KR102211795B1 - Colored resin composition, colored filter and display device - Google Patents

Abstract

［식(I) 중,
R¹ 및 R²는, 각각 독립적으로, 치환기를 갖고 있어도 좋은 탄소수 1~8의 탄화수소기를 나타낸다.
X¹ 및 X²는, 각각 독립적으로, 수소 원자, 시아노기, 또는 카르바모일기를 나타낸다.
L¹ 및 L²는, 각각 독립적으로, 치환기를 갖고 있어도 좋은 탄소수 1~8의 2가의 탄화수소기를 나타낸다.
k는, 0 이상 4 이하의 정수를 나타낸다.
M ⁿ⁺는, 임의의 양이온을 나타낸다.
n은, 1 이상 5 이하의 정수를 나타낸다.］The present invention provides a colored curable resin composition capable of forming a color filter excellent in contrast.
The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant contains a compound represented by formula (I).

[In formula (I),
Each of R ¹ and R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
Each of X ¹ and X ² independently represents a hydrogen atom, a cyano group, or a carbamoyl group.
L ¹ and L ² each independently represent a C 1 to C 8 divalent hydrocarbon group which may have a substituent.
k represents an integer of 0 or more and 4 or less.
M ⁿ⁺ represents an arbitrary cation.
n represents the integer of 1 or more and 5 or less.]

Description

A colored curable resin composition, a color filter, and a display device TECHNICAL FIELD [COLORED RESIN COMPOSITION, COLORED FILTER AND DISPLAY DEVICE]

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

A color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display, or a solid-state imaging device such as a CCD or CMOS sensor is made of a colored curable resin composition. As such a colored curable resin composition, a composition containing a compound represented by formula (3) as a colorant is known (Patent Document 1).

Japanese Patent Publication No. 2009-235392

However, the conventionally known color filter formed from the above-described colored curable resin composition may not sufficiently satisfy the contrast. Here, the present invention provides a colored curable resin composition capable of forming a color filter excellent in contrast.

The present invention includes the following inventions.

[1] Including a colorant, a resin, a polymerizable compound, and a polymerization initiator,

The colored curable resin composition containing the compound represented by the formula (I) in the 　 coloring agent.

[In formula (I),

Each of R ¹ and R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Each of X ¹ and X ² independently represents a hydrogen atom, a cyano group, or a carbamoyl group.

L ¹ and L ² each independently represent a C 1 to C 8 divalent hydrocarbon group which may have a substituent.

k represents an integer of 0 or more and 4 or less.

M ⁿ⁺ represents an arbitrary cation.

n represents the integer of 1 or more and 5 or less.]

[2] A color filter formed from the colored curable resin composition according to [1].

[3] A display device including the color filter described in [2].

According to the present invention, a colored curable resin composition capable of forming a color filter excellent in contrast is provided.

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as the colorant (A), a compound represented by formula (I) is included. do.

The colored curable resin composition of the present invention may further contain a polymerization initiator (D1), a solvent (E), and a leveling agent (F).

In the present specification, the compounds exemplified as each component can be used alone or in combination of multiple types unless otherwise specified.

<Coloring agent (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 the colorant (A).

[In formula (I),

Each of R ¹ and R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Each of X ¹ and X ² independently represents a hydrogen atom, a cyano group, or a carbamoyl group.

L ¹ and L ² each independently represent a C 1 to C 8 divalent hydrocarbon group which may have a substituent.

k represents an integer of 0 or more and 4 or less.

M ⁿ⁺ represents an arbitrary cation.

n represents the integer of 1 or more and 5 or less.]

The hydrocarbon group having 1 to 8 carbon atoms which may have a substituent represented by R ¹ and R ² is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 8 carbon atoms which may have a substituent And more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ¹ and R ² may be linear, branched or cyclic.

As a linear or branched aliphatic hydrocarbon group, a linear aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl; isopropyl, isobutyl, isopene And branched-chain aliphatic hydrocarbon groups such as a butyl group, a neopentyl group, and a 2-ethylhexyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 8, more preferably 3 to 6.

Examples of the aromatic hydrocarbon group having 6 to 8 carbon atoms in R ¹ and R ² include a phenyl group, a tolyl group, a xylyl group, a phenethyl group, and an α-methylbenzyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ and R ² may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; a nitro group; a cyano group; an amino group; a hydroxyl Period; C1-C6 alkoxy group such as methoxy group and ethoxy group; Sulfanyl group; C1-C6 alkylsulfanyl group such as methylsulfanyl group and ethylsulfanyl group; Carboxyl group; Carbamoyl group; Methoxycarbonyl group, Alkoxycarbonyl groups having 1 to 6 carbon atoms such as ethoxycarbonyl groups; sulfo groups; sulfamoyl groups; alkoxysulfonyl groups having 1 to 6 carbon atoms such as methoxysulfonyl groups and ethoxysulfonyl groups; and the like. It is more preferable that the hydrocarbon group having 1 to 8 carbon atoms does not have a substituent.

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

Each of X ¹ and X ² is independently preferably a carbamoyl group or a cyano group, and more preferably a cyano group. Moreover, although X ¹ and X ² may be the same or different, the same is preferable.

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by L ¹ and L ² is a divalent group derived by removing two arbitrary hydrogen atoms from a hydrocarbon having 1 to 8 carbon atoms, and a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms Or a C6-C8 divalent aromatic hydrocarbon group is mentioned.

Examples of the divalent aliphatic hydrocarbon group include a divalent chain hydrocarbon group having 1 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

The divalent chain aliphatic hydrocarbon group is a methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane Alkanediyl groups, such as -1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group, etc. are mentioned.

As a divalent alicyclic hydrocarbon group, cyclopropane-1,1-diyl group, cyclopropane-1,2-diyl group, cyclobutane-1,1-diyl group, cyclobutane-1,2-diyl group, cyclobutane -1,3-diyl group, cyclopentane-1,1-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,1-diyl group, cyclohexane -1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, and groups represented by formulas (L-a1) to (L-a6), etc. are mentioned. .

Examples of the divalent aromatic monocyclic hydrocarbon group include o-phenylene group, m-phenylene group, p-phenylene group, and groups represented by formulas (L-b1) to (L-b6).

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by L ¹ and L ² is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a divalent chain hydrocarbon group having 1 to 8 carbon atoms, and further preferably Preferably, it is a C1-C8 alkanediyl group, Especially preferably, it is a C1-C8 linear alkanediyl group.

In addition, the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 4.

The divalent hydrocarbon group having 1 to 8 carbon atoms in L ¹ and L ² may have a substituent, and the substituent is the same as the substituent which may have a hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ and R ² . It is more preferable that the divalent hydrocarbon group does not have a substituent.

L ¹ and L ² are each independently, preferably a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, or a formula (L-b1) to a formula (L- b6), more preferably a methylene group, an ethylene group, a propane-1,3-diyl group, or a butane-1,4-diyl group. Further, L ¹ and L ² may be the same or different, but the same is preferable.

k is preferably 3 or less, more preferably 2 or less, and still more preferably 1. In addition, in Formula (I), the carbon-carbon double bond represented by arrows s and t may be either an E configuration or a Z configuration. That is, formula (I) is defined as including all geometric isomers resulting from the carbon-carbon double bonds indicated by arrows s and t.

M ⁿ⁺ is preferably a hydrogen ion, an n-valent metal ion, or a substituted or unsubstituted ammonium ion.

Examples of n-valent metal ions represented by M ⁿ⁺ include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, zirconium ions, and chromium ions, Transition metal ions such as 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; etc. have.

Further, examples of the substituted or unsubstituted ammonium ion represented by M ⁿ⁺ include quaternary ammonium ions such as tetraalkyl ammonium ions.

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

The number of M ⁿ⁺ is one less than the sum of the number of -SO ₃ -present in Formula (I). For this reason, compound (I) has a valence of 0, that is, becomes an electrically neutral compound.

M ⁿ⁺ is preferably a hydrogen ion or an n-valent metal ion, more preferably a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion, more preferably a hydrogen ion, sodium ion, potassium ion, magnesium ion, or barium ion. , Hydrogen ions or barium ions are more preferable.

Examples of the compound (I) include compounds represented by formulas (I-1) to (I-420) shown in Tables 1 to 5. Compound (I) is

It is preferably a compound represented by formula (I-1) to formula (I-168),

More preferably, it is a compound represented by formula (I-29) to formula (I-56) or a compound represented by formula (I-113) to formula (I-140),

More preferably, it is a compound represented by a formula (I-33)-a formula (I-36) or a compound represented by a formula (I-117)-a formula (I-120).

In addition, in Tables 1-5, Me represents a methyl group, and Et represents an ethyl group. In addition, L ¹ and L ² represent a divalent hydrocarbon group represented by formulas (L-1) to (L-7). In formulas (L-1) to (L-7), *n means a bond with a nitrogen atom, and *s means a bond with a sulfur atom.

When M ⁿ⁺ is a hydrogen ion, the compound represented by formula (Ia) can be produced by reacting a compound represented by formula (pt1) and a compound represented by formula (pt2) under acidic or basic conditions. In this reaction, the amount of the compound represented by formula (pt1) to be used is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by formula (pt2).

When M ⁿ⁺ is a cation other than a hydrogen ion, the compound represented by formula (Ib) is a compound represented by formula (Ia) and a halide containing an n-valent metal ion or a substituted or unsubstituted ammonium ion (preferably a chloride ), acetate, phosphate, sulfate, silicate or cyanide can be reacted.

[In formula (pt1), R ³ is the same as R ¹ or R ² , X ³ is the same as X ¹ or X ² , and L ³ is the same as L ¹ or L ² .

In formula (pt2), R ^c is a hydrogen atom, a nitro group, or a halogen atom. k is the same as above.

In formulas (Ia) and (Ib), R ¹ , R ² , X ¹ , X ² , L ¹ , L ² , k, M ⁿ⁺ and n are the same as above.]

The content of the compound (I) is preferably 0.1 to 150 parts by mass, more preferably 1 to 100 parts by mass, and still more preferably 5 to 80 parts by mass based on 100 parts by mass of the resin (B).

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 a known dye can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like. Examples of dyes include compounds classified as having colors other than pigments in the color index (published by The Society of Dyers and Colorists), and known dyes described in dye notes (color dyes). . In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, a Cridine 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 a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) can be mentioned.

As a pigment, 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, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 and other 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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ；

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as pigment black 1 and 7, etc. are mentioned.

The content rate of the colorant (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 with respect to the total amount of the solid content.

The content rate of the compound (I) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the total amount of the coloring agent (A).

Here, the "total amount of solid content" in this specification refers to the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin, and at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as ``(a)'' may be A resin having a structural unit derived from) is more preferable. Resin (B) is a structural unit derived from a monomer (b) having an ethylenically unsaturated bond and a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as "(b)"), (a ) And copolymerizable monomer (c) (however, (a) and (b) are different) (hereinafter sometimes referred to as ``(c)'') a structural unit derived from, and an ethylenically unsaturated bond in the side chain It is preferable to have at least one structural unit selected from the group consisting of structural units having.

As (a), specifically, for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono [2-(meth)acrylo Monooxyethyl] and the like, and preferably acrylic acid, methacrylic acid, and maleic anhydride.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group Is preferred.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 type selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

As (b), for example, 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, etc. are mentioned, Preferably, glycidyl (meth)acrylate, 3,4-epoxytricyclo[ 5.2.1.0 ^2,6 ] Decyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

As (c), 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 , Vinyl toluene, and the like, preferably styrene, vinyl toluene, 2-hydroxyethyl (meth) acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. Do.

Resin having a structural unit having an ethylenically unsaturated bond in the side chain, (b) is added to the copolymer of (a) and (c), or (a) is added to the copolymer of (b) and (c). It can be manufactured by making it. The resin may be a resin in which (a) is added to the copolymer of (b) and (c) and further reacted with carboxylic anhydride.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000.

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

The content rate of the resin (B) 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 amount of the 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), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like, preferably It 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 trimethyrolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic. Rate, 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, and more preferably 250 or more and 1,500 or less.

When the polymerizable compound (C) is included, the content rate of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, further preferably based on the total amount of the solid content. It is 17 to 55% by mass.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, etc. by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. As a polymerization initiator generating an active radical, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfide) Panylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morph Polyno-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'-tetraphenylbiimidazole, etc. are mentioned.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Hagi is 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, since there is a tendency that the sensitivity is increased and the exposure time is shortened, the productivity of the color filter is improved.

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 polymerization of a polymerizable compound in which polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

As the polymerization initiation aid (D1), 4,4'-bis(dimethylamino)benzophenone (commonly known as Mihirazketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone, N-phenylglycine, and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. 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 the color filter 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 a solvent commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, and not -COO-), alcohol solvent (containing OH in the molecule,- Solvents that do not contain O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As a solvent,

Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and ester solvents such as γ-butyrolactone (in the molecule- Solvent containing COO- 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, and diethylene glycol methyl ethyl ether (in the molecule -O- A solvent that contains, and does not contain -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, and diethylene glycol monoethyl ether acetate (in the molecule Solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, and cyclohexanone (including -CO- in the molecule, not containing -COO-) solvent);

Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvent 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; and the like.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is included, the content rate of the solvent (E) is preferably 70 to 95 mass%, and more preferably 75 to 92 mass% with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application is improved, and the color density is not insufficient when the color filter is formed, so that 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)>

As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom may be mentioned. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Industries, Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan joint company), etc. I can.

Examples of the above fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florade (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, wing F171, wing F172, wing F173, wing F177, wing F183, wing F554, wing R30, copper RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (Mitsubishi Material Electronic Chemicals Corporation), Surfron (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.), and the like.

Examples of the silicone-based surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megapack (registered trademark) R08, copper BL20, copper F475, copper F477 and copper 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 mass%, more preferably 0.002 to 0.1 mass% with respect to the total amount of the colored curable resin composition. In addition, the content of the pigment dispersant is not included in this content. 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 contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, as necessary.

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention includes a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and a polymerization initiator (D1), a solvent (E) used as necessary. , It can be prepared by mixing the leveling agent (F) and other components.

<Production method of color filter>

As a method for producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be mentioned. Among them, the photolithography method is preferred.

When the colored curable resin composition contains the compound (I) as a colorant, a color filter having particularly excellent contrast can be produced. This color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

[Example]

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

Example 1

12.9 parts of a compound represented by formula (1-1) and 5.5 parts of a compound represented by formula (1-2) were added to 18 parts of acetic anhydride, and mixed at room temperature. Subsequently, after adding 8 parts of triethylamine, it stirred at 40 degreeC? for 5 hours. After completion of the reaction, 100 parts of ethyl acetate was added to precipitate crystals and filtered. It washed three times with 80 parts of ethyl acetate, and the crystal was dried under reduced pressure at 60°C to obtain 13.3 parts of a compound represented by formula (I-33).

.

.

Example 2

11 parts of the compound represented by formula (I-33) were added to 100 parts of water to prepare a solution (aqueous solution 1) in which the compound represented by formula (I-33) was dissolved. Separately, a solution (aqueous solution 2) in which 19.5 parts of barium chloride dihydrate was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was added dropwise to the aqueous solution 1 at 40°C over 2 hours, followed by stirring for 4 hours. After cooling, it was filtered and washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100° C. to obtain 20 parts of a compound represented by formula (I-117).

[Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping lot, and a stirrer, an appropriate amount of nitrogen was flowed to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate were added, followed by heating to 80°C while stirring. Next, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- A solution in which 289 parts of a mixture of 9-ylacrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was 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 in which 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise in the flask over about 6 hours using another dropping pump. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight (Mw) of the obtained copolymer was 9200, the dispersion degree was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin (B-2) had the following structural units.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of the resin was performed by gel permeation chromatography (GPC method) under the following conditions.

Equipment; HLC-8120 GPC (manufactured by Tosoh Corporation)

Column; TSK-GELG2000HXL

Column temperature; 40°C

Solvent; T HF

Flow rate; 1.0 mL/min

Test solution solid content concentration; 0.001 to 0.01 mass%

Injection volume; 50 μL

Detector; RI

Standard substances 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 weight average molecular weight and number average molecular weight in terms of polystyrene obtained above was taken as the dispersibility.

Examples 3-4

[Production of dispersion (P-1)]

10 parts of the compound represented by formula (I-33), 4 parts of the solid content of the dispersant BYK-LP　N6919 (manufactured by BYK), 5 parts of the resin (B-2) solution (solid content 35.0%) as a solid content, propylene glycol monomethyl After weighing 181 parts of ether acetate, 300 parts of 0.4 µm zirconia beads were put, stirred for 6 hours using a paint conditioner (manufactured by LAU), and the zirconia beads were removed by filtration to prepare a dispersion (P-1).

[Production of dispersion (P-2)]

A dispersion (P-2) was prepared in the same manner as the dispersion (P-1) except that the compound represented by the formula (I-33) was replaced with the compound represented by the formula (I-117).

[Preparation of colored curable resin composition]

Each component was mixed so that it might become the composition shown in Table 6, and the colored curable resin composition was obtained.

Comparative Example 1

Except having changed the dispersion liquid (P-1) to the coloring agent (A-1), it carried out similarly to Example 3, and obtained the colored curable resin composition.

In Table 6, each component represents the following compounds.

Coloring agent (A-1): Compound represented by formula (3)

Resin (B-2): Resin (B-2) (solid content conversion)

Polymerizable compound (C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.)

Polymerization initiator (D-1): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE　01; BASF company make)

Solvent (E-1): Propylene glycol monomethyl ether acetate

<Production of colored patterns>

After applying the colored curable resin composition by spin coating on a 5 cm-cornered glass substrate (Eagle 2000; manufactured by Corning), it was prebaked at 100°C for 3 minutes to obtain a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used, and an exposure amount of 150 mJ/cm 3 (365 nm) Standard). As a photomask, a 100 µm line and space pattern was used. The colored composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, washed with water, and then post-treated in an oven at 200°C for 20 minutes. Baking was performed to obtain a colored pattern.

<Contrast evaluation>

About the colored patterns obtained in Examples 3 and 4 and Comparative Example 1, a contrast meter (CT-1; manufactured by Tsubosaka Electric Corporation, a color difference meter BM-5A; manufactured by Topcon, a light source; F-10, a polarizing film; Tsubo Saka Electric Co., Ltd.) was used to measure the contrast with a blank value of 30000. Table 7 shows the results.

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

Claims (3)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colored curable resin composition containing the compound represented by Formula (I) in the said coloring agent.

[In formula (I),
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,
X ¹ and X ² each independently represent a hydrogen atom, a cyano group, or a carbamoyl group,
L ¹ and L ² each independently represent a C 1 to C 8 divalent hydrocarbon group which may have a substituent,
k represents an integer of 0 or more and 4 or less,
M ⁿ⁺ represents an arbitrary cation,
n represents the integer of 1 or more and 5 or less.] 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.