TWI825269B - Yellow colored hardening composition - Google Patents

Abstract

The present invention provides a yellow colored curable composition capable of producing a color filter having good yellow color characteristics. A yellow colored curable composition, including a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) includes C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185, the content rate of C.I. Pigment Yellow 138 in 100 mass% of the colorant (A) is 70 mass% or more, and the content rate of C.I. Pigment Yellow 185 is 2 mass% or more.

Description

Yellow colored hardening composition

The present invention relates to a yellow colored curable composition, in particular to a yellow colored curable composition containing Dye Index (Color Index, C.I.) Pigment Yellow 138 and C.I. Pigment Yellow 185 as colorants (A). sexual components.

In recent years, color filters used in solid-state imaging devices such as Charge Coupled Devices (CCD) and Complementary Metal Oxide Semiconductor (CMOS) sensors, which are being developed, are composed of complex A coloring composition of color composition is formed and has high color properties. As a means to achieve a complex color composition, a yellow colored composition excellent in yellow color properties is required.

Patent Document 1 discloses a yellow resin composition that forms a color filter used in a liquid crystal display device and an organic light-emitting display device. In order to design a color filter with high brightness and high contrast that suppresses the precipitation of pigment aggregates, the yellow pigment dispersion contained in the yellow resin composition contains: C.I. Pigment Yellow 138 as a quinphthalone pigment, and isoindoline Pigment C.I. Pigment Yellow 139, and acyl imine alkylated derivatives of quinophthalone pigments.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2012-211266

However, the present inventors conducted research and found the following problem: in a yellow resin composition containing C.I. Pigment Yellow 138 and C.I. Pigment Yellow 139 as in Patent Document 1, C.I. Pigment Yellow 139 has a wavelength near 400 nm to 460 nm. It has weak absorption on the short wavelength side, and has absorption over a wide range from the short wavelength side near the wavelength of 400nm to 460nm to the long wavelength side near the wavelength of 500nm. Therefore, the yellow resin composition containing this yellow pigment also has absorption up to 500nm. There is absorption in a wide range to the vicinity, the transmittance curve from the short wavelength side to the long wavelength side becomes gentle, and the yellow color characteristics are poor.

Therefore, an object of the present invention is to provide a yellow coloring curable composition useful for manufacturing a color filter having good yellow color characteristics.

The inventors of the present invention have conducted diligent research in order to solve the above-mentioned problems, and as a result found that in a yellow colored curable composition, if C.I. Pigment Yellow 138 and C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 has excellent yellow color characteristics, and therefore a colored curable composition that can solve the above problems can be obtained, and the present invention has been completed.

That is, the gist of the yellow colored curable composition of the present invention is as follows.

[1] A yellow colored curable composition containing a colorant (A) and a resin (B), the polymerizable compound (C) and the polymerization initiator (D), as the colorant (A), include C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185, in 100% by mass of the colorant (A) The content rate of the C.I. Pigment Yellow 138 is 70% by mass or more, and the content rate of the C.I. Pigment Yellow 185 is 1 mass% or more.

[2] The yellow colored curable composition according to [1], wherein the content rate of the C.I. Pigment Yellow 185 in 100 mass% of the colorant (A) is 2 mass% or more.

[3] The yellow colored curable composition according to [1] or [2], wherein the colorant (A) further contains yellows other than the C.I. Pigment Yellow 138 and the C.I. Pigment Yellow 185 Color material.

[4] A color filter formed from the yellow colored curable composition according to any one of [1] to [3].

[5] A solid-state imaging element including the color filter according to [4].

According to the present invention, it is possible to provide a color filter excellent in yellow color characteristics.

The yellow colored curable composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). As the colorant (A), in the colorant (A) contains C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 in a specific proportion or more. If a yellow coloring curable composition containing C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is used in a specific ratio or above, yellow color characteristics can be obtained Excellent color filters.

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

<Color(A)>

The yellow colored curable composition of the present invention contains C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 as colorants (A).

In this specification, the "total amount of solid content" means the total amount of components excluding the solvent (E) from the yellow colored curable composition of the present invention. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis method such as liquid chromatography (Liquid Chromatography) or gas chromatography (Gas Chromatography).

Furthermore, as the colorant (A), a pigment (hereinafter, sometimes referred to as a pigment (A1)) and/or a dye (hereinafter, sometimes called a pigment) other than C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 may also be included. called dye (A2)).

The pigment (A1) is not particularly limited, and known pigments may be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be used. of paint.

Examples of pigments classified as pigments include: 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, 137, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment orange (pigment orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment red (pigment red) 9, 97 , 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, 291 and other red pigments; C.I. Pigment blue (pigment blue) 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment violet (pigment violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments ; C.I. Pigment green (pigment green) 7, 36, 58 and other green pigments; C.I. Pigment brown (pigment brown) 23, 25 and other brown pigments; C.I. Pigment black (pigment black) 1, 7 and other black pigments, etc.

In addition, the pigment (A1) may be an isoindoline yellow pigment that is not classified as the above pigment, and examples thereof include compounds represented by formula (Y).

[In formula (Y), R ¹ to R ⁵ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, and a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

R ⁶ and R ⁷ represent an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group.

L ¹ and L ² represent -CO- or -SO ₂ -. ]

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁷ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.

The heterocyclic group represented by R ¹ to R ⁷ may be a monocyclic ring or a polycyclic ring.

R ¹ to R ⁵ are preferably hydrogen atoms.

As R ⁶ and R ⁷ , an aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent is preferred, an aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent is more preferred, and even more preferred is an aromatic hydrocarbon group having a carboxyl group as a substituent. Aromatic hydrocarbon group with 6 to 10 carbon atoms.

As L ¹ and L ² , -CO- is preferred.

As the pigment (A1), preferred are C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, Yellow pigments such as 125, 128, 137, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, and isoindoline yellow pigment represented by formula (Y).

These pigments (A1) may be used individually or in two or more types.

C.I. Pigment Yellow 138, C.I. Pigment Yellow 185 and Pigment (A1) may be subjected to rosin treatment, surface treatment using pigment derivatives or pigment dispersants introducing acidic groups or basic groups, use of polymer compounds, etc. if necessary. Grafting treatment on the pigment surface, micronization treatment using the sulfuric acid micronization method, etc., or cleaning treatment using organic solvents or water to remove impurities, and use of ion exchange for ionic impurities. Removal processing of methods, etc. In addition, the pigment preferably has a uniform particle size. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, surfactants can be used, for example, including silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, acrylic-based, etc. surfactants, etc. Examples of the surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid-modified polyesters. , tertiary amine-modified polyurethanes, polyethylenimines, etc., and the trade names include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.) Manufactured), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Japan Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (BYK-Chemie) manufacturing), etc. As a dispersing agent, resin (B) described below can also be used.

These may be used individually or in combination of 2 or more types.

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

C.I. Pigment Yellow 138, C.I. Pigment Yellow 185 and Pigment (A1) can be purchased separately Mix when used as a pigment dispersion. In addition, when two or more pigments (A1) are used, they may be mixed when each is used as a pigment dispersion liquid.

The solvent used in the pigment dispersion is not particularly limited, and examples thereof include the same solvents as the solvent (E) described below. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 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 (also known as diacetone alcohol), N, N-dimethylformamide, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, etc.

The usage amount of the solvent in the pigment dispersion is not particularly limited. The solvent is preferably such that the solid content concentration in the pigment dispersion can be adjusted to 5% to 35% by mass, preferably 10% to 30% by mass. way to use.

The dye (A2) is not particularly limited, and known dyes can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds having hues other than pigments classified in the Dye Index (published by The Society of Dyers and Colorists), or compounds described in the Dyeing Notes (Dyeing Company) Well-known dyes. In addition, based on the chemical structure, examples include: azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, even Nitromethine dyes, squarylium dyes, acridine dyes, styrene-based dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. That's right Among them, organic solvent-soluble dyes are preferred. These dyes (A2) may be used individually or in two or more types.

In addition, yellow pigments and/or yellow dyes are collectively referred to as yellow color materials.

In order to form a yellow composition, the yellow coloring curable composition preferably contains 90 mass % or more of a yellow color material component in 100 mass % of the colorant (A).

The content rate of C.I. Pigment Yellow 138 in 100% by mass of the colorant (A) is 70% by mass or more, more preferably 80% by mass or more. In addition, the content rate of C.I. Pigment Yellow 138 in 100 mass% of the colorant (A) is preferably 99 mass% or less.

The content rate of C.I. Pigment Yellow 185 in 100 mass% of the colorant (A) is 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more, particularly preferably 5 mass% or more. In addition, the content rate of C.I. Pigment Yellow 185 in 100 mass% of the colorant (A) is preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 10 mass% or less.

When using yellow color materials other than C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185, yellows other than C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 will be added based on 100 parts by mass of the total amount of C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185. The content of the color material is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less. As the yellow color material, it is preferable that it has a maximum absorption between a wavelength of 400nm and 500nm, and more preferably it has a maximum absorption between a wavelength of 400nm and 480nm. When the absorbance is measured with a commercially available absorptiophotometer, the maximum absorption is preferably an absorbance of 0.5 or more. The yellow color material only needs to have maximum absorption in the above wavelength range, and may also have absorption in other wavelength ranges.

Moreover, as a yellow color material, a yellow pigment is preferable, and a compound represented by Formula (Y) is more preferable.

Moreover, in 100 mass % of colorants (A), the total amount of C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is preferably 75 mass % or more, more preferably 80 mass % or more.

In 100% by mass of the solid content of the yellow coloring curable composition, the content of the colorant (A) is preferably 20% by mass to 60% by mass, more preferably 25% by mass to 55% by mass, and even more preferably 30% by mass. %~50% by mass.

If the content rate of the colorant (A) in the yellow colored curable composition is high, a color filter with strong color and excellent color characteristics can be obtained. In addition, by setting the content to 60% by mass or less, good pattern formation can be maintained.

<Resin(B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one resin (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as The resin is a structural unit called "(a)"). The resin (B) further preferably has at least one structural unit selected from the group consisting of the monomer (b) derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. ) (hereinafter sometimes referred to as "(b)") is a structural unit derived from monomer (c) copolymerizable with (a) (wherein, it is different from (a) and (b)) (hereinafter sometimes referred to as "(c)") structural unit and a structural unit having an ethylenically unsaturated bond in the side chain.

Specific examples of (a) include: acrylic acid, methacrylic acid acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth)acryloxyethyl] ester, etc., preferably acrylic acid , methacrylic acid, maleic anhydride.

(b) Preferably, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and (methane) base) acryloxy-based monomer.

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

Examples of (b) include: (meth)glycidyl acrylate, vinylbenzyl glycidyl ether, and (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester. , 3-ethyl-3-(meth)acryloxymethyloxetane, (meth)acrylic acid tetrahydrofurfuryl ester, etc., preferably glycidyl (meth)acrylate, (meth)acrylate ) 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloxymethyloxetane.

Examples of (c) include: (methyl)acrylate, butyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[ 5.2.1.0 ^2,6 ]Decan-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N - Cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, etc., preferably styrene, benzyl (meth)acrylate, vinyltoluene, N-phenylmaline Leimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc.

A resin having a structural unit having an ethylenically unsaturated bond in a side chain may It is produced by adding (b) to the copolymer of (a) and (c), or by adding (a) to the copolymer of (b) and (c). This resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting a carboxylic acid anhydride.

The polystyrene-reduced weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000. When the weight average molecular weight is within the above range, the solubility of the unexposed portion to the developer is high, and the resulting pattern tends to have a high residual film rate or hardness.

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

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH/g to 200 mg-KOH/g, more preferably 20 mg-KOH/g to 180 mg-KOH/g, and even more preferably 25 mg-KOH/g. g~150mg-KOH/g. Here, the acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined by titration using a potassium hydroxide aqueous solution, for example.

In 100% by mass of the solid content of the yellow colored curable composition, the content of the resin (B) is preferably from 2 to 50% by mass, more preferably from 3 to 40% by mass, and even more preferably from 10% by mass to 10% by mass. 30% by mass. When the content of the resin (B) is within the above range, the solubility of the unexposed portion to the developer tends to be high.

<Polymerizable compound (C)>

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) and/or an acid. Examples thereof include polymerizable compounds having an ethylenically unsaturated bond. Compounds etc.

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Acrylate, pentaerythritol ten (meth)acrylate, pentaerythritol 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 dipentaerythritol hexa(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone Ester-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 3,000, more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably 20 to 200 parts by mass, more preferably 80 to 180 parts by mass relative to 100 parts by mass of the resin (B) in the yellow colored curable composition.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include: N-benzoyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzene Formaldehyde Benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3- Cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylmercaptophenyl)-3-cyclohexylpropane-1-one-2-imine (hereinafter , also known as 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(o-acetyl oxime)), 2-methyl-2- Morpholinyl-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1- Ketone, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , more preferably 2 parts by mass to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<Polymerization starting aid (D1)>

The yellow colored curable composition of the present invention may also contain a polymerization starting aid (D1). The polymerization starting aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound started by the polymerization initiator. When the polymerization initiating aid (D1) is included, it can be used in combination with the polymerization initiator (D).

Examples of the polymerization starting aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like. Among them, thioxanthone compounds are preferred. Two or more polymerization starting aids (D1) may be contained.

Examples of the amine compound include: triethanolamine, methyldiethanolamine, triethanolamine Isopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylamine benzoate ethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (common name Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone, etc., among which, Preferred is 4,4'-bis(diethylamino)benzophenone. In addition, as the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of the thioxanthone compound include: 2-isopropylthianthrone, 4-isopropylthianthrone, 2,4-diethylthianthrone, and 2,4-dichlorothianthone. Anthrone and 1-chloro-4-propoxythiaxanthone, etc.

Examples of carboxylic acid compounds include: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylmercaptoacetic acid, and methoxyphenylmercaptoacetic acid. Acetic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylmercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine And naphthyloxyacetic acid, etc.

When using these polymerization starting aids (D1), the content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), more preferably Preferably, it is 1 to 20 parts by mass. If the amount of the polymerization starting aid (D1) is within the above range, coloring can be formed with higher sensitivity. patterns, and there is a tendency to improve the productivity of color filters.

<Solvent (E)>

The yellow colored curable composition of the present invention preferably contains a solvent (E). Examples of the solvent (E) include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH but not -O-, - CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetate acetate, Ethyl acetate acetate, Ring Hexanol acetate and γ-butyrolactone, etc.

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, 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenylethyl ether and methyl anisole, etc.

Examples of the ether ester solvent include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2- Ethyl methoxypropionate, 2-methoxypropylpropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionate Methyl ester, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether ethyl Acid ester, 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 Alcohol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

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

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

Examples of aromatic hydrocarbon solvents 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.

Two or more of these solvents (E) may be used in combination.

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

The content rate of the solvent (E) in the total amount of the yellow colored curable composition is preferably 70 mass% to 95 mass%, more preferably 75 mass% to 92 mass%. In other words, in the total amount of the yellow colored curable composition, the content rate of the solid content of the yellow colored curable composition is preferably 5% to 30% by mass, more preferably 8% to 25% by mass. When the content rate of the solvent (E) is within the above range, the flatness during coating becomes good, and the color density will not be insufficient when forming the color filter, so the characteristics tend to become good.

<Leveling agent (F)>

The yellow colored curable composition of the present invention may contain a leveling agent (F). Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, and the like. These may also have a polymerizable group on a side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone 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 Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, 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 Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (manufactured by Daikin Fine Chemicals Research Institute) and E5844 (manufactured by Daikin Fine Chemicals Research Institute), etc.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F473 and Megafac F554 (manufactured by DIC Co., Ltd.), etc.

The content rate of the leveling agent (F) is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.1 mass % or less, based on the total amount of the yellow coloring curable composition, and still more preferably 0.0035 mass% or more and 0.05 mass% or less. In addition, this content rate does not include the content rate of the pigment dispersant. When the content rate of the leveling agent (F) is within the above range, the color filter can have good flatness.

<Other ingredients>

In the yellow colored curable composition of the present invention, fillers, other polymer compounds, adhesion accelerators, antioxidants, thiol compounds, ultraviolet absorbers, anti-aggregation agents, organic acids, organic amine compounds, Additives known in the technical field such as hardeners.

<Production method of yellow colored curable composition>

The yellow colored curable composition of the present invention can be prepared by containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a mixed solvent (E) and leveling It is prepared by adding agent (F), polymerization starting aid (D1) and other ingredients.

C.I. Pigment Yellow 138, C.I. Pigment Yellow 185, and the pigment used as the pigment (A1) if necessary, are preferably mixed with part or all of the solvent (E) in advance and dispersed to the average particle size of the pigment using a bead mill or the like. It is about 0.2μm or less. At this time, part or all of the pigment dispersant and resin (B) may be prepared as necessary. By mixing the remaining pigment into the pigment dispersion obtained in the above manner so as to have a prescribed concentration. The remaining ingredients can be used to prepare a yellow colored hardening composition.

<Manufacturing method of color filter>

Examples of methods for producing a colored pattern from the yellow colored curable composition of the present invention include photolithography, inkjet, and printing. Among them, photolithography is preferred. The photolithography method is a method of applying the yellow colored curable composition on a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a light mask. In the photolithography method, by not using a photomask during exposure and/or not performing development, a colored coating film that is a hardened product of the colored composition layer can be formed. The colored pattern or colored coating film formed in the above manner is the color filter of the present invention.

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

The use of photolithography to form each color pixel can be performed under well-known or customary devices or conditions. For example, it can be produced as follows.

First, a colored curable composition is applied to a substrate, and is dried by heating and drying (prebaking) and/or drying under reduced pressure to remove volatile components such as solvents, thereby obtaining a smooth colored composition layer.

Examples of coating methods include spin coating, slit coating, slit and spin coating, and the like.

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

When drying under reduced pressure is performed, it is preferably carried out under a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C.

Then, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on this photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As a light source used for exposure, a light source that generates light with a wavelength of 250 nm to 450 nm is preferred. For example, for light less than 350nm, a filter can be used to cut off the wavelength range, or for light near 436nm, 408nm, and 365nm, a bandpass filter can be used to selectively extract light in these wavelength ranges. . Specifically, examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

In order to uniformly irradiate the entire exposure surface with parallel light or to accurately align the photomask and the substrate on which the colored composition layer is formed, exposure devices such as a mask aligner and a stepper are preferably used.

The exposed colored composition layer is developed by contacting it with a developer, thereby forming a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration of these basic compounds in the aqueous solution is preferably 0.01 mass% to 10 mass% %, more preferably 0.03 mass% to 5 mass%. Furthermore, the developer may contain a surfactant.

The development method may be any of liquid coating method, dipping method, spray method, etc. Furthermore, the substrate can be tilted to any angle during development.

After development, it is preferred to wash with water.

Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150°C~250°C, and more preferably 160°C~235°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 3 minutes to 60 minutes.

Since the film thickness of the obtained color filter affects adjacent pixels, it is preferably as thin as possible. If the film thickness is thick, color mixing with light from adjacent pixels may occur. The film thickness of the color filter after post-baking is, for example, preferably 3 μm or less, more preferably 2.8 μm or less, further preferably 2.5 μm or less, still more preferably 2.0 μm or less. The lower limit of the film thickness of the color filter is not particularly limited, but is usually 0.3 μm or more, and may be 0.5 μm or more.

Regarding the yellow colored curable composition of the present invention, when the yellow colored curable composition is used to form a colored pattern or a colored coating film with a film thickness of 0.6 μm, the transmittance is preferably 7% or less at a wavelength of 430 nm, and It is more than 85% at a wavelength of 500nm. In addition, it is preferable that the transmittance curve from the short wavelength side to the long wavelength side is not smooth and not too steep. Specifically, it is preferable that the difference between the transmittance at 460 nm and the transmittance at 485 nm (transmittance (485 nm) -Transmittance (460nm)) is 55 or more and 75 or less. If the transmittance and transmittance curve are within the above range, the color characteristics of yellow can be improved. Furthermore, as the transmittance at a wavelength of 430 nm, More preferably, it is 6% or less, and still more preferably, it is 5% or less. The transmittance at a wavelength of 500 nm is more preferably 86% or more, and further preferably 87% or more. The difference between the transmittance at 460 nm and the transmittance at 485 nm is more preferably 60 or more.

By using the yellow colored curable composition of the present invention, it is possible to produce a color filter having good yellow color characteristics especially for use as a solid-state imaging device. The color filter can be used in solid-state imaging elements, but can also be effectively used as a color filter used in other display devices (such as liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.).

This application claims the benefit of priority based on Japanese Patent Application No. 2019-036599 filed on February 28, 2019. The entire specification of Japanese Patent Application No. 2019-036599 filed on February 28, 2019 is incorporated by reference in this application.

[Example]

The following examples are given to illustrate the present invention in more detail. However, the present invention is not limited to the following examples. Of course, the present invention can also be implemented with appropriate changes within the scope suitable for the foregoing/later-described gist. All are included in the technical scope of the present invention. In addition, in the following, unless otherwise specified, "part" means "mass part" and "%" means "mass %".

Synthesis example 1

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere. 340 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Next, 57 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 A mixed solution of 54 parts of a mixture of ^2,6 ]decan-9-yl acrylate (the molar ratio is 1:1), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate. . On the other hand, a solution in which 40 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. . After the dripping of the initiator solution was completed, it was kept at 80°C for 3 hours and then cooled to room temperature to obtain a viscosity of 127 mPa measured with a B-type viscometer (23°C). s. Copolymer (resin B1) solution with a solid content of 37.0%. The weight average molecular weight Mw of the produced copolymer was 9.4×10 ³ , the dispersion degree was 1.89, and the acid value in terms of solid content was 114 mg-KOH/g. Resin B1 has the following structural units.

[Preparation of pigment dispersion liquid (A-1)]

Mix and fully disperse C.I. Pigment Yellow 138 using a bead mill to obtain a pigment dispersion (A-1).

[Preparation of pigment dispersion liquid (A-2)]

Mix and fully disperse C.I. Pigment Yellow 185 using a bead mill to obtain a pigment dispersion (A-2).

[Preparation of pigment dispersion liquid (A-3)]

Mix and fully disperse C.I. Pigment Yellow 138 using a bead mill to obtain a pigment dispersion (A-3).

[Preparation of pigment dispersion liquid (A-4)]

Mix and use a bead mill to fully disperse the yellow color material Y4, thereby obtaining a pigment dispersion liquid (A-4).

Here, the yellow color material Y4 represents 4,4'-(2,2'-((1Z,3Z)-isoindoline-1,3-diylidene)bis(2-cyanoacetyl) ))Dibenzoic acid.

[Preparation of pigment dispersion liquid (A-5)]

Mix and fully disperse C.I. Pigment Yellow 139 using a bead mill to obtain a pigment dispersion (A-5).

Examples 1 to 6 and Comparative Examples 1 to 5

[Preparation of yellow colored curable composition]

The components described in Table 1 were mixed to obtain a yellow colored curable composition. In addition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the yellow colored curable composition became 15%.

In Table 1, each ingredient is as follows.

Colored dispersion (A1): Pigment dispersion (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 solution (B1): Resin B1 obtained above

Polymerizable compound (C): dipentaerythritol polyacrylate

Polymerization initiator (D): 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyl oxime) (PBG-327 ;Made by Trolly Company)

Leveling agent (F): Fluorinated oligomer (Megafac (registered trademark) F554; manufactured by DIC Co., Ltd.)

[Creation of coloring patterns]

After coating the yellow colored curable composition on a 4-inch silicone substrate by spin coating, pre-baking at 80° C. for 2 minutes to obtain a colored composition layer. After cooling, an exposure machine (NSR-1755i7A; manufactured by Nikon Co., Ltd.) was used to irradiate the colored composition layer formed on the substrate with an exposure dose of 300 mJ/cm ² . The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23°C for 50 seconds. After washing with water, it is post-baked in an oven at 230°C for 10 minutes. This results in a coloring pattern.

[Film thickness measurement]

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

[Transmittance evaluation]

The obtained colored pattern was spectrometrically measured using a spectrophotometric device (LvmicroV; manufactured by Lambda Vision Co., Ltd.), and the transmittance was evaluated. The results are shown in Table 2. When the transmittance at a wavelength of 430 nm is 7% or less, the yellow color characteristics (430 nm) are considered to be good (○). When the transmittance at a wavelength of 500 nm is 85% or more, the yellow color characteristics (500 nm) are considered to be good (○). ). Cases outside the above range were regarded as poor yellow color characteristics (×). In addition, the transmittance curve from the short wavelength side to the long wavelength side was evaluated as follows. If the difference between the transmittance at 460nm and the transmittance at 485nm (transmittance (485nm) - transmittance (460nm)) is greater than 75, the transmittance curve is too steep. If it is less than 55, the transmittance curve is flat, so it is set to The yellow color characteristics are poor (×). If the difference between the transmittance at 460nm and the transmittance at 485nm (transmittance (485nm) - transmittance (460nm)) is 55 or more and 75 or less, good yellow color characteristics can be obtained , so the yellow color characteristics are considered to be good (○).

[Industrial availability]

According to the yellow colored curable composition of the present invention, a color filter with excellent yellow color characteristics can be produced.

Claims (5)

A yellow colored hardening composition, including colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D), The colorant (A) includes Dye Index Pigment Yellow 138 and Dye Index Pigment Yellow 185, The content rate of the dye index pigment yellow 138 in 100 mass % of the colorant (A) is 70 mass % or more, and the content rate of the dye index pigment yellow 185 is 1 mass % or more. The yellow coloring curable composition according to claim 1, wherein the content rate of the dye index pigment yellow 185 in 100 mass% of the colorant (A) is 2 mass% or more. The yellow coloring curable composition according to claim 1 or 2, wherein the colorant (A) further contains a yellow color material other than the dye index pigment yellow 138 and the dye index pigment yellow 185. A color filter formed from the yellow colored curable composition according to any one of claims 1 to 3. A solid-state imaging element including the color filter according to claim 4.