

<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 aid (D1), the antioxidant (J), and other components.

<Method of manufacturing color filter>
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, 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 photolithographic method, a colored coating film that is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing. The colored pattern or the colored coating film thus formed can be used as the color filter of the present invention.

Examples of the substrate include quartz glass, borosilicate glass, alumina silicate glass, glass plate such as silica-coated soda lime glass, resin plate such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, silicon, and the above substrate. Aluminum, silver, silver/copper/palladium alloy thin film, etc. are used. Other color filter layers, resin layers, transistors, circuits and the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or commonly used apparatus and conditions. For example, it can be manufactured as follows.
First, the colored photosensitive resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.
30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
When performing drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.
The thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As a light source used for exposure, a light source that emits light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. 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 stepper because it can irradiate parallel light rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred.
A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide. 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 a paddle method, a dipping method, a spray method or 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 perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking 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, it is preferable that the coating film be as thin as possible. Especially when a thick film is used, light from a light source may leak through pixels of two or more colors when a liquid crystal panel is manufactured. May be lost. The coating film after post-baking is preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the coating film is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more.

Further, the higher the brightness of the coating film is, the more preferable it is, it is preferably 38.5 or more, more preferably 39 or more, and the upper limit is not particularly limited, but it is usually 70 or less.

The colored coating film and the colored pattern formed by the colored photosensitive resin composition of the present invention are useful as a color filter. The color filter is used as a color filter used in a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

Synthesis example 1
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flushed with an appropriate amount of nitrogen to replace the atmosphere with nitrogen, 280 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Subsequently, 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 by mass of propylene glycol monomethyl ether acetate. Part of the mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution of 33 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) 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 kept at the same temperature for 4 hours, then cooled to room temperature, and had a B-type viscosity (23° C.) of 125 mPa·s, a solid content of 37.0 mass %, and a solution acid value of 27 mg-KOH/g. Was obtained (hereinafter sometimes referred to as resin solution (B1)). The produced copolymer had a weight average molecular weight Mw of 9,200 and a polydispersity of 2.08. The obtained copolymer showed almost no absorption at 500 to 600 nm.

The polystyrene-converted weight average molecular weight Mw and number average molecular weight Mn of the resin obtained in the above Synthesis Example were measured by the GPC method under the following conditions.
Device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40°C
Solvent: Tetrahydrofuran [THF]
Flow rate: 1.0 mL/min
Test liquid solid content concentration: 0.001-0.01 mass%
Injection volume: 50 μL
Detector ；RI
Calibration standard; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

[Preparation of Pigment Dispersion A-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 to prepare a pigment dispersion liquid. (A-1) was obtained.
Here, the polyhalogenated zinc phthalocyanine (a1) was synthesized by the method described in Japanese Patent No. 4368157.
The obtained polyhalogenated zinc phthalocyanine (a1) contained an average of 10 bromine atoms in one molecule according to the halogen content analysis by mass spectrometry.
When the spectral spectrum of the above polyhalogenated zinc phthalocyanine (a1) was measured by the following procedure, the wavelength of maximum transmittance was 515 nm.
〔Measurement procedure〕
A composition in which the concentration of the polyhalogenated zinc phthalocyanine (a1) in the solid content was 30 mass% was prepared by mixing the pigment dispersion A-1 and the resin solution (B1). The composition obtained was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by a spin coating method, prebaked at 100° C. for 3 minutes, and then cooled. Further, the obtained film was post-baked in an oven at 230° C. for 30 minutes to obtain a coating film. The transmittance (T1) of the coating film is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation, light source: halogen lamp, pinhole diameter 50 μm).
Further, the transmittance (T2) of the coating film prepared by the same procedure as that of the coating film except that the polyhalogenated zinc phthalocyanine (a1) was not contained was measured under the same conditions as above.
Then, the spectral transmittance spectrum was created from a value (=T1-T2) obtained by subtracting (T2) from the transmittance (T1).

[Preparation of Pigment Dispersion Liquid A-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 to obtain a pigment dispersion liquid (A-2). Got
C. I. Pigment Green 58 was found to contain an average of 14 bromine atoms in one molecule according to the halogen content analysis by mass spectrometry.
When the color measurement was performed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) in the same manner as in the case of the pigment dispersion A-1, the wavelength of maximum transmittance was 525 nm.

[Preparation of Pigment Dispersion A-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 to obtain a pigment dispersion (A-3). Got

[Preparation of Pigment Dispersion Liquid A-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 is sufficiently dispersed using a bead mill to give a pigment dispersion (A- 4) was obtained.

[Preparation of Pigment Dispersion Liquid A-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 to obtain a pigment dispersion liquid (A-5). Got

[Preparation of Pigment Dispersion Liquid A-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 to prepare a pigment dispersion liquid (A-6). Got

Examples 1-10 and Comparative Examples 1-4
[Preparation of colored photosensitive resin composition]
The components shown in Tables 8 to 9 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 the “solid content (%)” in Tables 8 to 9.

In Tables 8-9, each component is as follows.
Coloring dispersant (A1); Pigment dispersion (A-1) obtained above
Coloring dispersant (A2); Pigment dispersion (A-2) obtained above
Coloring dispersant (A3); Pigment dispersion (A-3) obtained above
Coloring dispersant (A4); Pigment dispersion (A-4) obtained above
Coloring dispersant (A5); Pigment dispersion (A-5) obtained above
Coloring Dispersant (A6); Pigment Dispersion Liquid (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)octan-1-one-2-imine (Product name: Irgacure OXE01; BASF Co.; O-acyl oxime compound)
Polymerization initiator (D2); Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (Product name: Irgacure OXE02; Manufactured by BASF; O-acyl oxime compound)
Polymerization initiator (D3); compound represented by formula (1A) (prepared by the method described in Japanese Patent Publication No. 2011-132215)

Leveling agent (F1); polyether modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Fabrication of pattern]
The colored photosensitive resin composition was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100° C. for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an atmosphere of air with an interval between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask having a pattern being 100 μm. , 150 mJ/cm ² light exposure (365 nm standard). As the photomask, a mask on which a 50 μm line and space pattern was formed was used. After the light irradiation, the coating film is immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24° C. for 60 seconds to develop, washed with water, and then in an oven at 230° C. Post-baking was performed for 30 minutes to obtain a pattern.

[Film thickness measurement]
The film thickness FT (μm) of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 8-9. In the table, the case where the film thickness is 3 μm or less is “◯”, and the case where the film thickness exceeds 3 μm is “X”.

[Chromaticity evaluation]
With respect to the obtained pattern, the spectrum is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corp.), and the xy chromaticity coordinates (in the XYZ color system of CIE using the characteristic function of the C light source). x, y) and lightness Y were measured. The results are shown in Tables 8-9. In the table, when the lightness was 38.5 or more, it was designated as "O", and when it was less than 38.5, it was designated as "X".

[Pattern shape]
The obtained pattern was observed with an optical microscope (magnification: 500 times), and when the end of the pattern was a straight line, it was evaluated as “◯”, and when it was jagged due to chipping or the like, it was evaluated as “x”. The results are shown in Tables 8-9.

From the colored photosensitive resin composition of the present invention, a thin film color filter having a good pattern shape and high brightness can be produced. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (8)

Contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As the colorant (A), a polyhalogenated zinc phthalocyanine containing an average of less than 13 bromine atoms in one molecule and having a maximum transmittance of 500 to 520 nm in a spectral transmittance spectrum at 380 to 780 nm. A colored photosensitive resin composition comprising (a1) and a blue dye. The colored photosensitive resin composition according to claim 1, further comprising a green pigment other than the polyhalogenated zinc phthalocyanine (a1) as the colorant (A). As the colorant (A), C.I. I. The colored photosensitive resin composition according to claim 1, which contains Pigment Green 58. The blue dye is C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6, and at least one kind selected from 60, The colored photosensitive resin composition according to any one of claims 1 to 3. The blue dye is C.I. I. Pigment Blue 15:3 and at least one kind selected from 15:4, The colored photosensitive resin composition according to any one of claims 1 to 4. A coating film formed from the colored photosensitive resin composition according to claim 1. A color filter formed from the colored photosensitive resin composition according to claim 1. A display device including the color filter according to claim 7.