JP6921577B2 - Color curable resin composition - Google Patents

Description

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

Color filters used in liquid crystal display devices, electroluminescence display devices, display devices such as plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As such a color-curable resin composition, a composition containing a compound represented by the formula (3) as a colorant is known (Patent Document 1).

JP-A-2009-235392

However, the color filter formed from the above-mentioned color-curable resin composition known conventionally may not sufficiently satisfy the contrast. Therefore, the present invention provides a color-curable resin composition capable of forming a color filter having excellent 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の炭化水素基を表す。
Ｘ^１及びＸ^２は、それぞれ独立に、水素原子、シアノ基、又はカルバモイル基を表す。
Ｌ^１及びＬ^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２価の炭化水素基を表す。
ｋは、０以上４以下の整数を表す。
Ｍ^ｎ＋は、任意のカチオンを表す。
ｎは、１以上５以下の整数を表す。］
［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 invention includes the following inventions.
[1] Contains a colorant, a resin, a polymerizable compound and a polymerization initiator.
A color curable resin composition in which the colorant contains a compound represented by the formula (I).

[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 divalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
k represents an integer of 0 or more and 4 or less.
M ^{n +} represents any cation.
n represents an 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 according to [2].

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

<Coloring curable resin composition>
The color curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and is represented by the formula (I) as the colorant (A). Includes the compounds represented.
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 the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

<Colorant (A)>
The color curable resin composition of the present invention contains the compound represented by the formula (I) (hereinafter, may be referred to as compound (I)) as the colorant (A).

[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 divalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
k represents an integer of 0 or more and 4 or less.
M ^{n +} represents any cation.
n represents an 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 having 1 to 8 carbon atoms which may have a substituent. It is an aromatic hydrocarbon group having 6 to 8 carbon atoms which may have a group or 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.}
Examples of the linear or branched aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; Examples thereof include branched chain aliphatic hydrocarbon groups such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 4 carbon atoms.
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, a cyclohexyl group and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.

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 xsilyl group, a phenethyl group, an α-methylbenzyl group and the like. The aromatic hydrocarbon group preferably has 6 carbon atoms.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ and R ² may have a substituent, and the substituent includes a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom. Nitro group; 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 having 1 to 6 carbon atoms such as methyl sulfanyl group and ethyl sulfanyl 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 having 1 to 6 carbon atoms such as methoxysulfonyl group and ethoxysulfonyl group. ; Etc. can be mentioned. It is more preferable that the hydrocarbon group having 1 to 8 carbon atoms has no substituent.

R ¹ and R ² are 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. R ¹ and R ² may be the same or different, but are preferably the same.

Independently, X ¹ and X ² are preferably a carbamoyl group or a cyano group, and more preferably a cyano group. Note that X ¹ and X ² may be the same or different, but are preferably the same.

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 the hydrocarbon having 1 to 8 carbon atoms. Examples thereof include divalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms and divalent aromatic hydrocarbon groups having 6 to 8 carbon atoms.
Examples of the divalent aliphatic hydrocarbon group include a divalent chain hydrocarbon group having 1 to 8 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

The divalent chain aliphatic hydrocarbon groups are methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5. Examples thereof include an alkandiyl group such as a −diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group and an octane-1,8-diyl group.
Examples of the divalent alicyclic hydrocarbon group include cyclopropane-1,1-diyl group, cyclopropane-1,2-diyl group, cyclobutane-1,1-diyl group, cyclobutane-1,2-diyl group, and the like. 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- Examples thereof include a 1,2-diyl group, a cyclohexane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a group represented by the formulas (La1) to (La6).

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

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, and more preferably 1 to 8 carbon atoms. It is a divalent chain hydrocarbon group of, more preferably an alkanediyl group having 1 to 8 carbon atoms, and particularly preferably a linear alkanediyl group having 1 to 8 carbon atoms.
The divalent hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

The divalent hydrocarbon groups having 1 to 8 carbon atoms in ^{L 1} and L ² may have a substituent, and the substituents have 1 to 8 carbon atoms represented by ^{R 1} and R ^2. It is the same as the substituent which the hydrocarbon group may have. It is more preferable that the divalent hydrocarbon group has no substituent.

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

k is preferably 3 or less, more preferably 2 or less, and even more preferably 1. In the formula (I), the carbon-carbon double bond indicated by the arrows s and t may have 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 the 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 the ^n- valent metal ion represented by M n + 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 ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion; typical metal such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion, etc. Ions; etc.
Examples of the substituted or unsubstituted ammonium ion represented by M ^{n +} include a quaternary ammonium ion such as a tetraalkylammonium ion.
n is preferably 4 or less, more preferably 3 or less, and even more preferably 1 or 2.

M ^{n +} the number of, -SO ₃ present in Formulas (I) ^- the one fewer than the sum of the number of. Therefore, the compound (I) has a valence of 0, that is, is 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, and even more preferably a hydrogen ion, a sodium ion, a potassium ion, a magnesium ion, or a barium ion. , Hydrogen ions or barium ions are even more preferred.

Examples of the compound (I) include compounds represented by the formulas (I-1) to (I-420) shown in Tables 1 to 5. Compound (I) is
It is preferably a compound represented by the formulas (I-1) to (I-168).
More preferably, it is a compound represented by the formulas (I-29) to (I-56) or a compound represented by the formulas (I-113) to (I-140).
More preferably, it is a compound represented by the formulas (I-33) to (I-36) or a compound represented by the formulas (I-117) to (I-120).

In Tables 1 to 5, Me represents a methyl group and Et represents an ethyl group. Further, L ¹ and L ² represent divalent hydrocarbon groups represented by the 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 the formula (Ia) reacts the compound represented by the formula (pt1) with the compound represented by the formula (pt2) under acidic or basic conditions. It can be manufactured by letting it. In this reaction, the amount of the compound represented by the formula (pt1) to be used is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt2).
When M ^{n +} is a cation other than hydrogen ion, the compound represented by the formula (Ib) is a compound represented by the formula (Ia) and a halogen containing an n-valent metal ion or a substituted or unsubstituted ammonium ion. It can be produced by reacting a compound (preferably chloride), acetate, phosphate, sulfate, silicate, cyanide or the like.

[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 described 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 5 to 80 parts by mass with respect to 100 parts by mass of the resin (B). Is more preferable.

The color-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, and mordant dyes. Examples of dyes include compounds classified by the Color Index (published by The Society of Dyers and Colorists) as having hues other than pigments, and known dyes described in dyeing notes (color dyeing company). Be done. 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, acrydin dye, styryl dye, coumarin. Examples include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

As the pigment (A2), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment 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. 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 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, still more preferably 1 to 50% by mass, based on the total amount of solids. %.
The content of the compound (I) is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more based on the total amount of the colorant (A).
Here, the "total amount of solid content" in the present specification means an 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 to the total amount can be measured by a 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 at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter, "(a)"). A resin having a structural unit derived from) is more preferable. The resin (B) is a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). Structural units derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and side. It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, oxalic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

In (b), 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 oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group is preferable. ..
In addition, in this specification, "(meth) acrylic acid" represents at least one kind 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, and 3-ethyl-3-. Examples thereof include (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( Meta) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-8. -Il (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like can be mentioned, with preference given to styrene. , Vinyl toluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to the copolymer of (a) and (c) or by adding (b) to the copolymer of (b) and (c). It can be manufactured by adding (a) to. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting 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 even 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 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and even 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 obtained by titration using, for example, an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids.

<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 compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three 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, and dipentaerythritol hexa (dipentaerythritol hexa (). Meta) acrylate and the like can be mentioned.

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 contained, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, based on the total amount of solids. , More preferably 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 active radicals, acids and the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholino-1-( 4-Methylsulfanylphenyl) Propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone, 2,4-bis (trichloromethyl) ) -6-Piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl Biimidazole and the like can be mentioned.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30% by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts, more preferably 1 to 20 parts 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, so that 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 initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (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 these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 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 coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

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 usually used in the art 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 in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

As a solvent
Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (intramolecular-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, and diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule and 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 (intramolecular-COO- 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 and not -COO-);
Alcohol solvents such as butanol, cyclohexanol, and 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; 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 contained, 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 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 coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

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 a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK), etc. Can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.%, based on the total amount of the color curable resin composition. It is 002 to 0.1% by mass. 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 color curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiator (D1) used as necessary. ), Solvent (E), Leveling Agent (F) and other components.

<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. Above all, the photolithography method is preferable.

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

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

Example 1
12.9 parts of the compound represented by the formula (1-1) and 5.5 parts of the compound represented by the formula (1-2) were added to 18 parts of acetic anhydride and mixed at room temperature. Then, after adding 8 parts of triethylamine, the mixture was stirred at 40 ° C. for 5 hours. After completion of the reaction, 100 parts of ethyl acetate was added to precipitate crystals, and the mixture was filtered. The crystals were washed 3 times with 80 parts of ethyl acetate, and the crystals were dried under reduced pressure at 60 ° C. to obtain 13.3 parts of the compound represented by the formula (I-33).

Example 2
11 parts of the compound represented by the formula (I-33) was added to 100 parts of water to prepare a solution (aqueous solution 1) in which the compound represented by the 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, and then for 4 hours. Stirred. After cooling, the mixture was filtered, 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 the compound represented by the formula (I-117).

[Synthesis Example 1]
An appropriate amount of nitrogen was flowed 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 mixture was heated to 80 ° C. with stirring. Then, 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 ] A solution of 289 parts of a mixture of decan-9-ylacrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) in 125 parts of propylene glycol monomethyl ether acetate was dissolved in 125 parts using a dropping pump. It was added dropwise over about 5 hours. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate is added dropwise into the flask over about 6 hours using another dropping pump. bottom. After completion of the dropping, the mixture was kept 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 dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The 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.
Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made 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.

Examples 3-4
[Preparation of dispersion liquid (P-1)]
10 parts of the compound represented by the formula (I-33), 4 parts of the solid content of the dispersant BYK-LP N6919 (manufactured by BYK), and the solid content of the resin (B-2) solution (solid content 35.0%). After weighing 5 parts and 181 parts of propylene glycol monomethyl ether acetate, add 300 parts of 0.4 μm zirconia beads, shake for 6 hours using a paint conditioner (manufactured by LAU), and remove the zirconia beads by filtration. A dispersion liquid (P-1) was prepared.
[Preparation of dispersion liquid (P-2)]
A dispersion liquid (P-2) was prepared in the same manner as the dispersion liquid (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 Color Curable Resin Composition]
Each component was mixed so as to have the composition shown in Table 6 to obtain a colored curable resin composition.

Comparative Example 1
A color curable resin composition was obtained in the same manner as in Example 3 except that the dispersion liquid (P-1) was changed to the colorant (A-1).

樹脂（Ｂ−２）：樹脂（Ｂ−２）（固形分換算）
重合性化合物（Ｃ−１）：ジペンタエリスリトールヘキサアクリレート（カヤラッド（登録商標）ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｄ−１）：Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン（イルガキュア（登録商標）ＯＸＥ ０１；ＢＡＳＦ社製）
溶剤（Ｅ−１）：プロピレングリコールモノメチルエーテルアセテート In Table 6, each component represents the following compound.
Colorant (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 Kayaku Co., Ltd.)
Polymerization Initiator (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate

<Making a coloring pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored composition layer. After allowing 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 in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven for 200. Post-baking was performed at ° C. for 20 minutes to obtain a coloring pattern.

<Contrast evaluation>
Contrast meter (CT-1; Tsubosaka Electric Co., Ltd., color difference meter BM-5A; Topcon Co., Ltd., light source; F-10, polarizing film; The contrast was measured using a Tsubosaka Electric Co., Ltd.) with a blank value of 30,000. The results are shown in Table 7.

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

Claims (3)

Contains colorants, resins, polymerizable compounds and polymerization initiators
A color curable resin composition in which the colorant contains a compound represented by the formula (I).

[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 divalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
k represents an integer of 0 or more and 4 or less.
M ^{n +} represents any cation.
n represents an 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 including the color filter according to claim 2.