TWI705302B - Colored photosensitive resin composition - Google Patents

Abstract

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as a colorant (A), it contains a halogenated zinc phthalocyanine Pigment, CI Pigment Yellow 185, and CI Pigment Blue 15:3 or CI Pigment Blue 15:4.

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used to manufacture color filters in display devices such as liquid crystal display panels. In recent years, in order to expand the color reproduction area that can be displayed on the display, continuous development has been made. As part of this, the color filter is also required to have a deeper color. In order to meet this requirement, a method of increasing the concentration of the colored material in the color filter can be cited. However, if the concentration of the colored material increases, the pattern shape may deteriorate, and the performance as a photosensitive composition may deteriorate.

Patent Document 1 describes the following green photosensitive resin composition, which contains CI Pigment Green G58, a blue colored material and a yellow colored material containing coloring agent, resin, in order to design a darker green color filter Polymerizable monomer, photopolymerization initiator, and solvent.

[Prior Technical Literature] [Patent Literature]

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

The object of the present invention is to obtain a coloring photosensitive resin composition with higher brightness.

The present invention includes the following inventions.

[1] A colored photosensitive resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as a colorant (A), a halogenated Zinc phthalocyanine pigment, CI Pigment Yellow 185, and CI Pigment Blue 15:3 or CI Pigment Blue 15:4.

[2] The colored photosensitive resin composition as described in [1], wherein the halogenated zinc phthalocyanine pigment is C.I. Pigment Green 58.

[3] The colored photosensitive resin composition as described in [1] or [2], wherein the content of C.I. Pigment Yellow 185 is 10 to 50 parts by mass relative to 100 parts by mass of the polymerizable compound (C).

[4] The colored photosensitive resin composition as described in any one of [1] to [3], wherein the total amount of the colorant (A) is 100 parts by mass of the solid content of the colored photosensitive resin composition 20-50 parts by mass.

[5] A color filter formed of the colored photosensitive resin composition as described in any one of [1] to [4] above.

A color filter with good brightness can be manufactured from the colored photosensitive resin composition of the present invention.

Fig. 1 is a schematic diagram showing the cross-sectional shape of the pattern. Fig. 1(p1) shows a good cross section where cracks or peeling is less likely to occur in the inorganic film when an inorganic film is laminated on a colored pattern, and Fig. 1(p2) shows a cross section where cracks or peeling easily occurs on the inorganic film.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

The colored photosensitive resin composition of the present invention preferably further contains a solvent (E).

The colored photosensitive resin composition of the present invention may further contain a leveling agent (F) And at least one of the group consisting of thiol compounds.

A color filter with high brightness can be manufactured from the colored photosensitive resin composition of the present invention. Furthermore, the colored photosensitive resin composition is less likely to produce a release sheet derived from the colored photosensitive resin composition during the production of a pattern, and it is also possible to produce a pattern with a good pattern shape.

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

<Colorant (A)>

In the colored photosensitive resin composition of the present invention, as the colorant (A), C.I. Pigment Blue 15:3 or C.I. Pigment Blue 15:4, halogenated zinc phthalocyanine pigment, and C.I. Pigment Yellow 185 are contained.

As the halogenated zinc phthalocyanine pigment, C.I. Pigment Green 58 can be cited.

The content of the halogenated zinc phthalocyanine pigment is usually 10 to 120 parts by mass, preferably 20 to 110 parts by mass, and more preferably 25 to 70 parts by mass relative to 100 parts by mass of the polymerizable compound (C). If the content of the zinc halide phthalocyanine pigment is within the above range, a color filter with particularly good brightness can be obtained.

The content of CI Pigment Yellow 185 relative to 100 parts by mass of the polymerizable compound (C) is usually 10-50 parts by mass, preferably 20-50 parts by mass, more preferably 25-45 parts by mass, and still more preferably 25~ 40 parts by mass. If the content of C.I. Pigment Yellow 185 is within the above range, a color filter with excellent brightness and pattern shape can be obtained.

The total content of CI Pigment Blue 15:3 and CI Pigment Blue 15:4 relative to 100 parts by mass of the polymerizable compound (C) is usually 1-30 parts by mass, preferably 1-25 parts by mass, more preferably 5~ 15 parts by mass, more preferably 5-9 parts by mass. If the content of C.I. Pigment Blue 15:3 or C.I. Pigment Blue 15:4 is within the above range, a color filter with particularly excellent pattern shape can be obtained.

In the colorant (A), as a green pigment, it is preferable to contain only a zinc halide phthalocyanine pigment It is more preferable to contain only C.I. Pigment Green 58.

The colorant (A) may also contain other well-known pigments. However, in the colored photosensitive resin composition of the present invention, it is preferable to contain only C.I. Pigment Green 58, C.I. Pigment Yellow 185, and C.I. Pigment Blue 15:3 or C.I. Pigment Blue 15:4 as the coloring agent.

The coloring agent (A) preferably further contains C.I. Pigment Yellow 138.

The total amount of the coloring agent (A) is usually 20-50 parts by mass, preferably 20-45 parts by mass, and more preferably 20-35 parts by mass with respect to 100 parts by mass of the solid content of the colored photosensitive resin composition. More preferably, it is 20-30 mass parts.

Here, the "total amount of solid content" in this specification refers to the amount obtained by excluding the solvent content from the total amount of the colored photosensitive resin composition. The total amount of solid components and the content of each component corresponding to it can be measured, for example, by a known analysis method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but an alkali-soluble resin is preferred. As resin (B), the following resin [K1]~[K6] etc. are mentioned.

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as "(a)"), and those with 2 to 4 carbon atoms A copolymer of cyclic ether structure and ethylenically unsaturated bond monomer (b) (hereinafter referred to as "(b)").

Resin [K2]: (a), (b), and monomer (c) that can be copolymerized with (a) (however, different from (a) and (b)) (hereinafter referred to as "(c)" Situation) of the copolymer.

Resin [K3]: a copolymer of (a) and (c).

Resin [K4]: A resin obtained by reacting the copolymer of (a) and (c) and (b).

Resin [K5]: A resin obtained by reacting the copolymer of (b) and (c) and (a).

Resin [K6]: A resin obtained by reacting the copolymer of (b) and (c) and (a), and then reacting with carboxylic anhydride.

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；順丁烯二酸酐、甲基順丁烯二酸酐、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)等不飽和二羧酸酐；琥珀酸單[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]酯等二元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯；以及丙烯酸α-(羥基甲基)酯等在同一分子中含有羥基及羧基之不飽和丙烯酸酯等。 As (a), for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho, meta, and p-vinyl benzoic acid; maleic acid, fumaric acid, methyl cis Butenedioic acid, methyl fumaric acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-lower

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, methyl maleic anhydride, itaconic anhydride, 3 -Vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic acid anhydride) and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2 -(Meth) acrylate oxyethyl] ester, phthalic acid mono [2-(meth) acrylate oxyethyl] ester and other unsaturated mono [(methyl) ) Allyloxyalkyl] ester; and α-(hydroxymethyl) acrylate 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 an aqueous alkali solution.

(b) For example, it refers to a cyclic ether structure having a carbon number of 2 to 4 (for example, selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring) At least one of) and ethylenically unsaturated bond polymerizable compound. (b) Preferably, it is a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloxy group.

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

Examples of (b) include: monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond. Saturated bond monomer (b2) (hereinafter referred to as "(b2)"), monomer with tetrahydrofuran group and ethylenically unsaturated bond (b3) (hereinafter referred to as "(b3)") Wait.

(b1) Examples include: monomer (b1-1) having a structure obtained by epoxidizing unsaturated aliphatic hydrocarbon (hereinafter referred to as "(b1-1)"), having an unsaturated aliphatic ring The monomer (b1-2) of the structure formed by the epoxidation of the hydrocarbon (hereinafter referred to as "(b1-2)").

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (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, Celloxide2000; 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 (meth)acrylate (for example, Cyclomer M100; Daicel Chemical Industrial (Stock) Manufacturing), the compound represented by formula (I), the compound represented by formula (II), etc.

[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 may be replaced by the hydroxyl group.

X ^a and X ^b each independently represents a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - R c -NH-.

R ³ 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, sec-butyl, and t-butyl.

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 ¹ and R ² , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group are mentioned.

Examples of alkanediyl groups include: methylene, ethylene, 1,2-propanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1, 6-Hexanediyl and so on.

Examples of X ¹ and X ² preferably include: single bond, methylene group, ethylene group, *-CH ₂ -O- (* represents a bond with O) group, *-CH ₂ CH _2- O-group, and 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. It may be better to 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. It may be better to 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), and formula (II-15) can be cited.

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 is calculated in molar ratio, preferably 5:95~95:5 in formula (I): formula (II), more preferably 10:90~90:10, More 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-methacryloyloxymethyloxetane, 3-ethyl-3-propene Oxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, etc.

As the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable.

As (b3), specifically, tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc. are mentioned.

酯、(甲基)丙烯酸金剛烷酯、(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；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯；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；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、3-順丁烯二醯亞胺苯甲酸N-丁二醯亞胺酯、4-順丁烯二醯亞胺丁酸N-丁二醯亞胺酯、6-順丁烯二醯亞胺己酸N-丁二醯亞胺酯、3-順丁烯二醯亞胺丙酸N-丁二醯亞胺酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物；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 Esters, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl (meth)acrylate (in this technical field Among them, as a common name, it is called "dicyclopentyl (meth)acrylate." In addition, there are cases where it is called "tricyclodecyl (meth)acrylate"), tricyclic (meth)acrylate [5.2. 1.0 ^2,6 ] Decene-8-yl ester (in this technical field, as a common name, called "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentyloxyethyl Esters, (meth) acrylic iso

Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid Benzyl esters and other (meth)acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; diethyl maleate , 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, 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-di (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[ 2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexoxycarbonylbicyclo [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- Bicyclic unsaturated compounds such as 2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylcis Butylene diimide, N-benzyl maleimide, 3-maleimide benzoate N-butane diimidate, 4-maleimide butyric acid N-butanediimidate, 6-maleimide hexanoic acid N-butanediimidate, 3-maleimide propionate N-butanediimidate, N -(9-Acridinyl)maleimide and other dicarbonylimines derivatives; styrene, α-methylstyrene, m-methylstyrene, 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, and N-phenylmaleic acid are preferred. Imine, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo[2.2.1]hept-2-ene, etc. In terms of excellent developability at the time of pattern formation, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable.

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

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

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

If the ratio of the structural unit of the resin [K1] is in the above range, there is a tendency that storage stability, developability, and solvent resistance of the obtained pattern are excellent.

The resin [K1] can be described in, for example, the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Publishing House: Chemical Doujin (Stock), First Edition, First Printing, Issued on March 1, 1972) The method and the cited documents described in this document are manufactured by reference.

Specific examples include a method of charging specific amounts of (a) and (b), polymerization initiator, solvent, etc., into a reaction vessel, and performing stirring, heating, and heat preservation in a deoxidizing environment. Furthermore, the polymerization initiator, solvent, etc. used here are not particularly limited, and can be used by any user generally in the field. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The oxide (benzyl peroxide, etc.) can be any solvent that dissolves each monomer, and as a solvent for the colored photosensitive resin composition, the following solvent (E) can be used.

The obtained copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by reprecipitation and other methods can be used. In particular, during the polymerization, the following solvent (E) is used as a solvent, whereby the solution after the reaction can be used directly, and the manufacturing steps can be simplified.

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

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

The structural unit derived from (b): 2~95 mol% (more preferably 5~80 mol%)

The 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 in the above range, there is a tendency that storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern are excellent.

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

Specific examples include a method of charging specific amounts of (a), (b) and (c), a polymerization initiator, and a solvent into a reaction vessel, and performing stirring, heating, and heat preservation in a deoxygenated environment. The obtained copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by reprecipitation and other methods can be used.

In the resin [K3], the ratio of the structural units derived from each component to all the structural units constituting the resin [K3] is preferably in the following range.

(a) 2~55 mol%, more preferably 10~50 mol%

(c) 45~98 mole%, more preferably 50~90 mole%

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

The resin [K4] can be manufactured by the following method, namely, obtain the copolymer of (a) and (c), make (b) the cyclic ether with carbon number 2~4 and (a) the carboxyl Acid and/or carboxylic anhydride addition.

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 unit derived from each component among all the structural units constituting the copolymer of (a) and (c) is preferably in the following range.

(a) 5~50 mol%, more preferably 10~45 mol%

(c) 50~95 mole%, more preferably 55~90 mole%

Then, the cyclic ether having 2 to 4 carbon atoms in (b) is partially reacted with 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 was replaced with air from nitrogen, and (b), and the reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (tris(dimethyl) Aminomethyl)phenol, etc.) and polymerization inhibitors (hydroquinone, etc.) are added to the flask and reacted at 60~130°C for 1~10 hours to obtain resin [K4].

The usage amount of (b) relative to (a) 100 mol, preferably 5 to 80 mol, more preferably 10 to 75 mol. By setting it in this range, there are storage stability, developability, solvent resistance, and The balance of heat, mechanical strength, and sensitivity tends to become better. Regarding the high reactivity of the cyclic ether, the unreacted (b) is less likely to remain, as (b) for the resin [K4], (b1) is preferred, and (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), 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 loading method, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment or heat generation due to polymerization. In addition, it is possible to appropriately adjust the charging method and the reaction temperature in consideration of manufacturing equipment, heat generation due to polymerization, etc., in the same manner as the polymerization conditions.

Regarding the resin [K5], as the first stage, a copolymer of (b) and (c) was obtained in the same manner as the method for producing the resin [K1] described above. 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) obtained by reprecipitation or the like can also be used.

The ratio of the structural units derived from (b) and (c) to the total number of moles of all the structural units constituting the copolymer is preferably in the following range.

The structural unit derived from (b): 5~95 mol% (more preferably 10~90 mol%)

The 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 carboxylic acid or carboxylic anhydride contained in (a) and the copolymer of (b) and (c) are derived from the ring in (b) Like ether reaction, thereby obtaining resin [K5].

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

Resin [K6] is a resin obtained by further reacting resin [K5] with carboxylic anhydride. 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, methyl maleic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5 ,6-Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene anhydride (bicycloheptene dicarboxylic acid anhydride) and the like.

Specific examples of the resin (B) include: 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0 ^2,6 ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl maleimide copolymer Resins such as 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/( Resins such as meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [K3]; The resin obtained by adding glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth)acrylic acid copolymer to make glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/ Resin obtained by addition of styrene/(meth)acrylic acid copolymer, copolymerization of glycidyl (meth)acrylate with tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid Resins such as resins obtained by addition of substances [K4]; resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and (meth) Acrylic acid and (meth)acrylate tricyclodecyl ester/styrene/(meth)acrylate glycidyl ester copolymer resin and other resins [K5]; make tetrahydrophthalic anhydride and make (methyl) ) Resins such as resins obtained by reacting acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymers to obtain resins [K6], etc.

These resins may be used alone, or two or more types may be used in combination.

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000~ 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is in 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 acid value of the resin (B) is preferably 50 to 180 mg-KOH/g, more preferably 60 to 150 mg-KOH/g.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) relative to the solid content of the colored photosensitive resin composition is preferably 7-65% by mass, more preferably 13-60% by mass, still more preferably 17-55% by mass, and particularly preferably 17-40% 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 weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less. The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by irradiating light, and examples thereof include polymerizable ethylenically unsaturated bonds. Compound etc.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylic acid Esters, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate , Pentaerythritol deca(meth)acrylate, pentaerythritol nine(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate Base) acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylic acid Ester, 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 mentioned.

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it can generate living radicals by the action of light or heat to initiate polymerization of the polymerizable compound (C), and a known radical polymerization initiator can be used. Agent.

化合物、醯基氧化膦化合物、肟化合物、及聯咪唑化合物，尤其是進而較佳為含有肟化合物之聚合起始劑。 The polymerization initiator (D) is preferably a compound that generates active free radicals by the action of light, more preferably alkylphenone compounds, three

The compound, the phosphine oxide compound, the oxime compound, and the biimidazole compound are particularly preferably a polymerization initiator containing an oxime compound.

Examples of the O-phenyloxime compound include: N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy -1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl) Yl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3- Dimethyl-2,4-dioxolylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (the above are made by BASF), and N-1919 (made by ADEKA) can also be used.

The colored photosensitive resin composition of the present invention may also contain a polymerization initiation assistant (D1). When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound (C) that starts polymerization by the polymerization initiator (D).

化合物、羧酸化合物、硫醇化合物等，較佳為硫醇化合物。該等聚合起始助劑可單獨使用，亦可併用2種以上。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxysulfur

The compound, carboxylic acid compound, thiol compound, etc. are preferably thiol compounds. These polymerization initiation aids may be used alone or in combination of two or more kinds.

The content of the polymerization initiator (D) is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 3 to 10% by mass relative to the solid content of the colored photosensitive resin composition.

In the case of using the polymerization initiator (D1), its content is relative to 1 mol of the polymerization initiator (D), preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol.

The total content of the polymerization initiator (D) and the polymerization initiator (D1) relative to the solid content of the colored photosensitive resin composition is preferably 1 to 35% by mass, more preferably 1 to 25% by mass, More preferably, it is 1-20 mass %, More preferably, it is 5-20 mass %.

It is preferable that the colored photosensitive resin composition of this invention contains a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. For example, it can be selected from ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ketones other than ester solvents Choose and use solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, 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, 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、甲基 苯甲醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and 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, 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-methyl ethyl propionate, 3-methoxy butyl acetate, 3-methyl-3-methoxy butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, two Propylene 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, isophorone, etc.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

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

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

Among the above solvents, 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, N,N-dimethylformamide Etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, lactic acid Ethyl ester, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.

If the content of the solvent (E) is in the above range, the flatness during coating becomes good, and the color density is not insufficient when forming a color filter, so there is a tendency for the display characteristics to become good.

<Leveling Agent (F)>

As the leveling agent (F), silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms, and the like can be cited. These may have a polymerizable group in the side chain.

As the polysiloxane-based surfactant, a surfactant having a siloxane bond in the molecule, etc. can be cited. Specific 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 (stock)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) Wait.

As the above-mentioned fluorine-based surfactant, a surfactant having a fluorocarbon chain in the molecule and the like can be cited. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), 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 Electronic Chemicals (stock)), 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 Co., Ltd.), etc.

As the polysiloxane-based surfactant having a fluorine atom, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule can be cited. Specific examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (F) relative to the total amount of the colored photosensitive resin composition 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 0.01 Mass% or more and 0.05 mass% or less. Furthermore, this content does not include the content of the aforementioned pigment dispersant.

The colored photosensitive resin composition of the present invention may optionally contain additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents.

The colored photosensitive resin composition of the present invention can be used to mix the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent ( E) or leveling agent (F) and other additives are stirred and mixed to produce.

Preferably, after mixing, filter with a filter with a pore size of about 0.05 to 5.0 μm.

C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, halogenated zinc phthalocyanine pigment, and C.I. Pigment Yellow 185 contained as the colorant (A) are preferably mixed with other components in the form of a pigment dispersion.

Each pigment dispersion liquid can be prepared by dispersing any one of the above-mentioned pigments in the solvent (E) containing the pigment dispersant.

The pigment dispersant may be used alone or in combination of two or more kinds.

As the pigment dispersing agent, known pigment dispersing agents such as acrylic surfactants can be cited. In terms of trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Avecia), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno (stock)), Disperbyk (registered trademark) (manufactured by BYK-Chemie) Wait.

The amount of the pigment dispersant used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less relative to the pigment. If the usage amount of the pigment dispersant is in this range, a uniformly dispersed pigment dispersion liquid can be obtained.

When dispersing the pigment in the solvent (E), a known dispersing machine such as a bead mill can be used.

The colored photosensitive resin composition of the present invention is useful as a material for coating films such as color filters (hereinafter, coating films obtained by resolving certain shapes may be referred to as "patterns"). The pattern shape of the color filter obtained from the colored photosensitive resin composition is preferable.

As a method of forming a pattern from the colored photosensitive resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. can be cited. Among them, the photolithography method is preferred.

The photolithography method is a method of obtaining a pattern by applying the colored photosensitive resin composition described above to a substrate, drying, exposing through a photomask, and developing.

As said substrate, glass, metal, plastic, etc. are mentioned, for example, and it may be a plate shape or a film shape. Structures such as color filters, various insulating or conductive films, and driving circuits may also be formed on these substrates.

For coating the substrate, for example, spin coater, slit & spin coater, slit coater (sometimes called die nozzle coater, curtain type flat coater, non- Spin coater), inkjet and other coating devices.

As a drying method of the colored photosensitive resin composition applied to the substrate, for example, Examples: heating drying, natural drying, ventilating drying, vacuum drying and other methods. It is also possible to combine plural methods. The drying temperature is preferably 10 to 120°C, more preferably 50 to 100°C. Moreover, as the heating time, 10 seconds to 60 minutes are preferable, and 30 seconds to 10 minutes are more preferable. Drying under reduced pressure is preferably performed under a pressure of 50 to 150 Pa and a temperature of 20 to 25°C.

The film obtained by drying is exposed through a photomask for forming the target pattern.

The pattern shape on the mask at this time is not particularly limited, and the pattern shape corresponding to the target application is 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, a filter that cuts off the wavelength region can be used to cut off light below 350nm, or a bandpass filter that extracts these wavelength regions can be used to selectively extract light near 436nm, 408nm, and 365nm. . Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like.

In order to be able to irradiate the entire exposure surface with parallel light uniformly, or to accurately align the photomask with the substrate, it is preferable to use a photomask alignment exposure machine, stepping exposure machine and other devices.

After the exposure, the unexposed part is brought into contact with the developer solution to dissolve, thereby performing development. By this development, a pattern can be obtained. As the developer, an organic solvent can also be used. However, in order to prevent dissolution or swelling of the exposed part of the coating film due to the developer, and to obtain a pattern with a good shape, an aqueous solution of an alkaline compound is preferred.

The development method may be any of immersion method, dipping method, spray method and the like. Furthermore, the substrate may be inclined at any angle during development.

It is preferable to wash with water after development.

Examples of the above basic compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, boric acid Inorganic basic compounds such as potassium and ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethyl Organic basic compounds such as base amine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. Among them, potassium hydroxide, sodium bicarbonate, and tetramethylammonium hydroxide are preferred.

The concentration in the aqueous solution of the basic compound is preferably 0.01-10% by mass, more preferably 0.03-5% by mass.

The aqueous solution of the above-mentioned basic compound may also contain a surfactant.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, ethylene oxide/propylene glycol block copolymers, and sorbitol anhydride Non-ionic surfactants such as fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc.; Anionic surfactants such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfonate; Cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01-10% by mass, more preferably 0.05-8% by mass, and particularly preferably 0.1-5% by mass.

You may further perform post-baking as needed. The post-baking is preferably performed in the range of 150 to 250°C for 1 to 240 minutes.

The film thickness of the post-baking coating film can be adjusted appropriately, preferably 0.5~5μm, particularly preferably 0.5~3μm.

The pattern obtained by the colored photosensitive resin composition of the present invention is more useful as a color filter.

The color filter can be used in display devices (liquid crystal display devices, organic EL (Electroluminescence, electroluminescence) devices, etc.), solid-state imaging devices, and electronic devices in a well-known manner. Sub-paper and other machines related to colored images.

[Example]

Next, the present invention will be explained more specifically by citing examples. The "%" and "parts" in the examples and comparative examples are mass% and mass parts unless otherwise specified.

Synthesis example 1

A 1L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was introduced with a proper amount of nitrogen and replaced with a nitrogen atmosphere. 280 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Then, 38 parts by weight of acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]dec-8 or/and 9-yl ester of acrylic acid, and propylene glycol monomethyl ether were added dropwise over 5 hours A mixed solution of 125 parts by weight of acetate. On the other hand, a mixed solution obtained by dissolving 33 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts by weight 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℃) of 125mPa. s, the solid content is 37.0% by weight, the solution acid value is 27mg-KOH/g copolymer solution (resin B-1 solution). The weight average molecular weight Mw of the obtained copolymer (resin B-1) was 9,200, and the degree of dispersion was 2.08.

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 performed using the GPC (Gel Permeation Chromatography) method under the following conditions.

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

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran [THF]

Flow rate: 1.0mL/min

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

Injection volume: 50μL

Detector: RI (Refractive Index, refractive index)

Standard material for calibration: TSK STANDARD POLYSTYRENE

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

(Manufactured by Tosoh Co., Ltd.)

[Preparation of Pigment Dispersion Liquid 1]

Add 13.0 parts of C.I. Pigment Green 58, 2.0 parts of acrylic pigment dispersant, and 85.0 parts of propylene glycol monomethyl ether acetate

Mixing and using a bead mill to fully disperse the pigment, thereby obtaining a pigment dispersion liquid (A-1).

[Preparation of Pigment Dispersion Liquid 2]

Add 5.0 parts of C.I. Pigment Yellow 185, 3.5 parts of acrylic pigment dispersant, and 91.5 parts of propylene glycol monomethyl ether acetate

By mixing and using a bead mill, the pigment is sufficiently dispersed to obtain a pigment dispersion liquid (A-2).

[Preparation of Pigment Dispersion Liquid 3]

12.0 parts of C.I. Pigment Blue 15:3, 4.0 parts of acrylic pigment dispersant, and 84.0 parts of propylene glycol monomethyl ether acetate

The mixture was mixed and a bead mill was used to sufficiently disperse the pigment dispersion liquid (A-3).

[Preparation of Pigment Dispersion 4]

15.0 parts of C.I. Pigment Yellow 138, 4.5 parts of acrylic pigment dispersant, and 80.5 parts of propylene glycol monomethyl ether acetate

By mixing and using a bead mill, the pigment is sufficiently dispersed to obtain a pigment dispersion liquid (A-4).

[Preparation of Pigment Dispersion Liquid 5]

Add 11.0 parts of C.I. Pigment Green 7, 3.0 parts of acrylic pigment dispersant, and 86.0 parts of propylene glycol monomethyl ether acetate

By mixing and using a bead mill, the pigment is sufficiently dispersed to obtain a pigment dispersion liquid (A-5).

Examples 1 to 6 and Comparative Examples 1 to 2

[Preparation of colored photosensitive resin composition]

The components described in Table 1 were mixed to obtain a colored photosensitive resin composition. Propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition became the "solid content (%)" in Table 1.

In Table 1, the components are as follows.

Coloring dispersant (A1): pigment dispersion (A-1)

Coloring dispersant (A2): Pigment dispersion (A-2)

Coloring dispersant (A3): pigment dispersion (A-3)

Coloring dispersant (A4): Pigment dispersion (A-4)

Coloring dispersant (A5): pigment dispersion (A-5)

Resin (B1): Resin B-1 solution

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

Polymerization initiator D1: N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyl Oxime compound)

[Pattern making]

The colored photosensitive resin composition was coated on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) by a spin coating method, and then prebaked at 100°C for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON (Stock)) was used in an atmospheric environment , Light irradiation is performed with an exposure amount of 150mJ/cm ² (365nm standard). As the photomask, a photomask with a pattern of lines and gaps with a line width of 50μm (pitch 50μm) is used. After light irradiation, the above coating film is immersed in an aqueous developer containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds to develop. After washing with water, place in an oven In, post-baking was performed at 230°C for 30 minutes to obtain a pattern.

[Film thickness measurement]

For the obtained pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[Chromaticity Evaluation]

For the obtained pattern, use a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) to measure the spectroscopy, and use the characteristic function of the C light source to measure the CIE (International Commission on Illumination, International Commission on Illumination) XYZ color system Among the xy chromaticity coordinates (x, y) and brightness Y. The results are shown in Table 2.

[Pattern shape]

Regarding the cross section of the obtained pattern, a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies (stock)) was used to observe the shape. If it is the shape shown in FIG. 1 (p1), it is evaluated as ○, and if it is the shape shown in FIG. 1 (p2), it is evaluated as ×. If it is the shape shown in Figure 1 (p1), when the inorganic film is laminated on the pattern, the inorganic film tends to be less likely to crack or peel off. The results are shown in Table 2.

[Observation of peeling film]

In the pattern making, visually observe the developing solution after development. The case where the release sheet derived from the colored photosensitive resin composition was not observed in the developer was evaluated as ○, and the case where the release sheet was observed was evaluated as ×. If a release sheet derived from the colored photosensitive resin composition is observed in the developer, it may adhere to the pattern as a foreign matter, which may cause a defect, so it is not preferable. The results are shown in Table 2.

[Industrial availability]

A color filter with high brightness can be manufactured from the colored photosensitive resin composition of the present invention.

Claims (5)

A colored photosensitive resin composition containing a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as a coloring agent (A), containing a halogenated zinc phthalocyanine Pigment, CI Pigment Yellow 185, and CI Pigment Blue 15:3 or CI Pigment Blue 15:4. The coloring photosensitive resin composition of claim 1, wherein the halogenated zinc phthalocyanine pigment is C.I. Pigment Green 58. According to the coloring photosensitive resin composition of claim 1, wherein the content of C.I. Pigment Yellow 185 is 10-50 parts by mass relative to 100 parts by mass of the polymerizable compound (C). The colored photosensitive resin composition of claim 1, wherein the total amount of the colorant (A) is 20-50 parts by mass relative to 100 parts by mass of the solid content of the colored photosensitive resin composition. A color filter, which is formed of the coloring photosensitive resin composition of claim 1.

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