JP7233831B2 - Colored curable resin composition, color filter, and display device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored curable resin composition, a color filter and a display device.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays and solid-state imaging devices such as CCD and CMOS sensors are produced from colored curable resin compositions. As such a colored curable resin composition, C.I. I. A composition containing Pigment Red 269 is known (Patent Document 1).

JP 2016-170324 A

However, conventionally known color filters formed from the above colored curable resin compositions have not been sufficiently satisfactory in terms of contrast. Accordingly, the present invention provides a colored curable resin composition capable of forming a color filter excellent in contrast.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよい炭素数１～８の炭化水素基、ハロゲン原子、または－ＯＲ^３基を表す。
Ｒ^３は、置換基を有していてもよい炭素数１～８の炭化水素基を表す。
Ｍ^ｋ＋は、ｋ価のカチオンを表す。
ｋは、１以上５以下の整数を表す。
ｍは、０以上４以下の整数を表し、ｍが２以上のとき複数のＲ^１は同一でも異なっていてもよい。
ｎは、１以上５以下の整数を表し、ｎが２以上のとき複数のＲ^２は同一でも異なっていてもよい。］
［２］ ［１］記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［３］ ［２］記載のカラーフィルタを含む表示装置。 The present disclosure includes the following inventions.
[1] including a coloring agent, a resin, a polymerizable compound and a polymerization initiator,
The colored curable resin composition, wherein the coloring agent contains a compound represented by formula (I).

[in the formula (I),
R ¹ and R ² each independently represent an optionally substituted hydrocarbon group having 1 to 8 carbon atoms, a halogen atom, or a —OR ³ group.
R ³ represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms.
Mk ⁺ represents a k-valent cation.
k represents an integer of 1 or more and 5 or less.
m represents an integer of 0 or more and 4 or less, and when m is 2 or more, multiple R ^1s may be the same or different.
n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different. ]
[2] A color filter formed from the colored curable resin composition described in [1].
[3] A display device including the color filter described in [2].

ADVANTAGE OF THE INVENTION According to this invention, the coloring curable resin composition which can form a color filter excellent in contrast is provided.

<Colored curable resin composition>
The colored curable resin composition of the present invention contains a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and contains a compound represented by formula (I).
The colored curable resin composition of the present invention may further contain a polymerization initiation aid (D1), a solvent (E) and a leveling agent (F).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

<Colorant (A)>
The colored curable resin composition of the present invention contains a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) as a coloring agent (A).

[in the formula (I),
R ¹ and R ² each independently represent an optionally substituted hydrocarbon group having 1 to 8 carbon atoms, a halogen atom, or a —OR ³ group.
R ³ represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms.
Mk ⁺ represents a k-valent cation.
k represents an integer of 1 or more and 5 or less.
m represents an integer of 0 or more and 4 or less, and when m is 2 or more, multiple R ^1s may be the same or different.
n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different. ]

The optionally substituted C 1-8 hydrocarbon groups represented by R ¹ , R ² and R ³ are preferably optionally substituted C 1-8 An aliphatic hydrocarbon group or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms, more preferably an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms It is a hydrogen group.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms for R ¹ , R ² and R ³ may be linear, branched or cyclic.
Linear or branched aliphatic hydrocarbon groups include linear aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; branched chain aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 4 carbon atoms.
A cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3-8, more preferably 3-6.

Examples of the aromatic hydrocarbon group having 6 to 8 carbon atoms for R ¹ , R ² and R ³ include phenyl group, tolyl group, xylyl group, phenethyl group and α-methylbenzyl group. The aromatic hydrocarbon group preferably has 6 carbon atoms.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ may have a substituent, and the substituent may be a fluorine atom, a chlorine atom, an iodine atom or a bromine atom. cyano group; amino group; hydroxy group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; sulfanyl group; Alkylsulfanyl group; carboxy group; carbamoyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; sulfo group; sulfamoyl group; Alkoxysulfonyl group of; and the like.

R ¹ , R ² and R ³ are each independently preferably a methyl group, an ethyl group, a propyl group, a trifluoromethyl group or a phenyl group, more preferably a methyl group or an ethyl group. R ¹ , R ² and R ³ may be the same or different.

The halogen atom represented by R ¹ or R ² includes a fluorine atom, a chlorine atom, an iodine atom, a bromine atom and the like, preferably a chlorine atom.

The —OR ³ groups represented by R ¹ or R ² are particularly preferably methoxy or ethoxy.

Mk ⁺ is preferably a hydrogen ion, a k-valent metal ion or a substituted or unsubstituted ammonium ion.
The k-valent metal ions represented by Mk ⁺ include alkali metal ions such as lithium ion, sodium ion and potassium ion; alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion and barium ion; titanium ion; Transition metal ions such as zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions ion; and the like.
Substituted or unsubstituted ammonium ions represented by Mk ⁺ include quaternary ammonium ions such as tetraalkylammonium ions.
Mk ⁺ is preferably a hydrogen ion or a k-valent metal ion, more preferably a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion, still more preferably an alkaline earth metal ion. Mk ⁺ is preferably hydrogen ion, sodium ion, potassium ion, magnesium ion, strontium ion, barium ion, zirconium ion, manganese ion, or zinc ion, and more preferably hydrogen ion or barium ion.

k is preferably 4 or less, more preferably 3 or less, and still more preferably 1 or 2.

m is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and even more preferably 0. When m is 2 or more, a plurality of R ¹ may be the same or different.

n is preferably 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and particularly preferably 3. When n is 2 or more, multiple R ² may be the same or different.

Compound (I) preferably has a valence of 0, that is, an electrically neutral compound.

Compound (I) is preferably a compound represented by formula (II) (hereinafter sometimes referred to as compound (II)).

[in the formula (II),
R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom or an —OR ³ group, and at least one or more of R ²¹ to R ²⁵ is a halogen atom or —OR ³ group.
R ¹ , m, R ³ , M ^k+ and k are the same as above. ]

The halogen atom in the formula (II) includes fluorine atom, chlorine atom, iodine atom, bromine atom and the like, preferably chlorine atom.

Preferably, two or more (preferably four or less) of R ²¹ to R ²⁵ are halogen atoms and/or —OR ³ groups, more preferably three of R ²¹ to R ²⁵ are halogen atoms and/or or -OR ³ group.

In formula (II), it is preferred that either one of R ²¹ or R ²³ or both R ²¹ and R ²³ , more preferably R ²¹ and R ²³ are —OR ³ groups.
In formula (II), either one of R ²⁴ or R ²⁵ or both R ²⁴ and R ²⁵ , more preferably R ²⁴ is preferably a halogen atom.

The compound (II) is at least one selected from compounds represented by formula (II-a), compounds represented by formula (II-b), and compounds represented by formula (II-c). preferable. Among them, the compound represented by the formula (II-b) or the compound represented by the formula (II-c) is preferable, and the compound represented by the formula (II-b) is more preferable, since the contrast is good. be.

[In formula (II-a), formula (II-b), and formula (II-c), R ²¹ to R ²⁵ , M ^k+ and k are the same as above. ]

Examples of compound (I) include compounds represented by formulas (I-1) to (I-216) shown in Tables 1 to 3, and the like.
Compound (I) is
Preferably compounds represented by formulas (I-13) ~ formula (I-20), compounds represented by formulas (I-85) ~ formula (I-92), formulas (I-157) ~ formula (I -164) is a compound represented by
More preferably compounds represented by formulas (I-13) to (I-16), compounds represented by formulas (I-85) to (I-88), formulas (I-157) to ( I-160) is a compound represented by
More preferred are compounds represented by formulas (I-85) to (I-88) and compounds represented by formulas (I-157) to (I-160).

In Tables 1 to 3, OMe represents a methoxy group and OEt represents an ethoxy group.
Further, in Tables 1 to 3, “PH” represents a phenyl group to which SO ₃ ^— and (R ¹ ) _m are bonded in formula (I) (* represents a bond with a nitrogen atom). means a group represented by formulas (Ph1) to (Ph3).

The compound represented by the formula (I) (where M ^k+ =H ⁺ ) is obtained by reacting the compound represented by the formula (pt1) with a nitrite (e.g., sodium nitrite) in an acidic aqueous solution to form a diazonium salt. After production, it can be produced by reacting the produced diazonium salt with the compound represented by the formula (pt2). In this reaction, the amount of the compound represented by formula (pt1) to be used is preferably 0.5 to 1.5 mol per 1 mol of the compound represented by formula (pt2).
The compound represented by formula (I) (where M ^k+ ≠H ⁺ ) is a compound represented by formula (I) (where M ^k+ =H ⁺ ) and a k-valent cation M ^k+ (where M ^k+ ≠H ⁺ ) containing halides (preferably chlorides), acetates, phosphates, sulfates, silicates or cyanides.

[In Formula (pt1), Formula (pt2), and Formula (I), R ¹ , R ² , m, n, M ^k+ and k are the same as above. ]

The content of compound (I) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, and 50% by mass of the total amount of colorant (A). It is more preferably at least 80% by mass, particularly preferably at least 80% by mass, and most preferably at least 90% by mass.

The colored curable resin composition of the present invention may contain a dye (A1) and a pigment (A2) in addition to the compound (I) as the colorant (A).

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Staining Note (Shikisensha). be done. According to the chemical structure, azo dyes (excluding compound (I)), cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes , squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
Examples of pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
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. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

The content of the coloring agent (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass, relative to the total amount of solids. %.
Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin and contains at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter "(a)" is more preferable. The resin (B) further comprises a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond, A structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and a side It preferably has at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic mono[2-(meth ) acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, and maleic anhydride.

(b) is preferably a monomer having 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) and a (meth)acryloyloxy group. .
In this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.
Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-ethyl-3- (Meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate and the like, preferably glycidyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ( meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.

(c) includes, for example, methyl (meth)acrylate, butyl (meth)acrylate cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8 -yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, preferably styrene , vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferred.

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

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. .
The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, still more preferably 40 to 135 mg-KOH/g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution. .

The content of resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass, based on the total solid content.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D). is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate and the like.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total solid content. be.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include 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, 2-methyl-2-morpholino-1-( 4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl )-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

The colored curable resin composition of the present invention may contain a polymerization initiation aid (D1).

<Polymerization initiation aid (D1)>
The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-phenylglycine and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.

The colored curable resin composition of the present invention may contain a solvent (E).

<Solvent (E)>
The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As a solvent,
Ester solvents (-COO- solvent containing and not containing -O-);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule but not containing -COO- );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (-COO- and a solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- in the molecule but not containing -COO-);
Alcohol solvents such as butanol, cyclohexanol, propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-);
amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone;
More preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and 4-hydroxy-4-methyl-2-pentanone.

When the solvent (E) is included, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. is. In other words, the total solid content of the colored curable resin composition is preferably 5-30% by mass, more preferably 8-25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. .

The colored curable resin composition of the present invention may contain a leveling agent (F).

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. .

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

Examples of the fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.001 to 0.2% by mass, based on the total amount of the colored curable resin composition. 002 to 0.1% by mass. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention may optionally contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers and chain transfer agents. may include

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an optional polymerization initiation aid (D1). , solvent (E), leveling agent (F) and other ingredients.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred.

When the colored curable resin composition contains the compound (I) as a coloring agent, a color filter having particularly excellent contrast can be produced. The color filter is useful as a color filter for use in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

EXAMPLES Hereinafter, the colored curable resin composition of the present invention will be described in more detail with reference to examples. Unless otherwise specified, "%" and "parts" in the examples are % by mass and parts by mass.

[Synthesis Example 1]
After adding 100 parts of water to 17.3 parts of alternilic acid, 4.0 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 21.7 parts of a 35% sodium nitrite aqueous solution was added, and then 11.5 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.
37.6 parts of 5'-chloro-3-hydroxy-2',4'-dimethoxy-2-naphthanilide was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto over 15 minutes. After the dropwise addition was completed, the mixture was further stirred for 30 minutes to obtain a yellow suspension. The suspension was stirred for 1 hour and then for an additional hour. The red solid obtained by filtration was dried at 60° C. under reduced pressure to obtain 53.2 parts of the compound represented by formula (I-1).

5.4 parts of the compound represented by the formula (I-1) was added to 100 parts of water to prepare a liquid (aqueous solution 1) in which the compound represented by the formula (I-1) was dissolved. Separately, a liquid (aqueous solution 2) was prepared by dissolving 4.9 parts of barium chloride dihydrate in 80 parts of water. Stirred. After cooling, the crystals were filtered, washed twice with 100 parts of ion-exchanged water, and dried under reduced pressure at 100° C. to obtain 6.8 parts of the compound represented by the formula (I-13).

[Synthesis Example 2]
Compounds represented by formulas (I-73) and (I-85) were obtained in the same manner as in Synthesis Example 1, except that metanilic acid was used instead of orthonilic acid.

[Synthesis Example 3]
Compounds represented by formulas (I-145) and (I-157) were obtained in the same manner as in Synthesis Example 1, except that sulfanilic acid was used in place of orthonilic acid.

[Resin Synthesis Example 1]
A suitable amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2. A solution of 289 parts of a mixture of 1.0 ^2,6 ]decane-9-yl acrylate (content ratio is 1:1) dissolved in 125 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. . On the other hand, a solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over about 6 hours using another dropping pump. bottom. After the dropwise addition was completed, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 35.1%. The resulting copolymer had a weight average molecular weight Mw of 9200, a dispersity of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content. Resin (B-1) has the following structural units.

[Resin Synthesis Example 2]
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 85° C. while stirring. Then, 54 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 ^{2, 6} ] A mixed solution of 225 parts of a mixture of decan-9-yl acrylate (content ratio is 1:1), 81 parts of vinyl toluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the completion of the dropping of the initiator solution, it was held at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2 )) solution was obtained. The resulting copolymer had a weight average molecular weight Mw of 10,600, a dispersity of 2.01, and an acid value of 112 mg-KOH/g in terms of solid content. Resin (B-2) has the following structural units.

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel permeation chromatography (GPC method) under the following conditions.
Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40°C
Solvent; THF
Flow rate; 1.0 mL/min
Test liquid solid content concentration; 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene-equivalent weight-average molecular weight and the number-average molecular weight obtained above was defined as the degree of dispersion.

(Preparation of colored curable resin composition)
[Preparation of dispersion (P-1)]
10 parts of the compound represented by formula (I-13), dispersant (BYK-LPN21116 manufactured by BYK; 60% propylene glycol monomethyl ether acetate solution) 13.3 parts, resin (B-2) (solid content conversion) 8 20 parts of 4-hydroxy-4-methyl-2-pentanone and 149 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.2 μm zirconia beads are added, and a paint conditioner (manufactured by LAU Co.) is used for 6 shaken for an hour. After that, the zirconia beads were removed by filtration to obtain a dispersion (P-1).

[Preparation of dispersion (P-2)]
10 parts of the compound represented by the formula (I-85), dispersant (BYK BYK-LP N21116; 60% propylene glycol monomethyl ether acetate solution) 16.7 parts, resin (B-2) (solid content conversion) 8 parts, 20 parts of 4-hydroxy-4-methyl-2-pentanone and 145 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.2 μm zirconia beads are added, and a paint conditioner (manufactured by LAU) is used. Shake for 3 hours. After that, the zirconia beads were removed by filtration to obtain a dispersion (P-2).

[Preparation of dispersion (P-3)]
A dispersion (P-3) was prepared in the same manner as the dispersion (P-2) except that the compound represented by the formula (I-85) was replaced with the compound represented by the formula (I-157). .

[Preparation of dispersion (P-4)]
The compound represented by the formula (I-85) was prepared by C.I. I. A dispersion (P-4) was prepared in the same manner as the dispersion (P-2), except that Pigment Red 269 was used.

Each component was mixed so as to have the composition shown in Table 4 to obtain a colored curable resin composition.

In Table 4, each component represents the following compounds.
(B-1): Resin (B-1) (solid content conversion)
(C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(D-1): N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF)
(E-1): propylene glycol monomethyl ether acetate (E-2): 4-hydroxy-4-methyl-2-pentanone (F-1): polyether-modified silicone oil (Toray Silicone SH8400: Dow Corning Toray Co., Ltd. ) made)

<Production of color filter>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a colored composition layer. After standing to cool, it was post-baked in an oven at 230° C. for 20 minutes to obtain a color filter.

<Contrast evaluation>
Using a contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by Topcon Corporation, light source; F-10, polarizing film; manufactured by Tsubosaka Electric Co., Ltd.), Contrast was measured with a blank value of 30,000. Table 5 shows the results.

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

Claims (3)

including a coloring agent, a resin, a polymerizable compound and a polymerization initiator,
The colored curable resin composition, wherein the coloring agent contains one or more selected from compounds represented by formula (II-b) and compounds represented by formula (II-c).

[In formula (II-b) and formula (II-c),
R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom or a --OR ³ group. However, at least one or more of R ²¹ to R ²⁵ is a halogen atom, and at least one or more is —OR ³ group.
R ³ represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms.
M ^k+ represents a k-valent alkaline earth metal ion .
k represents 2 ; ] A color filter formed from the colored curable resin composition according to claim 1 . A display device comprising the color filter according to claim 2 .