TWI737597B - Colored photosensitive resin composition, coating film, color filter, and display device - Google Patents

Abstract

The object of the present invention is to provide a colored photosensitive resin composition that can be used as a thin film and has a clear pattern shape and a high brightness color filter.

The colored photosensitive resin composition of the present invention is characterized by containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and contains a polyhalogenated zinc phthalocyanine (a1), And blue pigment as the above-mentioned coloring agent (A), the polyhalogenated zinc phthalocyanine (a1) contains an average of less than 13 bromine in one molecule, and the maximum transmittance in the spectral transmittance spectrum under 380~780nm The wavelength is 500~520nm.

Description

Colored photosensitive resin composition, coating film, color filter, and display device

The present invention relates to a colored photosensitive resin composition.

In recent years, the development of display monitors to expand the color reproduction range that can be displayed is promoted. As part of the development, color filters are also required to have denser colors. In order to meet this requirement, a method of increasing the colorant concentration in the color filter can be cited. However, if the colorant concentration increases, the pattern shape deteriorates and the performance as a colored photosensitive resin composition deteriorates, which is not good. In addition, in order to have the target color characteristics, the color filter must be made as a thick film. However, when applied to a liquid crystal display device, color mixing with the light of adjacent pixels occurs, so the thick film is not good.

In Patent Document 1, it is described that in order to design a dense green color filter, a coloring agent including CI Pigment Green 58, CI Pigment Blue 15:3, CI Pigment Yellow 150, etc., resin, polymerizable monomer, light Green photosensitive resin composition of polymerization initiator and solvent.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-247539

Therefore, the present invention aims to provide a colored photosensitive resin composition that can be used as a thin film and has a good pattern shape and a high brightness color filter.

That is, the colored photosensitive resin composition of the present invention has the following points.

[1] A colored photosensitive resin composition characterized by containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and containing a polyhalogenated zinc phthalocyanine ( a1), and blue pigment as the above coloring agent (A), the polyhalogenated zinc phthalocyanine (a1) contains an average of less than 13 bromine in one molecule, and transmits in the spectral transmittance spectrum under 380~780nm The wavelength at which the rate becomes the largest is 500~520nm.

[2] The colored photosensitive resin composition as described in [1], which further contains a green pigment other than the polyhalogenated zinc phthalocyanine (a1) as the colorant (A).

[3] The colored photosensitive resin composition as described in [1], which further contains C.I. Pigment Green 58 as the colorant (A).

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the blue pigment is selected from CI Pigment Blue 15, 15:3, 15:4, 15:6, And at least one of 60.

[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the blue pigment is at least one selected from C.I. Pigment Blue 15:3 and 15:4.

[6] A coating film formed of the colored photosensitive resin composition as described in any one of [1] to [5].

[7] A color filter formed of the colored photosensitive resin composition as described in any one of [1] to [5].

[8] A display device comprising the color filter as described in [7].

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

The colored photosensitive resin composition of the present invention is characterized in that it contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and contains a polyhalogenated zinc phthalocyanine (a1) And a blue pigment as the above-mentioned coloring agent (A). 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 if it is a film.

In addition, the compound exemplified as each component in this specification can be used alone or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The colored photosensitive resin composition of the present invention contains as a coloring agent (A) a polyhalogenated zinc phthalocyanine (a1) and a blue pigment as essential components.

Polyhalogenated zinc phthalocyanine (a1) contains an average of less than 13 bromines in one molecule, and in the spectral transmittance spectrum at 380~780nm, the wavelength at which the transmittance becomes the maximum is 500~520nm. The above-mentioned bromine number can be quantified by halogen content analysis by mass spectrometry.

The above-mentioned spectral transmittance spectrum is a spectrum representing the following value: subtracted from the light transmittance (T1) measured by the colorimeter of the coating film (thickness 2μm) of the polyhalogenated zinc phthalocyanine (a1) produced in the following order The value (=T1-T2) obtained by measuring the transmittance value (T2) of the coating film produced in the same order as the above coating film except that it does not contain the polyhalogenated zinc phthalocyanine (a1).

Examples of this color measuring machine include OSP-SP-200 (manufactured by Olympus Co., Ltd.) and the like. This measurement is typically performed with a halogen lamp as a light source and the pinhole diameter is about 50 μm.

[Coating film production method]

Resin and pigment are prepared by mixing polyhalogenated zinc phthalocyanine (a1) and epoxy resin solution [resin concentration: about 30-40% by mass, solvent: ether ester solvent (propylene glycol monomethyl ether acetate, etc.)] The ratio of the pigment in the total amount is 30% by mass of the composition. Furthermore, at 2 English The composition was coated on a square glass substrate, and the obtained coating film was pre-baked at 100°C for 3 minutes, and temporarily cooled to room temperature, and then post-baked at 230°C for 30 minutes.

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

Polyhalogenated zinc phthalocyanine (a1) can be distinguished from C.I. Pigment Green 7, C.I. Pigment Green 58 in terms of the number of bromine in the molecule and the wavelength at which the transmittance becomes the maximum.

C.I. Pigment Green 7 is chlorinated copper phthalocyanine with no bromine in the molecule, and C.I. Pigment Green 58 contains an average of 14 bromine in the molecule. In addition, when the maximum transmittance spectrum of the coating film is 90%, CI Pigment Green 58 shows the maximum transmittance in the range of more than 520nm~530nm, and 50% of the transmittance in the range of 570~575nm. Rate. On the other hand, polyhalogenated zinc phthalocyanine (a1) shows the maximum transmittance in the range of 500~520nm, and 50% transmittance in the range of 560~565nm.

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

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

The polyhalogenated zinc phthalocyanine (a1) is preferably used in the state of a dispersion (pigment dispersion) uniformly dispersed in a solvent. The dispersion (pigment dispersion) can be used by adding the polyhalogenated zinc phthalocyanine (a1) Obtained by mixing in a solvent. The dispersant can also be mixed as needed.

The dispersant may be any of cationic, anionic, nonionic, and amphoteric dispersants, and examples of dispersants such as polyester, polyamine, and acrylic.

These dispersants may be used alone or in combination of two or more kinds. As decentralized Agents can be listed as trade names: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Corporation), Ajisper (manufactured by Ajinomoto Fine -Techno (manufactured by shares), Disperbyk (manufactured by BYK-Chemie), etc.

When the dispersant is contained in the above-mentioned pigment dispersion, the content of the dispersant in the pigment dispersion is preferably 100 parts by mass or less, and 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. . If the content of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in which the polyhalogenated zinc phthalocyanine (a1) is uniformly dispersed in the solvent.

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, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., More preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3- Ethoxy ethyl propionate and so on.

The solvent is preferably used in a manner that can adjust the solid content concentration in the pigment dispersion to 3-20% by mass, more preferably 5-18% by mass.

As blue pigments, blue pigments and blue dyes can be cited.

As the blue pigment, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. can be exemplified.

Examples of blue dyes include: CI 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, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139 and other CI solvent blue dyes; CI 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 other CI acid blue dyes; CI 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, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and other CI direct blue dyes; CI disperse blue CI disperse blue dyes such as 1, 14, 56, 60; CI basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, CI basic blue dyes such as 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 3 1, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 C.I. Mordant blue dye, etc.

Among them, the blue pigment is preferably a blue pigment, more preferably at least one selected from CI Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60, and more preferably selected from At least one of CI Pigment Blue 15:3 and 15:4.

Furthermore, as the coloring agent (A), a pigment (sometimes called "second pigment") and/or dye (sometimes called "second dye") may be contained as a polyhalogenated zinc phthalocyanine (a1) And coloring agents other than blue pigments (sometimes referred to as "second coloring agents").

Examples of the second pigment include organic and inorganic pigments other than the polyhalogenated zinc phthalocyanine (a1) and the above-mentioned blue pigment. Examples include compounds classified as pigments in the Dye Index (published by The Society of Dyers and Colourists) .

Examples of organic pigments include: CI 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, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments ; CI Pigment Green 7, 36, 58 and other green pigments other than polyhalogenated zinc phthalocyanine (a1); etc.

The second pigment is preferably a green pigment other than the polyhalogenated zinc phthalocyanine (a1), more preferably C.I. Pigment Green 7, 36, 58, and even more preferably C.I. Pigment Green 58.

Moreover, it is preferable to contain a yellow pigment as a 2nd pigment. As the yellow pigment, more preferably at least one selected from C.I. Pigment Yellow 138, 139, 150, and 185, more preferably C.I. Pigment Yellow 138 or 185, and even more preferably C.I. Pigment Yellow 185.

Two or more types of the second pigment can also be used.

The above-mentioned pigments can also be subjected to rosin treatment, surface treatment using pigment derivatives or pigment dispersants introduced with acidic or basic groups, grafting treatment of the pigment surface by polymer compounds, etc., and the use of sulfuric acid particles. Micronization treatment by chemical method, etc., or cleaning treatment and separation by organic solvent or water to remove impurities Sub-impurities are removed by ion exchange methods, etc. In addition, the pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, commercially available surfactants can be used, including: silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic Department of surfactants and so on. As the above-mentioned surfactants, in addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines In addition to modified polyurethanes, polyethyleneimines, etc., trade names can also be listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse ( Zeneca (manufactured by shares), EFKA (manufactured by BASF Japan (shares)), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno (shares)), Disperbyk (manufactured by BYK-Chemie), etc. These can be used individually, respectively, and can also be used in combination of 2 or more types.

When the pigment dispersion liquid contains a pigment dispersant, its content is preferably 100 parts by mass or less, and more preferably 5-50 parts by mass relative to 100 parts by mass of the pigment. If the content of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、次甲基偶氮染料、方酸鎓染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。於該等中，較佳為有機溶劑可 溶性染料。 As the above-mentioned second dye, known dyes other than the above-mentioned blue dye can be used, and examples thereof include solvent dyes (organic solvent-soluble dyes), acid dyes, direct dyes, and mordant dyes. Examples of dyes include: compounds classified as having a hue in addition to pigments in the Dyes Index (published by The Society of Dyers and Colourists), or known dyes described in the dyeing notes (Sei Dyers Society) except for blue Dyes other than dyes. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes,

Dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, methine azo dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, Quinoline dyes and nitro dyes, etc. Among them, organic solvent-soluble dyes are preferred.

Regarding the content of the polyhalogenated zinc phthalocyanine (a1), in 100% by mass of the colorant (A), it is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, and further More preferably, it is 20% by mass or more. In addition, the content of 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, or 30% by mass or less .

In the case of containing green pigments other than polyhalogenated zinc phthalocyanine (a1), the content of green pigments other than polyhalogenated zinc phthalocyanine (a1) is relative to 100 parts by mass of polyhalogenated zinc phthalocyanine (a1), Preferably it is 1 part by mass or more, more preferably 10 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 4000 parts by mass or less It is more preferably 1000 parts by mass or less, still more preferably 300 parts by mass or less, even if it is 100 parts by mass or less.

Regarding the content of the blue pigment (the total of the blue pigment and the blue dye, preferably the blue pigment), relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1), preferably 0.001 to 300 parts by mass, more preferably It is 0.05-100 parts by mass, more preferably 0.1-20 parts by mass, and particularly preferably 1-20 parts by mass.

Regarding the total content of the yellow pigment, relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine (a1), it is preferably 1 to 1000 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 10 to 80 parts by mass, and further More preferably, it is 10-40 parts by mass.

Regarding the total content of the coloring agent (A), in 100% by mass of the solid content of the colored photosensitive resin composition, it is preferably 20-60% by mass, more preferably 25-50% by mass, and still more preferably 35 ~50% by mass.

Furthermore, 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, and more preferably 50% by mass or less , And more preferably 10% by mass or less.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin, preferably having at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)") The polymer of structural unit.

The copolymer having the structural unit derived from the above (a) preferably has a monomer (b) selected from the group consisting of a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (hereinafter sometimes referred to as A copolymer of at least one of the group consisting of the structural unit of "(b)") and the structural unit having an ethylenically unsaturated bond. The copolymer may further have other structural units. As another structural unit, the structural unit derived from the monomer (c) which can be copolymerized with (a) (However, it is different from (a) and (b). Hereinafter, it may be called "(c)") is mentioned.

As resin (B), the following resin [K1]~[K6] etc. are mentioned.

Resin [K1] has a copolymer of structural units derived from (a) and structural units derived from (b).

The resin [K2] has a copolymer of structural units derived from (a), structural units derived from (b), and structural units derived from (c).

Resin [K3] has a copolymer of structural units derived from (a) and structural units derived from (c).

The resin [K4] has a polymer having a structural unit formed by reacting (b) and a structural unit derived from (a) (preferably an addition).

The resin [K5] has a polymer having a structural unit obtained by reacting (a) and a structural unit derived from (b) (preferably an addition).

Resin [K6] has a structural unit derived from (a) and a structural unit derived from (b) (preferably addition), and further reacted with a carboxylic anhydride (preferably addition), and derived from (c ) Is a copolymer of structural units.

烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物類；順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐(雙環庚烯二甲酸酐)等不飽和二羧酸類酐；丁二酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸之類的於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 As (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid; Acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5- drop

Ene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 -Alkenes, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic acid anhydride) and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2- Unsaturated mono [(methyl) of polycarboxylic acid with more than two valences, such as (meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl]ester, etc. Acrylic oxyalkyl] esters; α-(hydroxymeth)acrylic acid and other unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among them, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred in terms of copolymerization reactivity or solubility in alkaline aqueous solution.

(b) It refers to a cyclic ether structure with a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring) 1) and polymerizable compounds of ethylenically unsaturated bonds, preferably (b) is a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloxy group.

In addition, in this specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include: monomer (a1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond Bond monomer (b2) (hereinafter sometimes referred to as "(b2)"), monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

Regarding (b1), examples include: monomers (b1-1) having a structure obtained by epoxidizing unsaturated aliphatic hydrocarbons (hereinafter sometimes referred to as "(b1-1)"), and monomers having a structure obtained by epoxidizing unsaturated aliphatic hydrocarbons; The monomer (b1-2) of the structure formed by epoxidation of a hydrocarbon of the formula (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, and glycidyl vinyl ether , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)benzene Ethylene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)benzene Ethylene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidoxymethyl) Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

Examples of (b1-2) include: vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl) 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd.) ) Manufacturing), the compound represented by the formula (I), the compound represented by the formula (II), etc.

[化1]

[In the formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group of which may be substituted with a hydroxyl group.

X ¹ and X ² independently represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Indicates the bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, and the like.

Examples of alkyl groups in which hydrogen atoms are substituted with hydroxy groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

As R ^a and R ^b, preferred include a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably include a hydrogen atom, a methyl group.

Examples of alkanediyl groups include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5 -Diyl, hexane-1,6-diyl, etc.

Examples of X ¹ and X ² preferably include a single bond, a methylene group, an ethylene group, *-CH ₂ -O- (* represents a bond with O) group, and * -CH ₂ CH ₂ -O- Group, more preferably single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15), and the like. Preferably can enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)~Formula (I-15). More preferably, formula (I-1), formula (I-7), formula (I-9), and formula (I-15) can be cited.

As the compound represented by formula (II), compounds represented by formula (II-1) to formula (II-15) and the like can be mentioned. Preferably can enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) ~ formula (II- 15). More preferably, formula (II-1), formula (II-7), formula (II-9), Formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used independently, respectively. In addition, these can be mixed in any ratio. In the case of mixing, the mixing ratio in terms of molar ratio is preferably Formula (I): Formula (II) is 5:95~95:5, more preferably 10:90~90:10. Preferably, it is 20:80 to 80:20.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methylpropenyloxyethyl oxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

The monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuran group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含有羥基之(甲基)丙烯酸酯類； 順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯；雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (c) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and third (meth)acrylate Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technology It is called "dicyclopentyl (meth)acrylate" as a common name in the field. Also, it is sometimes called "tricyclodecyl (meth)acrylate") and tricyclo (meth)acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (called "dicyclopentenyl (meth)acrylate" as a common name in this technical field), dicyclopentyloxyethyl (meth)acrylate, (Meth) acrylic iso

Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth) (Meth)acrylates such as benzyl acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other (meth)acrylates containing hydroxyl groups; maleic acid Diethyl ester, diethyl fumarate, diethyl itconate and other dicarboxylic acid diesters; 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 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[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-tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1 ]Hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, N-butanediimino-3-maleimide benzoate, N-butanedi Amino-4-maleiminobutyrate, N-butanediimidinyl-6-maleiminohexanoate, N-butanediimidinyl-3 -Dicarbonyliminium derivatives such as maleimide propionate and N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methyl Styrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate , 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among them, in terms of copolymerization reactivity and heat resistance, benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleic Amide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo[2.2.1]hept-2-ene, etc. Moreover, in terms of excellent developability when forming a pattern, (meth)acrylic is more preferable Benzyl acid, tricyclodecyl (meth)acrylate.

In the resin [K1], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K1].

Structural unit derived from (a): 2~50 mol% (more preferably 10~45 mol%)

The structural unit derived from (b), especially the structural unit derived from (b1): 50~98 mol% (more preferably 55~90 mol%)

If the ratio of the structural unit of the resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.

Resin [K1] can refer to the method described in the literature "Experimental method of polymer synthesis" (Otsu Takayuki Publishing Co., Ltd., the first edition of the chemical doujin first edition, issued on March 1, 1972) and the literature Manufactured by the cited literature.

Specifically, a method of adding specific amounts of (a) and (b) (especially (b1)), polymerization initiator, solvent, etc. to the reaction vessel and stirring, heating, and insulating in a deoxygenated environment can be cited . In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and can be used for any of ordinary users in the field. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (Benzyl peroxide, etc.) As the solvent, any one that dissolves each monomer may be used, and the solvent (E) described below as a solvent for the colored photosensitive resin composition can be used.

Furthermore, the obtained copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) extracted by methods such as reprecipitation can also be used. In particular, since the following solvent (E) is used as the solvent during the polymerization, the solution after the reaction can be used as it is, and the production steps can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].

Structural unit derived from (a): 4~45 mol% (more preferably 10~30 mol%)

The structural unit derived from (b), especially the structural unit derived from (b1): 2~95 mol % (Preferably 5~80 mol%)

Structural unit derived from (c): 1~65 mol% (more preferably 5~60 mol%)

If the ratio of the structural units of the resin [K2] is within the above range, the storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern tend to be excellent.

The resin [K2] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1].

Specifically, the specific amounts of (a), (b) (especially (b1)) and (c), polymerization initiator and solvent are added to the reaction vessel and stirred, heated, and heated in a deoxygenated environment. Method of heat preservation. The obtained copolymer can be directly used as a solution after the reaction, can be used as a concentrated or diluted solution, or can be extracted in the form of a solid (powder) by reprecipitation or other methods.

In the resin [K3], the ratio of the structural units derived from each is preferably within the following range among 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): 45~98 mol%, more preferably 50~90 mol%

The resin [K3] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1].

Resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and making the cyclic ether with 2 to 4 carbon atoms in (b), especially the oxirane ring in (b1) It is produced by addition with carboxylic acid and/or carboxylic anhydride possessed by (a).

First, the copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the copolymer of (a) and (c).

Structural unit derived from (a): 5~50 mol%, more preferably 10~45 mol%

Structural unit derived from (c): 50~95 mol%, more preferably 55~90 mol%

Secondly, make the cyclic ether with 2 to 4 carbon atoms in (b), especially the ring in (b1) The oxyethane ring reacts with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above-mentioned copolymer.

Following the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and the reaction catalyst of (b) (especially (b1)), carboxylic acid or carboxylic anhydride and cyclic ether (For example, tris(dimethylaminomethyl)phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) are added to the flask and reacted at 60~130℃ for 1~10 hours to obtain resin [K4].

Regarding the usage amount of (b), especially the usage amount of (b1), relative to (a) 100 mol, it is preferably 5 to 80 mol, and more preferably 10 to 75 mol. By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become favorable. Regarding (b), which has high reactivity of the cyclic ether and is unlikely to remain unreacted, (b) for the resin [K4] is preferably (b1), and more preferably (b1-1).

The amount of the reaction catalyst used is preferably 0.001 to 5% by mass relative to the total amount of (a), (b) (especially (b1)), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass relative to the total amount of (a), (b), and (c).

The reaction conditions such as the addition method, reaction temperature and time can be appropriately adjusted in consideration of the manufacturing equipment or the heat generated by the polymerization. In addition, the method of addition or the reaction temperature can be appropriately adjusted in consideration of the manufacturing equipment or the amount of heat generated by the polymerization in the same manner as the polymerization conditions.

Regarding the resin [K5], as the first stage, the copolymer of (b) (especially (b1)) and (c) is obtained in the same manner as the above-mentioned resin [K1] manufacturing method. Similar to the above, the obtained copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) extracted by reprecipitation or the like can also be used.

The ratio of the structural units derived from (b) (especially (b1)) and (c) is preferably within the following range with respect to the total number of moles of all the structural units constituting the above-mentioned copolymer.

The structural unit derived from (b), especially the 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%)

Furthermore, under the same conditions as the production method of resin [K4], the source of the carboxylic acid or carboxylic anhydride contained in (a) and the copolymer of (b) (especially (b1)) and (c) By reacting from the cyclic ether of (b), resin [K5] can be obtained.

The usage amount of (a) reacted with the above-mentioned copolymer is preferably 5 to 80 mol relative to (b) (especially (b1)) 100 mol. Regarding (b), which has high reactivity of the cyclic ether and is unlikely to remain unreacted, (b) for the resin [K5] is preferably (b1), and more preferably (b1-1).

Resin [K6] is a resin formed by further reacting carboxylic anhydride and resin [K5]. The carboxylic acid anhydride is reacted with the hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetra Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]heptan-2- Acrylic anhydride (bicycloheptene dicarboxylic acid anhydride) and the like.

Among the resins [K1]~[K6], the preferred resin is [K1] or [K2].

These resins may be used alone or in combination of two or more kinds.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, the solubility of the unexposed part in the developer is higher, and the residual film rate or hardness of the obtained pattern tends to be higher.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

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

Regarding the content of the resin (B), the solid component of the colored photosensitive resin composition Among 100% by mass, it is preferably 5-50% by mass, more preferably 10-40% by mass, and still more preferably 15-30% by mass. If the content of the resin (B) is within the above range, the unexposed part tends to have higher solubility in the developer.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized using living radicals and the like generated by the polymerization initiator (D), and examples thereof include compounds having polymerizable ethylenic unsaturated bonds. 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 examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Esters, pentaerythritol deca(meth)acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra( Meth) acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified Pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like can be cited.

Regarding the content of the polymerizable compound (C), in the total solid content, it is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. 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 that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat.

化合物、醯基氧化膦化合物等。聚合起始劑(D)可僅使用1種，亦可使用2種以上。較佳之聚合起始劑(D)為O-醯基肟化合物。 Examples of the polymerization initiator (D) include: O-acyl oxime compounds, phenalkyl ketone compounds, biimidazole compounds, three

Compounds, phosphine oxide compounds, etc. 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 above-mentioned O-acyl oxime compound is a compound having a structure represented by formula (d). In the following, * means a bonding key.

As the above-mentioned O-acyl oxime compound, it is preferably selected from a compound represented by formula (d1) (hereinafter sometimes referred to as compound (d1)) and a compound represented by formula (d2) (hereinafter sometimes referred to as compound ( d2)) and at least one of the group consisting of the compound represented by the formula (d3) (hereinafter sometimes referred to as the compound (d3)).

[In formulas (d1)~(d3), R ^d1 represents an aromatic hydrocarbon group with 6 to 18 carbons which may have a substituent, a heterocyclic group with 3 to 36 carbons which may have a substituent, and a carbon which may have a substituent An alkyl group of 1 to 15 or an aralkyl group of 7 to 33 carbons that may have a substituent. The methylene group (-CH ₂ -) contained in the above-mentioned alkyl group or aralkyl group may be substituted with -O -, -CO-, -S-, -SO ₂ -or -NR ^d5 -.

R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbons, a heterocyclic group with 3 to 36 carbons, or an alkyl group with 1 to 10 carbons.

R ^d3 represents an optionally substituted aromatic hydrocarbon group with 6 to 18 carbons or an optionally substituted heterocyclic group with 3 to 36 carbons.

R ^d4 represents an optionally substituted aromatic hydrocarbon group with 6 to 18 carbons or an optionally substituted aliphatic hydrocarbon group with 1 to 15 carbons, and the methylene group (-CH ₂ -) contained in the above aliphatic hydrocarbon group Can be substituted with -O-, -CO- or -S-, the methine group (-CH<) contained in the aliphatic hydrocarbon group can be substituted with -PO ₃ <, the hydrogen contained in the aliphatic hydrocarbon group Atoms can be substituted with OH groups.

R ^d5 represents an alkyl group with 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the alkyl group may be substituted with -O- or -CO-]

If the colored photosensitive resin composition of the present invention contains the O-acetoxime compound of formula (d1) to formula (d3), it is possible to produce a coating film with a pattern having a higher brightness and an excellent shape. In terms of making the shape of the obtained pattern good, the content of the O-acetoxime compound of formula (d1) to formula (d3) is preferably 0.5% by mass or more in 100% by mass of the solid content, more preferably It is 1% by mass or more, and more preferably 2% by mass or more. In terms of improving the brightness of the obtained coating film, the content is preferably 15% by mass or less in 100% by mass of the solid content, more preferably 12% by mass or less, and still more preferably 10% by mass or less.

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6-15, more preferably 6-12, and still more preferably 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a tertphenyl group, and the like. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.

In addition, ^{the aromatic hydrocarbon group represented by R d1} may have one or two or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl. Alkyl groups with 1 to 15 carbon atoms such as tetradecyl, tetradecyl, and pentadecyl; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom.

The carbon number of the alkyl group as the above-mentioned substituent is preferably 1-10, more preferably 1-7. The alkyl group as the substituent may be any of linear, branched, and cyclic, and may be a combination of a chain group and a cyclic group. _{The methylene group (-CH 2} -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. In addition, 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.

Regarding ^{the alkyl group as the substituent of the aromatic hydrocarbon group represented by R d1} , a group represented by the following formula and the like can be exemplified. In the formula, * represents the bonding bond.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^{d1 include groups represented by the following formula.} In the formula, * represents the bonding bond.

The optionally substituted aromatic hydrocarbon group 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 the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. m2 represents an integer from 1 to 5]

As the alkyl group represented by R ^d6, include an aromatic hydrocarbon group of R ^d1, as represented by the same substituent group of an alkyl group and a diagram of the embodiment. The carbon number of R ^d6 is preferably 2-7, more preferably 2-5. In addition, ^{the alkyl group represented by R d6} may be linear, branched, and cyclic, and is preferably chain.

Examples of the halogen atom that can replace ^{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 preferred. Furthermore, it is preferable ^{that 2 or more and 10 or less of the hydrogen atoms contained in R d6} are substituted with halogen atoms, and it is preferable that 3 or more and 6 or less are substituted with halogen atoms. The substitution position of the R ^d6 O- group is preferably the ortho position or the para position, and particularly preferably the para position.

In addition, m2 is preferably 1 to 2, and particularly preferably 1.

The carbon number of the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, and still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned.

In addition, ^{the heterocyclic group represented by R d1} may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by ^{R d1 may have.}

The carbon number of the alkyl group represented by R ^{d1 is preferably 1-12.} Examples of the alkyl group represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl , Tridecyl, tetradecyl and pentadecyl, etc. These alkyl groups may be any of linear, branched, and cyclic, and may be a group formed by combining a chain group and a cyclic group. In addition, in ^{the alkyl group represented by R d1} , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ -or -NR ^d5 -, and the hydrogen atom may be It is substituted with OH group or 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 chain (linear or branched) or cyclic, and it may be any of linear, branched, and cyclic, or it may be a combination of a chain group and a cyclic group. The base formed by the combination of shape base. In addition, in ^{the alkyl group of Rd5} , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

As ^{the alkyl group which may have a substituent represented by R d1} , specifically, the group represented by the following formula etc. are mentioned. * Indicates a bonding key.

Further, R ^d1 may have a substituent represented by the group of the aralkyl group is preferably an aromatic hydrocarbon group of R ^d1-derived and represented by the group R ^d1 represented by the combination of an alkoxy diyl group. The carbon number of the aralkyl group is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. The aralkyl group may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as ^{the aromatic hydrocarbon group represented by R d1} and the substituent that the alkyl group may have. As the aromatic hydrocarbon group represented by R ^d1 and the group derived therefrom by the R ^d1 alkanediyl group represented by the combination of the group, specific examples thereof include the groups represented by the following formula. In the formula, * represents the bonding bond.

R ^{d1 is} preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted alkyl group, more preferably an optionally substituted aromatic hydrocarbon group, and still more preferably an optionally substituted phenyl group. As the substituent in the above-mentioned aromatic hydrocarbon group and the above-mentioned 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~ Three methylene groups are substituted with alkoxy groups with 5-9 carbon atoms in the ether bond. These substituents preferably all have a branched structure.

The carbon number of the aromatic hydrocarbon group represented by R ^d2 is preferably 6-15, more preferably 6-12, and still more preferably 6-10. As this aromatic hydrocarbon group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, etc. are mentioned.

The carbon number of the heterocyclic group represented by R ^d2 is preferably 3-20, more preferably 3-10, and still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned.

The carbon number of the alkyl group represented by R ^d2 is preferably 1-7, more preferably 1-5, and still more preferably 1-3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group may be any one of linear, branched, and cyclic, and may be a combination of a chain group and a cyclic group.

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

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably 6-15, more preferably 6-12, and still more preferably 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a tertphenyl group, and the like, and a phenyl group and a naphthyl group are more preferable.

In addition, ^{the aromatic hydrocarbon group represented by R d3} may have one or two or more substituents. The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Alkyl groups with 1 to 15 carbons such as decyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl and other alkenes with 1 to 15 carbons Base and so on.

The carbon number of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by R ^d3 may have is preferably 1 to 7. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic, or The chain base and the cyclic base are combined to form a base. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) may be substituted with -N< .

As ^{the aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by Rd3} may have, the group represented by the following formula etc. are mentioned. In the formula, * represents the bonding bond.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^{d3 include groups represented by the following formula.} In the formula, * represents the bonding bond.

The carbon number of the heterocyclic group represented by R ^d3 is preferably 3-20, more preferably 3-10, and still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned.

In addition, ^{the heterocyclic group represented by R d3} may have one or two or more substituents, and examples of the substituent include the same as those exemplified as the substituents that the aromatic hydrocarbon group represented by ^{R d1 may have} base.

R ^{d3 is} preferably an aromatic hydrocarbon group having a substituent. As the substituent, a chain alkyl group having 1 to 7 carbon atoms (more preferably a carbon number 1 to 3) is preferred, and the number of substituents is preferably 2 or more and 5 or less.

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably 6-15, more preferably 6-12, and still more preferably 6-10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a tertphenyl group, and the like. A phenyl group and a naphthyl group are more preferable, and a phenyl group is still more preferable.

In addition, ^{the aromatic hydrocarbon group represented by R d4} may have one or two or more substituents. As this substituent, the same group as the substituent which the aromatic hydrocarbon group of ^{R d1 may have can be mentioned.}

The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, and still more preferably 4-9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Alkyl, tridecyl, tetradecyl and pentadecyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, Alkenyl groups such as decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl, etc. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In addition, in ^{the aliphatic hydrocarbon group of Rd4} , the methylene group (-CH ₂ -) can be substituted with -O-, -CO- or -S-, and the methine group (-CH<) can be substituted with -PO ₃ <, the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

As an ^{aliphatic hydrocarbon group which may have a substituent represented by R d4} , the group represented by the following formula etc. are mentioned. In the formula, * represents the bonding bond.

R ^{d4 is} preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group, and still more preferably a branched chain alkyl group.

Examples of the compound (d1) include the compound (d1-1) to the compound (d1-67) having the substituents described in the following table. In Tables 1~7, * represents a bonding key.

Among them, the compound represented by the formula (d1-3) ~ the compound represented by the formula (d1-6), the compound represented by the formula (d1-18) ~ the compound represented by the formula (d1-52), the formula The compound represented by (d1-55), the compound represented by formula (d1-56), the compound represented by formula (d1-60), the compound represented by formula (d1-61), more preferably the compound represented by formula (d1- 3) The compound represented by the formula (d1-6), the compound represented by the formula (d1-18), the compound represented by the formula (d1-41), and the compound represented by the formula (d1-24) The compound represented, the compound represented by the formula (d1-36) ~ the compound represented by the formula (d1-40), and the compound represented by the formula (d1-40) is particularly preferred.

The compound (d1) can be produced by the production method described in JP 2014-500852 A.

Compound (d2) is preferably the following compound: R ^d1 is an alkyl group with 1 to 15 carbon atoms, R ^d2 is an alkyl group with 1 to 10 carbon atoms, and R ^d3 is an alkyl group with 6 carbon atoms that may have a substituent ~18 aromatic hydrocarbon group, R ^d4 is an aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have substituents; more preferably the following compounds: R ^d1 represents methyl, ethyl or propyl, and R ^d2 represents methyl, ethyl or propyl group, R ^d3 represents a substituted phenyl group of methyl, R ^d4 is methyl, ethyl or propyl; further preferably R ^d1 and R ^d2 are methyl, R ^d3 is o-tolyl and R ^d4 It is an ethyl compound.

The compound (d3) is preferably a compound wherein R ^d1 is an optionally substituted alkyl group having 1 to 15 carbons and R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbons, more preferably R ^d1 is a hexyl group and R ^d2 is Phenyl compounds.

Examples of such O-oxime compounds include N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa Cyclopentylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2 -Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, a compound represented by the following formula, and the like.

[化18]

Commercial products such as Irgacure OXE01, Irgacure OXE02 (the above are manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) can also be used. In the case of these O-acetoxime compounds, there is a tendency to obtain color filters with excellent lithography performance.

The phenalkyl ketone 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.

啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲胺基-1-(4-

啉基苯基)-2-苄基丁烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]丁烷-1-酮等。亦可使用Irgacure 369、907、379(以上為BASF公司製造)等市售品。 Examples of the compound having the structure represented by formula (d4) include: 2-methyl-2-

Linyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4-

Linylphenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF) can also be used.

Examples of the compound having the structure represented by the formula (d5) include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 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 The oligomer, α,α-diethoxy acetophenone, benzyl dimethyl ketal, etc.

In terms of sensitivity, the phenalkyl ketone 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'-tetraphenyl Biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Japanese Patent Laid-Open No. 6-75373 etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl) Phenyl)-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 (for example, refer to Japan Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), 4,4',5,5'-position phenyl group substituted with alkoxycarbonyl group imidazole compound (for example, refer to Japanese Patent Kaiping No. 7-10913 Bulletin, etc.) and so on. Among them, preferred are compounds represented by the following formulae and mixtures thereof.

化合物，可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 As three

Compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

As the phosphine oxide compound, 2,4,6-trimethylbenzyldiphenyloxy Phosphine and so on.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; benzophenone, methyl phthalate , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)diphenyl Benzophenone compounds such as ketone, 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2- Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the following polymerization initiator (D1) (especially amines).

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

<Polymerization initiation aid (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to promote polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When it contains a polymerization initiator (D1), it is used in combination with a polymerization initiator (D).

化合物及羧酸化合物等。其中，較佳為9-氧硫

化合物。亦可含有2種以上之聚合起始助劑(D1)。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxysulfur

Compounds and carboxylic acid compounds, etc. Among them, 9-oxysulfur is preferred

Compound. It may also contain two or more kinds of polymerization initiation assistants (D1).

Examples of amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(di Methylamino)benzophenone (commonly known as Michele ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone ketone Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.

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

化合物，可列舉：2-異丙基9-氧硫

、4-異丙基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

、1-氯-4-丙氧基9-氧硫

等。 As 9-oxysulfur

Compounds include: 2-isopropyl 9-oxysulfur

, 4-isopropyl 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

, 1-Chloro-4-propoxy 9-oxysulfur

Wait.

Examples of carboxylic acid compounds include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methylbenzene Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

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

<Thiol Compound (T)>

The colored photosensitive resin composition of the present invention may also contain a thiol compound (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an O-acetoxime compound and/or a biimidazole compound. The thiol compound (T) is a compound having a mercapto group (-SH) in the molecule.

唑、2-巰基噻唑、2-巰基苯并咪唑、2-巰基苯并噻唑、2-巰基苯并

唑、2-巰基煙鹼酸、2-巰基吡啶、2-巰基吡啶-3-醇、2-巰基吡啶-N-氧化物、4-胺基-6-羥基-2-巰基嘧啶、4-胺基-6-羥基-2-巰基嘧啶、4-胺基- 2-巰基嘧啶、6-胺基-5-亞硝基-2-硫尿嘧啶、4,5-二胺基-6-羥基-2-巰基嘧啶、4,6-二胺基-2-巰基嘧啶、2,4-二胺基-6-巰基嘧啶、4,6-二羥基-2-巰基嘧啶、4,6-二甲基-2-巰基嘧啶、4-羥基-2-巰基-6-甲基嘧啶、4-羥基-2-巰基-6-丙基嘧啶、2-巰基-4-甲基嘧啶、2-巰基嘧啶、2-硫尿嘧啶、3,4,5,6-四氫嘧啶-2-硫醇、4,5-二苯基咪唑-2-硫醇、2-巰基咪唑、2-巰基-1-甲基咪唑、4-胺基-3-肼基-5-巰基-1,2,4-三唑、3-胺基-5-巰基-1,2,4-三唑、2-甲基-4H-1,2,4-三唑-3-硫醇、4-甲基-4H-1,2,4-三唑-3-硫醇、3-巰基-1H-1,2,4-三唑-3-硫醇、2-胺基-5-巰基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2-硫醇、2,5-二巰基-1,3,4-噻二唑、(呋喃-2-基)甲硫醇、2-巰基-5-噻唑烷酮、2-巰基噻唑啉、2-巰基-4(3H)-喹唑啉酮、1-苯基-1H-四唑-5-硫醇、2-喹啉硫醇、2-巰基-5-甲基苯并咪唑、2-巰基-5-硝基苯并咪唑、6-胺基-2-巰基苯并噻唑、5-氯-2-巰基苯并噻唑、6-乙氧基-2-巰基苯并噻唑、6-硝基-2-巰基苯并噻唑、2-巰基萘并咪唑、2-巰基萘并

唑、3-巰基-1,2,4-三唑、4-胺基-6-巰基吡唑并[2,4-d]吡啶、2-胺基-6-嘌呤硫醇、6-巰基嘌呤及4-巰基-1H-吡唑并[2,4-d]嘧啶等。 Examples of compounds having one mercapto group in the molecule include: 2-mercapto group

Azole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzo

Azole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amine 6-hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy- 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl -2-Mercaptopyrimidine, 4-hydroxy-2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2 -Thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole , 4-Amino-3-hydrazino-5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1 ,2,4-Triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto-1H-1,2,4-triazole-3 -Thiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto- 1,3,4-thiadiazole, (furan-2-yl)methyl mercaptan, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolinone , 1-Phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amine 2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthiazole Imidazole, 2-mercapto naphtho

Azole, 3-mercapto-1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purine thiol, 6-mercaptopurine And 4-mercapto-1H-pyrazolo[2,4-d]pyrimidine and so on.

Examples of compounds having two or more mercapto groups in the molecule include: hexamethylene dithiol, decane dithiol, 1,4-bis(methylthio)benzene, butanediol bis(3-mercaptopropionate) , Butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane tris(3-mercaptoacetate), butanediol bis(3-mercaptoacetate) Propionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra (3 -Mercaptoacetate), trihydroxyethyl tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate) and 1,4-bis(3-mercaptobutoxy)butane, etc.

As the thiol compound (T), a compound having one mercapto group in the molecule is preferred.

Regarding the content of the thiol compound (T), relative to 100 parts by mass of the polymerization initiator (D), it 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 share. When the content of the thiol compound (T) is within this range, the sensitivity becomes higher and the developability tends to become better.

<Solvent (E)>

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

Examples of ester solvents include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚及甲基苯甲醚等。 Examples of the ether solvent include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Ethylene 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-bis

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenylethyl ether and Methyl anisole and so on.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

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 alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

The solvent (E) can also use 2 or more types together.

In terms of coating properties and drying properties, an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm is preferred. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more Preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and 3-ethyl Ethyl oxypropionate.

Regarding the content of the solvent (E), in the colored photosensitive resin composition, it is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid component 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. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good, and since the color density is not insufficient when the color filter is formed, the display characteristics tend to become good.

<Leveling Agent (F)>

As a leveling agent (F), a silicone type surfactant, a fluorine type surfactant, etc. are mentioned. These may have a polymerizable group in the side chain.

As the polysiloxane-based surfactant, a surfactant having a siloxane bond in the molecule, and the like can be cited. Specifically, examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray 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) )Wait.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, it can include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M (Stock)), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Stock)), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Corporation), Surflon (registered trademark) S381 , Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute (Stock)), etc.

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

Regarding the content rate of the leveling agent (F), in the total amount of the colored photosensitive resin composition, it 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 or less, and more Preferably it is 0.005 mass% or more and 0.05 mass% or less. In addition, this content rate does not include the content rate of the said pigment dispersing agent.

<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, phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like can be used. Two or more antioxidants can also be used.

-2,4,6(1H,3H,5H)-三酮，BASF(股份)製造)、Irganox 3790(Irganox 3790：1,3,5-三((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮，BASF(股份)製造)、Irganox 1035(Irganox 1035：硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]，BASF(股份)製造)、Irganox 1135(Irganox 1135：苯丙酸，3,5-雙(1,1-二甲基乙基)-4-羥基，C7-C9側鏈烷基酯，BASF(股份)製造)、Irganox 1520L(Irganox 1520L：4,6-雙(辛硫基甲基)-鄰甲酚，BASF(股份)製造)、Irganox 3125(Irganox 3125，BASF(股份)製造)、Irganox 565(Irganox 565：2,4-雙(正辛硫基)-6-(4-羥基3',5'-二第三丁基苯胺基)-1,3,5-三

，BASF(股份)製造)、Adekastab AO-80(Adekastab AO-80：3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷，ADEKA(股 份)製造)、Sumilizer BHT(Sumilizer BHT，住友化學(股份)製造)、Sumilizer GA-80(Sumilizer GA-80，住友化學(股份)製造)、Sumilizer GS(Sumilizer GS，住友化學(股份)製造)、Cyanox 1790(Cyanox 1790，Cytec(股份)製造)及維生素E(衛材(股份)製造)等。 Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF (Stock)), Irganox 1076 (Irganox 1076: 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, manufactured by BASF (Stock)), Irganox 1330 (Irganox 1330: 3,3', 3",5,5',5"-hexatertiary butyl-a,a',a''-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF (Stock) ), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, manufactured by BASF (Stock)), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tertiary butyl-3-hydroxy- 2,6-Xylyl)methyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, manufactured by BASF (Co., Ltd.), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl) -4-hydroxyphenyl)propionate], manufactured by BASF (Stock), Irganox 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF (Stock), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF (Stock)), Irganox 3125 (Irganox) 3125, manufactured by BASF (Stock)), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-tertiary butylanilino)-1, 3,5-Three

, Manufactured by BASF (Stock), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propane Oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA (Stock), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.) ) And Vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of phosphorus-based antioxidants include: Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: tris[2- [[2,4,8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxphosphin-6-yl]oxy]ethyl]amine, BASF (shares ) Manufacturing), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF (Stock)), Adekastab 329K (Manufactured by ADEKA (Stock)), Adekastab PEP36 (manufactured by ADEKA (Stock)), Adekastab PEP-8 (manufactured by ADEKA (Stock)), 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-methyl (Phenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphepene) (manufactured by Sumitomo Chemical Co., Ltd.) )Wait.

Examples of sulfur-based antioxidants include dialkyl ester compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate or distearyl, and tetrakis[methylene (3-dodecane) Thio) propionate] β-alkylthio propionate compounds of polyols such as methane.

<Other ingredients>

In the colored photosensitive resin composition of the present invention, fillers, polymer compounds other than resin (B), adhesion promoters, ultraviolet absorbers, aggregation inhibitors, organic acids, organic amine compounds, and curing agents may also be used in combination as necessary. Agents and other additives.

Examples of fillers 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, polyfluoroalkyl acrylate, and the like.

Examples of adhesion promoters include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy)silane, and N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-condensation Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Furthermore, the above-mentioned 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is an example of a component containing a cyclic ether structure having 2 to 4 carbon atoms.

-2-基)-5-己氧基苯酚等三

系化合物等。 Examples of ultraviolet absorbers include benzotriazole-based compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4 -Octyloxybenzophenone and other benzophenone compounds; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzoic acid esters Series compound; 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-hexyloxyphenol, etc.

Department of compounds and so on.

Examples of the aggregation inhibitor include sodium polyacrylate and the like.

Organic acids are used to adjust developability. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid can be cited. Acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethyl Malonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid Aliphatic dicarboxylic acids such as, mesaconic acid; aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, aconitic acid, norbornanic acid; benzoic acid, toluic acid, cuminic acid, 2,3-dicarboxylic acid Aromatic monocarboxylic acids such as methyl benzoic acid and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Aromatic polycarboxylic acids such as trimellitic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,5-pyromellitic acid, and pyromellitic acid.

Examples of organic amine compounds include n-propyl amine, isopropyl amine, n-butyl amine, isobutyl amine, second butyl amine, tertiary butyl amine, n-pentyl amine, n-hexyl amine, Heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine and other monoalkylamines; cyclohexylamine, 2-methylcyclohexylamine, Monocyclic alkylamines such as 3-methylcyclohexylamine and 4-methylcyclohexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine Dialkylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-second butylamine, di-tertiary butylamine, di-n-pentylamine, di-n-hexylamine, etc. ; Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; dicycloalkylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethyl Amine, dimethyl n-propyl amine, diethyl n-propyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, tri-n-propyl amine, tri-isopropyl amine, tri-n-butyl Amine, triisobutylamine, tri-second butyl amine, tri-tertiary butyl amine, tri-n-pentyl amine, tri-n-hexyl amine and other trialkyl amines; dimethyl cyclohexyl amine, diethyl cyclohexyl Dialkyl monocycloalkylamines such as amines; monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine; 2-aminoethanol, 3-amino- Monoalkanolamines such as 1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol; Monocyclic alkanolamines such as 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, Dialkanolamines such as di-n-hexanolamine; Dicycloalkanolamines such as di(4-cyclohexanol)amine; Triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, etc.; tris(4-cyclohexanol) ) Tricyclic alkanolamines such as amines; 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-Diethyl Amino alkanediols such as amino-1,3-propanediol; aminocycloalkanediols such as 4-amino-1,3-cyclohexanediol and 4-amino-1,3-cyclohexanediol; 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol and other cycloalkanone methanol containing amino groups; 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylamine Cycloalkane methanol containing amine groups such as 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, 4-diethylaminocyclohexane methanol, etc.; β-propylamine Acid, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminobutyric acid Amino carboxylic acids such as valeric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline , M-methyl aniline, p-methyl aniline, p-ethyl aniline, p-n-propyl aniline, p-isopropyl aniline, p-n-butyl aniline, p-tertiary butyl aniline, 1-naphthyl amine, 2-naphthalene Amine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline and other aromatic amines; o-aminobenzyl alcohol, m-aminobenzyl alcohol, Amino benzyl alcohol such as p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-aminophenol Amino phenols such as diethylamino phenol; amino benzoic acid such as meta-amino benzoic acid, p-amino benzoic acid, p-dimethylamino benzoic acid, p-diethylamino benzoic acid, etc.

Examples of hardeners include: it can be made by reacting with the carboxyl group in the resin (B) by heating The resin (B) is a compound that crosslinks, a compound that can be polymerized alone to harden a colored pattern, and the like. Examples include epoxy compounds, oxetane compounds, and the like.

Here, examples of the epoxy compound include: bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy resin. Resins, other aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oils, or such epoxy resins Brominated derivatives of resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, isoprene (Co)polymer of epoxide, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate, etc.

Examples of commercially available epoxy resins include o-cresol novolac type epoxy resins, "Sumiepoxy (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of the oxetane compound include carbonate dioxetane, xylylene dioxetane, adipate dioxetane, and terephthalate dioxane. Etidine, cyclohexane dicarboxylic acid dioxetane, etc.

When the colored photosensitive resin composition of the present invention contains an epoxy compound, an oxetane compound, etc. as a curing agent, it may also contain an epoxy group that can make an epoxy compound or an oxygen that can be an oxetane compound. A compound in which the ethidium skeleton undergoes ring-opening polymerization. As this compound, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, an acid generator, etc. are mentioned.

Examples of polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5 ,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid and other aromatic polycarboxylic acids; succinic acid, glutaric acid, adipic acid, 1,2,3, Aliphatic polycarboxylic acids such as 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, Alicyclic polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc.

Examples of polycarboxylic acid anhydrides include aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride. ; Iconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1,2,3-propanetricarboxylic anhydride, maleic anhydride, 1,2,3,4-butane tetracarboxylic acid Aliphatic polycarboxylic acid anhydrides such as dianhydride; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic acid anhydride, 1,2,4 -Cyclohexane tricarboxylic acid anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, bicycloheptene dicarboxylic acid anhydride, vanadic anhydride and other alicyclic polycarboxylic acid anhydrides ; Ethylene glycol bitrimellitic acid, glycerol trimellitic anhydride and other ester-containing carboxylic acid anhydrides.

As a carboxylic anhydride, what is marketed as a hardening agent for epoxy resins can also be used. Examples of hardeners for epoxy resins include: brand name "Adeka Hardener (registered trademark) EH-700" (made by ADEKA (Co., Ltd.)), brand name "RIKACID (registered trademark) HH" (manufactured by Nippon Rika Co., Ltd.) ), the product name "MH-700" (manufactured by Nippon Rika Co., Ltd.), etc.

Examples of acid generators include: p-toluenesulfonic acid 4-hydroxyphenyl dimethyl sulfonium, 4-hydroxyphenyl dimethyl hexafluoroantimonate, p-toluenesulfonic acid 4-acetoxyphenyl dimethyl Benzene, 4-acetoxyphenyl hexafluoroantimonate‧Methyl‧Benzyl sulfonate, Triphenylsulfonate p-toluenesulfonate, Triphenylsulfonate hexafluoroantimonate, Diphenylsulfonate p-toluenesulfonate, Onium salts such as diphenyl iodonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc.

The curing agent may be used alone or in combination of two or more kinds.

<Production method of colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention can be prepared by containing colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D), and optionally mixed solvent (E), thiol compound (T), leveling agent (F), polymerization initiator (D1) , Antioxidant (J), and other ingredients.

<Manufacturing Method of Color Filter>

As a method of manufacturing a colored pattern from the colored photosensitive resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, the photolithography method is preferred. The photolithography method is a method of applying the above-mentioned colored photosensitive resin composition on a substrate, drying it to form a colored composition layer, exposing the colored composition layer through a photomask, and performing development. In the photolithography method, since a photomask is not used and/or development is not performed during exposure, a colored coating film can be formed as a cured product of the colored composition layer. The colored pattern or colored coating film thus formed can be used as the color filter of the present invention.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, or polycarbonate, polymethyl methacrylate, and poly-p-phenylene can be used. Resin plates such as ethylene dicarboxylate, silicon, aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of each color performed by the photolithography method can be performed using known or customary devices or conditions. For example, it can be produced as follows.

First, the colored photosensitive resin composition is coated on a substrate, and dried by removing volatile components such as solvents by heating and drying (pre-baking) and/or drying under reduced pressure, thereby obtaining a smooth coloring composition layer .

Examples of the coating method include spin coating, slit coating, slit & spin coating, and the like.

The temperature in the case of heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes.

In the case of drying under reduced pressure, it is preferably at a pressure of 50~150Pa at 20~ Performed within a temperature range of 25°C.

The film thickness of the colored composition layer is not particularly limited, as long as it is appropriately selected according to the film thickness of the target color filter.

Secondly, the coloring composition layer is exposed through a photomask for forming the target coloring pattern. The pattern on the mask is not particularly limited, and patterns suitable for the target purpose can be used.

As a light source for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, it is possible to use a filter that cuts off the wavelength region for light that does not reach 350nm, or use a bandpass filter that extracts these wavelength regions for light near 436nm, 408nm, and 365nm for selective extraction. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be mentioned.

In order to uniformly irradiate the entire exposure surface with parallel light, or to perform the correct alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use exposure devices such as a photomask alignment exposure machine and a stepping exposure machine. .

The coloring composition layer after exposure is brought into contact with a developing solution for development to form a coloring pattern on the substrate. By development, the unexposed part of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01-10% by mass, more preferably 0.03-5% by mass. Furthermore, the developer may contain a surfactant.

The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, it is also possible to tilt the substrate to an arbitrary angle during development.

It is preferable to wash with water after development.

Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably 150-250°C, more preferably 160-235°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 will affect the adjacent pixels, it is preferable that the coating film be as thin as possible. Especially when it is a thick film, when making a liquid crystal panel, light from a light source may leak through pixels of more than two colors. When the panel is viewed from an oblique direction, the vividness of the color 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, and it is usually 1 μm or more, and may be 1.5 μm or more.

In addition, the higher the brightness of the coating film, the better, preferably 38.5 or more, more preferably 39 or more, and the upper limit is not particularly limited, but 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 can be used as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[Example]

Hereinafter, the present invention will be explained more specifically with reference to examples, but the present invention is of course not limited by the following examples. In addition, in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

Synthesis example 1

An appropriate amount of nitrogen was introduced into a 1L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, 280 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Then, 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 ester of acrylic acid, and propylene glycol monomethyl ether were added dropwise over 5 hours. A mixed solution of 125 parts by mass of acetate. On the other hand, a mixed solution obtained by dissolving 33 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dripping is finished, keep it at the same temperature for 4 hours, and then cool to room temperature to obtain a type B viscosity (23°C) of 125mPa‧s, solid content of 37.0% by mass, and acid value of the solution 27mg-KOH/g The copolymer (hereinafter sometimes referred to as resin solution (B1)). The weight average molecular weight Mw of the resulting copolymer was 9,200, and the degree of dispersion was 2.08. The obtained copolymer has almost no absorption under 500~600nm.

The measurement of the polystyrene-converted weight-average molecular weight Mw and the number-average molecular weight Mn of the resin obtained in the above synthesis example was carried out under the following conditions using the GPC (Gel Permeation Chromatography) method.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran [THF]

Flow rate: 1.0mL/min

Concentration of solid content of the test liquid: 0.001~0.01% by mass

Injection volume: 50μL

Detector: RI

Standard material for calibration: TSK polystyrene standard

F-40, F-4, F-288, A-2500, A-500

(Manufactured by Tosoh (Stock))

[Preparation of Pigment Dispersion A-1]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-1).

Here, as the polyhalogenated zinc phthalocyanine (a1), it is synthesized by the method described in Japanese Patent No. 4368157.

The obtained polyhalogenated zinc phthalocyanine (a1) contains an average of 10 bromine in one molecule according to the halogen content analysis by mass spectrometry.

The measurement of the spectroscopic spectrum of the above-mentioned polyhalogenated zinc phthalocyanine (a1) was carried out in the following order. As a result, the wavelength of the maximum transmittance was 515 nm.

[Determination order]

By mixing the pigment dispersion liquid A-1 and the resin solution (B1), a composition having a concentration of the polyhalogenated zinc phthalocyanine (a1) in the solid content of 30% by mass was prepared. After coating the obtained composition by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), it was pre-baked at 100°C for 3 minutes, and then cooled. Furthermore, the obtained film was post-baked in an oven at 230°C for 30 minutes, thereby obtaining a coating film. For this coating film, the transmittance (T1) was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd., light source: halogen lamp, pinhole diameter of 50 μm).

Furthermore, for a coating film produced in the same order as the coating film except that it does not contain a polyhalogenated zinc phthalocyanine (a1), the transmittance (T2) was measured under the same conditions as described above.

In addition, the above-mentioned spectral transmittance spectrum is created based on the value (=T1-T2) obtained by subtracting (T2) from the transmittance (T1).

[Preparation of Pigment Dispersion A-2]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-2).

C.I. Pigment Green 58 contains an average of 14 bromine in one molecule according to the halogen content analysis performed by mass spectrometry.

As in the case of the pigment dispersion A-1, color measurement was carried out using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.). As a result, the wavelength of the maximum transmittance was 525 nm.

[Preparation of Pigment Dispersion A-3]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-3).

[Preparation of Pigment Dispersion A-4]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-4).

[Preparation of Pigment Dispersion A-5]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-5).

[Preparation of Pigment Dispersion A-6]

The following components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid (A-6).

Examples 1 to 10 and Comparative Examples 1 to 4

[Preparation of colored photosensitive resin composition]

The components described in Table 8 were mixed to obtain a colored photosensitive resin composition. Furthermore, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition became the "solid content (%)" in Table 8.

In Table 8, the components are as follows.

Coloring dispersant (A1): the above-obtained pigment dispersion (A-1)

Coloring dispersant (A2): the above-obtained pigment dispersion (A-2)

Coloring dispersant (A3): the above-obtained pigment dispersion (A-3)

Coloring dispersant (A4): the above-obtained pigment dispersion (A-4)

Coloring dispersant (A5): the above-obtained pigment dispersion (A-5)

Coloring dispersant (A6): the above-obtained pigment dispersion (A-6)

Resin solution (B1): the copolymer solution obtained in Synthesis Example 1

Polymerizable compound (C1): Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D1): N-benzyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (product name: Irgacure OXE01; manufactured by BASF; O-Acetioxime compound)

Polymerization initiator (D2): ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyl) Oxime) (product name: Irgacure OXE02; manufactured by BASF; O- oxime compound)

Polymerization initiator (D3): a 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 Dow Corning Toray Co., Ltd.)

[Pattern making]

After coating the colored photosensitive resin composition on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, it was pre-baked at 100°C for 3 minutes. After cooling, set the distance between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass mask to 100μm, and use an exposure machine (TME-150RSK; manufactured by TOPCON (Stock)) in an atmospheric environment Light irradiation is performed at an exposure amount of 150 mJ/cm ^{2 (365nm reference).} In addition, as the photomask, a photomask formed with a pattern of 50 μm lines and gaps was used. After light irradiation, the above-mentioned coating film was immersed and developed in an aqueous developer containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds. After washing with water, it was carried out at 230°C in an oven. Bake after 30 minutes to obtain a pattern.

[Film thickness measurement]

For the obtained pattern, the film thickness FT (μm) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9. In the table, the case where the film thickness is 3 μm or less is set as "○", and the case where the film thickness exceeds 3 μm is set as "×".

[Chromaticity Evaluation]

For the obtained pattern, use a color measuring machine (OSP-SP-200; manufactured by Olympus (Stock)) to measure the spectroscopy, and use the characteristic function of the C light source to measure the xy chromaticity coordinates (x, y) in the XYZ color system of CIE With brightness Y. The results are shown in Table 9. In the table, the case where the brightness is 38.5 or higher is set as "○", and the case where the brightness is less than 38.5 is set as "×".

[Pattern shape]

The obtained pattern was observed with an optical microscope (magnification 500 times). If the end of the pattern became a straight line, it was evaluated as "○", and if it became jagged due to notches or the like, it was evaluated as "×". The results are shown in Table 9.

[Industrial availability]

The colored photosensitive resin composition of the present invention can be used to produce a color filter having a good pattern shape and high brightness as a film. This color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (8)

A colored photosensitive resin composition characterized by containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the colorant (A) is suitable for coloring photosensitive The solid content of the resin composition is 20-60% by mass in 100% by mass, and contains polyhalogenated zinc phthalocyanine (a1) and a blue pigment as the colorant (A). The polyhalogenated zinc phthalocyanine (a1) a1) It contains an average of less than 13 bromine in one molecule, and in the spectral transmittance spectrum under 380~780nm, the wavelength at which the transmittance becomes the largest is 500~520nm. The content of the blue pigment is relative to the polyhalide phthalate 100 parts by mass of cyanine zinc (a1) are 0.1-20 parts by mass. The colored photosensitive resin composition of claim 1, which further contains a green pigment other than the polyhalogenated zinc phthalocyanine (a1) as the colorant (A). The colored photosensitive resin composition of claim 1 or 2, which further contains C.I. Pigment Green 58 as the colorant (A). The coloring photosensitive resin composition of claim 1 or 2, wherein the blue pigment is selected from at least one of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60. The coloring photosensitive resin composition of claim 1 or 2, wherein the blue pigment is at least one selected from C.I. Pigment Blue 15:3 and 15:4. A coating film formed of the colored photosensitive resin composition according to any one of claims 1 to 5. A color filter, which is formed of the colored photosensitive resin composition according to any one of claims 1 to 5. A display device comprising the color filter as claimed in claim 7.