KR102455993B1 - Colored photosensitive resin composition - Google Patents

Abstract

[Project] It aims at obtaining the coloring photosensitive resin composition from which the high definition color filter excellent in brightness and developability can be obtained even if it does not thicken it.
[Solution Means] 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), CI Pigment Blue 15 :3 or CI pigment blue 15:4, CI pigment green 58, and CI pigment yellow 138 are included, It is characterized by the above-mentioned.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used for color filter manufacture in display apparatuses, such as a liquid crystal display panel. In recent years, development for a display display to widen the color reproduction gamut that can be displayed is progressing. In order to satisfy the request|requirement, although the method of raising the color material density|concentration in a color filter is mentioned, since performance as a photosensitive resin composition, such as deterioration of a pattern shape, deteriorates when color material density|concentration rises, it is unpreferable. In addition, in order to have the desired color characteristics, it is necessary to manufacture the color filter as a thick film. However, when applied to a liquid crystal display device, color mixing with adjacent pixels occurs, so it is also desirable to make a thick film. don't

In Patent Document 1, in order to design a color filter of dark green color, C.I. Pigment Green 58 and C.I. Pigment Blue 15:3 and C.I. A green photosensitive resin composition comprising a colorant including Pigment Yellow 150 and the like, a resin, a polymerizable monomer, a photoinitiator, and a solvent is disclosed.

Japanese Patent Laid-Open No. 2012-247539

An object of this invention is to obtain the coloring photosensitive resin composition which can obtain the high-definition color filter excellent in brightness and developability, even if it does not thicken it.

The present invention includes the following inventions.

[1] It contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as the colorant (A), C.I. Pigment Blue 15:3 or C.I. Pigment Blue 15:4 and C.I. Pigment Green 58 and C.I. The colored photosensitive resin composition containing Pigment Yellow 138.

[2] A coating film formed from the colored photosensitive resin composition according to [1].

[3] A color filter formed from the colored photosensitive resin composition according to [1].

[4] A display device including the color filter according to [3].

ADVANTAGE OF THE INVENTION According to this invention, it is favorable developability within an appropriate film thickness, and a high definition color filter with high brightness can be manufactured.

The coloring photosensitive resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

It is preferable that the coloring photosensitive resin composition of this invention contains a solvent (E) further.

The coloring photosensitive resin composition of this invention may further contain at least 1 chosen from the group which consists of a leveling agent (F) and a thiol compound.

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

<Colorant (A)>

The coloring photosensitive resin composition of this invention, as a coloring agent (A), C.I. Pigment Green (hereinafter, may be referred to as "PG") 58 and C.I. Pigment yellow (hereinafter, may be referred to as "PY") 138 is included, and C.I. Pigment Blue (hereinafter sometimes referred to as "PB") 15:3, C.I. It further contains a copper phthalocyanine compound selected from Pigment Blue 15:4.

Especially, it is preferable that PG58, PY138, and PB15:3 are included as a coloring agent (A).

It is preferable that content of PG58 is 15 mass % or more in a coloring agent (A), More preferably, it is 20 mass % or more, More preferably, it is 25 mass % or more, It is preferable that it is 90 mass % or less, More preferably, 85 mass % or less, More preferably, it is 80 mass % or less.

Moreover, it is preferable that content of PY138 is 10 mass % or more in a coloring agent (A), More preferably, it is 15 mass % or more, More preferably, it is 20 mass % or more, It is preferable that it is 80 mass % or less, More preferably Preferably it is 75 mass % or less, More preferably, it is 70 mass % or less.

The content of PB15:3 or PB15:4 in the colorant (A) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, and preferably 12 mass% or less. And more preferably, it is 10 mass % or less, More preferably, it is 9 mass % or less.

The content of PB15:3 or PB15:4 is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of PG58 and PY138. and more preferably 0.8 parts by mass or more and 12 parts by mass or less.

Content of PB15:3 or PB15:4 is 0.1-15 mass parts normally with respect to 100 mass parts of total amounts of solid content in a composition, Preferably it is 0.3-10 mass parts, More preferably, it is 0.5-5 mass parts .

The total amount of a coloring agent (A) is 10-50 mass parts normally with respect to 100 mass parts of total amounts of solid content of a coloring photosensitive resin composition, and 30-48 mass parts is preferable from a viewpoint of designing a deep color color filter.

Here, the "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of the coloring photosensitive resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

As a coloring agent (A), you may further contain pigments (A2) other than PG58, PY138, PB15:3, and PB15:4. Examples of the pigment (A2) include pigments classified as pigments in the color index (published by The Society of Dyers and Colorists).

As the pigment (A2), for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 139 , 147, 148, 153, 154, 166, 173, 194, 214 yellow pigments;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Green pigments, such as pigment green 7 and 36; and the like.

When a pigment (A2) is included, it is preferable that the content is 0.1 mass % or more and 40 mass % or less in a coloring agent (A), More preferably, it is 0.5 mass % or more, 30 mass % or less, More preferably It is 1 mass % or more and 20 mass % or less.

The content ratio of the colorant (A) and the resin (B) to be described later (colorant (A)/resin (B)) is, for example, preferably 1.3 or more on a mass basis, more preferably 1.5 or more, still more preferably is 1.7 or more, preferably 4.00 or less, more preferably 3.00 or less, still more preferably 2.50 or less.

Moreover, in this invention, it is preferable that content of the total of PG58, PY138, PB15:3, PB15:4 contained in a coloring agent (A) is 80 mass % or more in a coloring agent (A), More preferably, 90 mass % or more, more preferably 95 mass% or more, particularly preferably 98 mass% or more, and most preferably 100 mass%. The color filter obtained by making a coloring agent (A) into a combination of a specific pigment WHEREIN: The brightness characteristic is exhibited effectively.

PG58, PY138, PB15:3, PB15:4 or the pigment (A2), if necessary, rosin treatment, surface treatment with a pigment derivative into which an acidic or basic group is introduced, graft treatment on the pigment surface with a polymer compound, etc. , an atomization treatment by a sulfuric acid atomization method or the like, a washing treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that a pigment has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

As said pigment dispersant, surfactant is mentioned, for example, Cationic type, anionic type, nonionic type, any surfactant of amphoteric type may be sufficient. Specifically, surfactants, such as a polyester type, a polyamine type, an acrylic type, etc. are mentioned. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As a pigment dispersant, as a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (made by BASF), Ajisper (trademark) (made by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (trademark) (made by Bikchemi), etc. are mentioned.

In the case of using a pigment dispersant, the amount used is preferably 1% by mass or more and 100% by mass or less with respect to the total amount of PG58, PY138, PB15:3, PB15:4 and the pigment (A2), more preferably is 5 mass % or more and 50 mass % or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

<Resin (B)>

Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin, It is more preferable that it is a polymer which has a structural unit derived from at least 1 sort(s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1] At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, and ethylenic properties A copolymer of a monomer (b) having an unsaturated bond (hereinafter sometimes referred to as “(b)”).

Resin [K2] (a) and (b), and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) copolymer.

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

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

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

Resin [K6] Resin obtained by making (a) react with the copolymer of (b) and (c), and further reacting carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl] of polyhydric carboxylic acid having more than divalence, such as monosuccinic acid [2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] esters;

and unsaturated acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point with respect to the aqueous alkali solution of resin obtained.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and ethylene It refers to a polymerizable compound having a sexually unsaturated bond. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

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

(b1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing a straight-chain or branched unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic and monomers (b1-2) having a structure in which hydrocarbons are epoxidized (hereinafter sometimes referred to as “(b1-2)”).

As (b1-1), the monomer which has a glycidyl group and an ethylenically unsaturated bond is preferable. Specifically, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl Ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl- p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene , 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3 and 6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4 -Epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, , cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[Formula 1]

[In formulas (I) and (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, even if the hydrogen atom contained in the alkyl group is substituted with a hydroxy group do.

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

R ^c represents a C1-C6 alkanediyl group.

* indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms for R ^a and R ^b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which the hydrogen atom of R ^a , R ^b is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, and 3-hydroxy group. hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

R ^a and R ^b are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically, preferably Preferably, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group for R ^c include a straight-chain or branched alkanediyl group, and specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group , a linear alkanediyl group such as a pentane-1,5-diyl group and a hexane-1,6-diyl group; branched chain alkanediyl groups such as propane-1,2-diyl groups; and the like.

As X ¹ and X ² , a single bond, *-R ^c -, or *-R ^c -O- is preferable, more preferably a single bond or *-R ^c -O-, and specifically, preferably is a single bond, a methylene group, an ethylene group, *-CH ₂ -O- (* represents a bond with O) group, *-CH ₂ CH ₂ -O- group, and more preferably a single bond, *—CH ₂ CH ₂ —O—.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1) - Formula (I-15) are mentioned. Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15) ) can be mentioned. More preferably, a formula (I-1), a formula (I-7), a formula (I-9), and a formula (I-15) are mentioned.

[Formula 2]

[Formula 3]

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1) - Formula (II-15) are mentioned. Preferably, a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9), a formula (II-11) - a formula (II-15) ) can be mentioned. More preferably, a formula (II-1), a formula (II-7), a formula (II-9), and a formula (II-15) are mentioned.

[Formula 4]

[Formula 5]

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95:5 in formula (I):formula (II), more preferably 10:90 to 90:10, still more preferably 20 :80 to 80:20.

As a monomer (b2) which has an oxetanyl group and an ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

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

As (b), it is preferable that it is (b1) from the point which can make reliability, such as heat resistance of the color filter obtained and chemical-resistance, higher. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of a coloring photosensitive resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, it is called "dicyclopentanyl (meth) acrylate" as a common name Also called "tricyclodecyl (meth)acrylate" in some cases), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (common name in the art) as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) (meth)acrylic acid esters such as acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Vinyl group-containing aromatic compounds, such as styrene, (alpha)-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides, such as acrylamide and methacrylamide; vinyl acetate; dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene; and the like.

Among these, as (c), (meth)acrylic acid ester, vinyl group-containing aromatic compound, dicarbonylimide derivatives, and bicyclo unsaturated compounds are preferable from the point of copolymerization reactivity and heat resistance. Specifically, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept- 2-ene and the like are preferable. Moreover, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable at the point which is excellent in the developability at the time of pattern formation.

In resin [K1], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K1].

a structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%)

a structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency excellent in storage stability, developability, and solvent resistance of the pattern obtained.

Resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (published by Takayuki Otsu, Chemical Dongin, 1st Edition, 1st Edition, March 1, 1972) and citations described in the document It can be prepared with reference to the literature.

Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are poured into a reaction vessel, and stirred, heated, and kept warm in a deoxidized atmosphere is exemplified. In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, Any of those commonly used in the said field|area can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide) etc.) are mentioned, What is necessary is just to melt|dissolve each monomer as a solvent, The solvent (E) etc. which are mentioned later can be used as a solvent of the coloring photosensitive resin composition.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the below-mentioned solvent (E) as a solvent at the time of this polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K2].

a structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%)

a structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)

a structural unit derived from (c); 1-65 mol% (more preferably 5-60 mol%)

When the ratio of the structural unit of the resin [K2] is within the above range, it tends to be excellent in storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the pattern obtained.

The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

Specifically, a method in which predetermined amounts of (a), (b) and (c), a polymerization initiator, and a solvent are poured into a reaction vessel, and stirred, heated, and kept warm in a deoxidized atmosphere can be exemplified. The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

In resin [K3], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K3].

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

(c) 45 to 98 mol%, more preferably 50 to 90 mol%

The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

Resin [K4] can be prepared by obtaining the copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and/or carboxylic acid anhydride of (a). can

First, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise the copolymer of (a) and (c).

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

(c) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Following the preparation of the copolymers of (a) and (c), the atmosphere in the flask is substituted from nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylamino Resin [K4] can be obtained by putting methyl)phenol etc.) and a polymerization inhibitor (for example, hydroquinone etc.) in a flask, and reacting at 60-130 degreeC for 1 to 10 hours, for example.

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable. Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass % is preferable with respect to the total amount of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass % is preferable with respect to the total amount of (a), (b), and (c).

Reaction conditions, such as the injection|pouring method of each reagent, reaction temperature, and reaction time, can take into consideration manufacturing equipment, the calorific value by polymerization, etc., and can be adjusted suitably. On the other hand, similarly to the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

When manufacturing resin [K5], as a 1st step, it carries out similarly to the manufacturing method of resin [K1] mentioned above, and obtains the copolymer of (b) and (c). Similarly to the above, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

In the first step, the ratio of the structural units derived from (b) and (c) is within the following range with respect to the total number of moles of all the structural units constituting the copolymer of (b) and (c). It is preferable to have

a structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)

a structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, as a second step, under the same conditions as in the production method of the resin [K4], the carboxylic acid or carboxylic acid of (a) in the cyclic ether derived from (b) possessed by the copolymer of (b) and (c) By reacting the main acid anhydride, resin [K5] can be obtained.

In the second step, the amount of (a) to be reacted with the copolymer of (b) and (c) is preferably 5 to 80 moles based on 100 moles of (b). Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin obtained by making resin [K5] further react with carboxylic acid anhydride. It can manufacture by making a carboxylic acid anhydride react with the hydroxyl group which arises by reaction of the cyclic ether (a) derived from (b), and carboxylic acid or carboxylic acid anhydride.

Examples of the carboxylic anhydride include 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, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically, as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth) resins such as acrylic acid copolymer [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, etc. of resin [K2]; Resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl(meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer [K3 ]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, and glycidyl (meth) to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate was added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; A resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resins [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride. . These resins may be used independently and may use 2 or more types together.

Especially, as resin (B), resin [K1] and resin [K2] are preferable, and resin [K1] is more preferable.

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When molecular weight exists in said range, the solubility with respect to the developing solution of an unexposed part is high, and there exists a tendency for the residual-film rate and hardness of the pattern obtained also to be high.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this. Preferably it is 50-180 mg-KOH/g, More preferably, it is 60-150 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required for neutralizing 1 g of resin, and can be calculated|required by titrating using potassium hydroxide aqueous solution, for example.

Content of resin (B) becomes like this in solid content of a coloring photosensitive resin composition, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When content of resin (B) exists in said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

<Polymerizable compound (C)>

It is preferable that the weight average molecular weight of a polymeric compound (C) is 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) when irradiated with light, for example, a compound having a polymerizable ethylenically unsaturated bond, etc. can

Especially, as a polymeric compound (C), it is preferable that it is a photopolymerizable compound which has three or more ethylenically unsaturated bonds, For example, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate. , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, Tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, Ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, Caprolactone-modified dipentaerythritol hexa(meth)acrylate and the like. Especially, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa (meth)acrylate, etc. are mentioned.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass % in the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 15-55 mass %. When content of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

To [ content of a polymeric compound (C) / 100 mass parts of resin (B) in the coloring photosensitive resin composition), Preferably it is 20-150 mass parts.

<Polymerization Initiator (D)>

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

As the polymerization initiator (D), compounds that generate active radicals by the action of light are preferable, and alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds (particularly O-acyloxime compounds) and imidazole compounds This is more preferable, and especially the polymerization initiator containing an oxime compound is still more preferable.

The alkylphenone compound is a compound having a partial structure represented by formula (d1) or a partial structure represented by formula (d2). Among these partial structures, the benzene ring may have a substituent. Hereinafter, * represents a bond.

[Formula 6]

Examples of the compound having a partial structure represented by formula (d1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl] butan-1-one; and the like. You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by the formula (d2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4 -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one of oligomers, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d1).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran) -2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis( and trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

As an oxime compound, an O-acyl oxime compound is preferable. The said O-acyl oxime compound is a compound which has a partial structure represented by Formula (d3).

[Formula 7]

Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulf). Panylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-{4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]- propan-1-one-2-imine and the like. You may use commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, BASF make), and N-1919 (made by ADEKA).

Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine and N-acetyloxy-1-[4- At least one selected from the group consisting of {4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propan-1-one-2-imine is preferable, and N-benzoyloxy-1-(4-phenyl Sulfanylphenyl)octan-1-one-2-imine and N-acetyloxy-1-[4-{4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propan-1-one-2- At least one selected from the group consisting of imine is more preferable. If it is these O-acyl oxime compounds, there exists a tendency for the color filter of high brightness to be obtained.

Specific examples of the imidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis( 2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc. see), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (For example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Unexamined Patent Publication) 62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (for example, Japanese Patent Application Laid-Open No. 7-10913, etc.) see) and the like.

Especially, the compound represented by Formula (d4) is preferable.

[Formula 8]

[In formula (d4), R ^d7 to R ^d10 each independently represent a hydrogen atom or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group). R ^d11 and R ^d12 each independently represent a hydrogen atom or a halogen atom (preferably a chlorine atom).]

Specific examples of the compound represented by the formula (d4) include compounds represented by the following formula, and a mixture thereof is preferable.

[Formula 9]

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

Especially, as a polymerization initiator (D), it is preferable that it is 1 or more types chosen from an alkylphenone compound, an oxime compound (especially O- acyl oxime compound), and an imidazole compound, An oxime compound (especially O- acyl oxime compound) And it is more preferable that at least one selected from the group consisting of imidazole compounds. In addition, a polymerization initiator (D) may be combined 2 or more types, and may be combined with the polymerization initiation adjuvant (D1) mentioned later. It is preferable to combine 2 or more types and a polymerization initiation adjuvant (D1) for a polymerization initiator (D). Moreover, as a polymerization initiator (D), it is preferable to contain at least one of an oxime compound (especially O-acyl oxime compound) and an imidazole compound, Both an oxime compound (especially O- acyl oxime compound) and an imidazole compound It is more preferable to include

When using an oxime compound and an imidazole compound together, the content ratio is on a mass basis, Preferably it is 1:9-9:1, More preferably, 2:8-8:2, More preferably, 4:6 -6:4.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

The coloring photosensitive resin composition of this invention may also contain a polymerization start adjuvant (D1). When a polymerization initiator auxiliary (D1) is included, it is usually used in combination with a polymerization initiator (D). A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound (C) which superposition|polymerization was started by a polymerization initiator (D), or a sensitizer.

As a polymerization initiation adjuvant (D1), an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, a thiol compound, etc. are mentioned, A thiol compound is preferable. These polymerization start adjuvant may be used independently and may use 2 or more types together.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; aminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 2-ethylhexyl 4-dimethylaminobenzoate; N,N-dimethylparatoluidine; Alkylamino such as 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone benzophenone; etc. are mentioned, Among these, alkylamino benzophenone is preferable and 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

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

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-pro Foxythioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

A thiol compound is a compound which has a sulfanyl group (-SH) in a molecule|numerator.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanyl. Benzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyridine Midine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino- 6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2- sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole- 2-thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino -5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3 -thiol, 3-sulfanyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3, 4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2- Sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6- Nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyra Zolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4- d] pyrimidine etc. are mentioned.

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

As a thiol compound, the compound which has one sulfanyl group in a molecule|numerator is preferable.

To [ content of a thiol compound / 100 mass parts of polymerization initiators (D) ], Preferably it is 0.5-20 mass parts, More preferably, it is 1-15 mass parts. When content of a thiol compound exists in this range, there exists a tendency for a sensitivity to become high and developability to become favorable.

When using a polymerization initiation auxiliary|assistant (D1), the content is with respect to 1 mol of polymerization initiator (D), Preferably it is 0.01-10 mol, More preferably, it is 0.01-5 mol.

In addition, the total content of the polymerization initiator (D) and the polymerization initiation auxiliary (D1) is preferably 1-35 mass %, more preferably 1-25 mass %, further preferably 1 to 35 mass % with respect to the solid content of the colored photosensitive resin composition. is 5 to 20 mass%.

It is preferable that the coloring photosensitive resin composition of this invention contains a solvent (E). The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O- and not containing -COO-), ether solvents (solvents containing -COO- and -O - containing solvents), ketone solvents other than ester solvents (solvents containing -CO- and not containing -COO-), alcohol solvents (containing OH in the molecule, -O-, -CO- and - COO--free solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. can be selected and used.

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

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylani A brush etc. are mentioned.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, 3-ethoxypropionate ethyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-methoxy-2 -Methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. are mentioned.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, Cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

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

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

These solvents may be used independently and may use 2 or more types together.

Among the above solvents, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferable. , propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionate ethyl, etc. are more preferable. do.

In the coloring photosensitive resin composition, content of a solvent (E) becomes like this. Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of the coloring photosensitive resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<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 a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicone DC3PA, Dong SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company); have.

As said fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Fluorad (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30, RS-718-K (manufactured by DIC Co., Ltd.), EFTO (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Sufflon (registered trademark) S381 , copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute), and the like.

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

Content of a leveling agent (F) becomes like this in the total amount of coloring photosensitive resin composition, Preferably they are 0.001 mass % or more and 0.2 mass % or less, Preferably they are 0.002 mass % or more and 0.1 mass % or less, More preferably, they are 0.01 mass % or more. 0.05 mass % or less. In addition, content of the said pigment dispersant is not contained in this content.

The coloring photosensitive resin composition of this invention may contain additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, and a hardening|curing agent, as needed.

<Method for producing colored photosensitive resin composition>

The coloring photosensitive resin composition of this invention is, for example, a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and the solvent (E) used as needed, a leveling agent ( It can prepare by mixing F), a polymerization start adjuvant (D1), and another component.

<Method for manufacturing color filter>

As a method of forming a pattern using the coloring photosensitive resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable.

The photolithography method is a method of obtaining a pattern by apply|coating the said coloring photosensitive resin composition to a board|substrate, drying, exposing through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

Examples of the substrate include quartz glass, borosilicate glass, alumina silicate glass, glass such as soda-lime glass coated with silica, silicon, metal, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like plastic. etc., what formed the thin film of aluminum, silver, silver/copper/palladium alloy etc. on the said board|substrate is mentioned, Plate shape may be sufficient, and film shape may be sufficient. Moreover, structures, such as a color filter, various insulating or conductive films, and a drive circuit, may be formed in these board|substrates.

Application to the substrate can be performed using, for example, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater, or a spinless coater), or an inkjet coating device.

As a drying method of the film|membrane apply|coated to the board|substrate, methods, such as heat drying, natural drying, ventilation drying, and reduced pressure drying, are mentioned. You may carry out combining several methods. As drying temperature, 10-120 degreeC is preferable and 50-100 degreeC is more preferable. Moreover, as a heating time, it is preferable that they are for 10 second - 60 minutes, and it is more preferable that they are 30 second - 10 minutes. It is preferable to perform reduced-pressure drying at the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The coating film after drying is exposed through the photomask for forming the target pattern. The pattern shape on the photomask at this time is not specifically limited, The pattern shape according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can do it. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use a device such as a mask aligner or a stepper because it is possible to uniformly irradiate parallel rays to the entire exposure surface or to accurately align the photomask and the substrate.

After exposure, a pattern can be obtained by making it contact with a developing solution, dissolving a predetermined part (for example, unexposed part), and developing. Although an organic solvent can also be used as a developing solution, since melt|dissolution and swelling of the exposed part of a coating film do not occur easily by a developing solution, and a favorable-shaped pattern is obtained, the aqueous solution of a basic compound is preferable.

The developing method may be any of a paddle method, a dipping method, and a spray method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development.

After image development, it is preferable to wash with water.

Examples of the basic compound 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, hydrogen carbonate Inorganic basic compounds, such as sodium, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, Organic basic compounds, such as ethanolamine, are mentioned. Among them, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferable.

The concentration in the aqueous solution of these inorganic and organic basic compounds is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The aqueous solution of the basic compound may contain a surfactant.

As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Nonionic surfactants, such as fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine;

anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium dodecylnaphthalenesulfonate;

Cationic surfactants, such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned.

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

Moreover, you may post-baking as needed. It is preferable to perform a post-baking in the range for 150-250 degreeC and 1-240 minutes, for example.

As for the film thickness of the coating film after a post-baking, since the film thickness of the obtained coating film has a large influence with an adjacent pixel, it is preferable that it is a film as thin as possible, and it is preferable that it is 3 micrometers or less. In addition, in the case of a thick film, when a liquid crystal display device (e.g., a liquid crystal panel) is manufactured, the light from the light source leaks through pixels of two or more colors. It is not preferable for the reasons of Moreover, it is preferable that the film thickness of the coating film after a post-baking is 0.5 micrometer or more.

The colored coating film and coloring pattern formed from the coloring photosensitive resin composition of this invention are useful as a color filter. The said color filter can be used for the apparatus related to various colored images, such as a display device (For example, a liquid crystal display device, an organic electroluminescent device, etc.), a solid-state image sensor, and electronic paper in a well-known aspect.

Example

Next, the present invention will be described in more detail by way of Examples. "%" and "part" in an example are mass % and mass part, unless there is a special note.

Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed to replace with a nitrogen atmosphere, 280 parts by weight of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80° C. while stirring. Subsequently, a mixed solution of 38 parts by weight of acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 or/and 9-yl acrylate, and 125 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. 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 completion of dripping, it was maintained at the same temperature for 4 hours, cooled to room temperature, and resin B-1 containing a copolymer having a B-type viscosity (23°C) of 125 mPas, a solid content of 37.0% by weight, and a solution acid value of 27 mg-KOH/g. A solution was obtained. The weight average molecular weight Mw of the produced|generated copolymer was 9200, and molecular weight distribution 2.08.

The polystyrene conversion weight average molecular weight Mw and number average molecular weight Mn of the resin obtained by the said synthesis example were measured using the GPC method on condition of the following.

Device; HLC-8120GPC (manufactured by Toso Co., Ltd.)

column; TSK-GELG2000HXL

column temperature; 40℃

menstruum; THF

flow rate; 1.0mL/min

test solution solids concentration; 0.001 to 0.01 mass %

injection volume; 50 μL

detector; RI

calibration standards; TSK STANDARD POLYSTYRENE

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

(manufactured by Toso Co., Ltd.)

[Preparation of pigment dispersion (A-1)]

C.I. Pigment Green 58 13.0 parts

2.0 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 85.0 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-1).

[Preparation of pigment dispersion (A-2)]

C.I. Pigment Yellow 138 15.0 parts

4.5 parts of acrylic pigment dispersant

80.5 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-2).

[Preparation of pigment dispersion (A-3)]

C.I. Pigment Blue 15:3 12.0 parts

4.0 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 84.0 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-3).

[Preparation of pigment dispersion (A-4)]

C.I. Pigment Yellow 150 11.9 parts

5.4 parts of acrylic pigment dispersant

82.7 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-4).

[Preparation of pigment dispersion (A-5)]

C.I. Pigment Green 7 11.0 parts

3.3 parts of acrylic pigment dispersant

81.3 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-5).

Examples 1-4 and Comparative Examples 1-3

[Preparation of colored photosensitive resin composition]

The components of Table 1 were mixed, and the coloring photosensitive resin composition was obtained. On the other hand, propylene glycol monomethyl ether acetate was mixed so that solid content of the coloring photosensitive resin composition might become "solid content (%)" of Table 1.

In Table 1, each component is as follows.

colored dispersion (A1); Pigment dispersion liquid (A-1) obtained above

colored dispersion (A2); Pigment dispersion (A-2) obtained above

colored dispersion (A3); Pigment dispersion (A-3) obtained above

colored dispersion (A4); Pigment dispersion (A-4) obtained above

colored dispersion (A5); Pigment dispersion (A-5) obtained above

resin (B1); Resin B-1 solution

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

polymerization initiator (D1); N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound)

polymerization initiator (D2); A mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge Corporation; biimidazole compound)

[Formula 10]

polymerization initiation aid (D3); 2-sulfanylbenzothiazole (Soxinol M; manufactured by Sumitomo Chemical Co., Ltd.; a compound represented by the following formula)

[Formula 11]

leveling agent (F1); Polyether-modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Production of colored coating film]

On a 2-inch edged glass substrate (Eagle XG; manufactured by Corning), the colored photosensitive resin composition was applied by spin coating, and then prebaked at 100°C for 3 minutes. After cooling, the substrate coated with the colored photosensitive resin composition was irradiated with light at an exposure dose (based on 365 nm) of 150 mJ/cm 2 in an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). After light irradiation, the obtained film is developed by immersing it in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, post-baking at 230°C for 30 minutes in an oven, , a colored coating film was obtained.

By repeatedly performing manufacture and chromaticity evaluation of a colored coating film, and adjusting the rotation speed of the spin coat at the time of apply|coating a colored photosensitive resin composition, the colored coating film which is x=0.235 and y=0.620 in chromaticity coordinates was obtained. Table 2 shows the brightness and film thickness of the obtained colored coating film. At this time, the brightness Y is preferably 42 or more, and the higher the numerical value, the more the power of the backlight is able to be displayed in the same way as the panel.

[Film thickness measurement]

About the obtained colored coating film, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

[Chromaticity evaluation]

With respect to the obtained colored coating film, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and xy chromaticity coordinates (x, y) in the CIE XYZ color system using the characteristic function of the C light source. ) and brightness Y were measured.

[Evaluation of dissolution time (development solubility)]

On a 2-inch edged glass substrate (Eagle XG; manufactured by Corning), the colored photosensitive resin composition was applied by spin coating in the same manner as above, and then prebaked at 100°C for 3 minutes. After cooling, an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide is sprayed at 0.05 hPa with a spin developer (SD-408R; manufactured by Oshigane Co., Ltd.) to dissolve the entire film applied on the substrate. The time to completion was measured. A result is shown in Table 2.

[Production of Colored Pattern]

On a 2-inch corner glass substrate (Eagle XG; manufactured by Corning), the colored photosensitive resin composition was applied by spin coating so as to have a film thickness shown in Table 2, and then dried under reduced pressure to 130 Pa with a reduced pressure dryer. Thereafter, the interval 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 Co., Ltd.) was used in an atmospheric atmosphere, 150 mJ/ It was irradiated with light at an exposure dose of cm 2 (based on 365 nm). On the other hand, as a photomask, a mask in which a 50 µm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for the dissolution time measured above +30 seconds, and after washing with water, in an oven at 230°C Post-baking was performed for 30 minutes to prepare a colored pattern.

[development type]

When it was made to be immersed in the developing solution during coloring pattern manufacture, the solubility with respect to the developing solution of an unexposed part was confirmed. When it melt|dissolved in a developing solution, when the solid material peeled from the glass substrate with "circle" and a peeling piece was confirmed, it evaluated as "x". A result is shown in Table 2. When it dissolves in a developing solution while generating a peeling piece, in the process of manufacturing a coloring pattern, after a peeling piece generate|occur|produces, since it adheres to another pixel and a normal coloring pattern is not obtained, a yield falls extremely.

[pattern shape]

In the colored pattern having a manufactured line-and-space pattern, when a 30 µm pattern is obtained, it is evaluated as “○” if the shape is forward taper, and “×” if the shape is reverse taper. did. A result is shown in Table 2.

From the coloring photosensitive resin composition of Examples 1-4, it was confirmed that a film thickness exists in an appropriate range, and can form a high-brightness colored coating film. In addition, when forming a colored pattern from the colored photosensitive resin composition of each Example, it was confirmed that a peeling piece did not generate|occur|produce in an unexposed part, and the solubility with respect to a developing solution was favorable, and the colored pattern with a good shape was obtained.

On the other hand, it was confirmed that the colored coating film obtained from each colored photosensitive resin composition of Comparative Example 1 and Comparative Example 3 had low brightness, and the colored photosensitive resin composition of Comparative Example 2 was difficult to thin, and the film thickness became thicker than 3 µm. . And when forming a coloring pattern from each coloring photosensitive resin composition of Comparative Examples 1-3, it peeled from the coating-film glass substrate of an unexposed part, and it was confirmed that solid substance generate|occur|produced. Moreover, in each coloring photosensitive resin composition of Comparative Examples 1 and 2, the coating film with a favorable pattern shape was not able to be obtained.

From the coloring photosensitive resin composition of this invention, within an appropriate film thickness, it is favorable developability, and a high definition color filter with high brightness can be manufactured.

Claims (4)

a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
The coloring photosensitive resin composition containing CI pigment blue 15:3 or CI pigment blue 15:4, CI pigment green 58, and CI pigment yellow 138 as said coloring agent (A). The coating film formed from the coloring photosensitive resin composition of Claim 1. The color filter formed from the coloring photosensitive resin composition of Claim 1. A display device comprising the color filter according to claim 3 .