JP2019157085A - Compound - Google Patents

Abstract

To provide a compound that is capable of forming a color filter with excellent thermal resistance.SOLUTION: The present invention provides a compound represented by chemical formula (I) [R-Rindependently represent H, a hydroxy group, a substituted/unsubstituted C1-20 alkyl group, a substituted/unsubstituted C1-20 alkoxy group; R-Rindependently represent a substituted/unsubstituted C1-20 hydrocarbon; at least one of R-Ris a C1-20 hydrocarbon having -COas a substituent; Qis an n-valent metal ion; n is an integer of 2 or greater; b is the number of Q; the total of negative charges contained in R-Ris defined as k, a is (n×b)/k].SELECTED DRAWING: None

Description

  The present invention relates to compounds.

Color filters used in liquid crystal display devices, electroluminescence display devices, plasma display devices and other solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored resin compositions. As a colorant used for such a colored resin composition, a compound represented by the formula (x) is known.

JP2015-86380A

  However, a color filter formed from a conventionally known colored resin composition containing the above compound may not be sufficiently satisfied with heat resistance. Therefore, the present invention provides a compound capable of forming a color filter having excellent heat resistance.

［式（Ｉ）中、
Ｒ¹〜Ｒ⁸は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数１〜２０のアルコキシ基を表す。
Ｒ⁹〜Ｒ¹²は、それぞれ独立に、置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ⁹〜Ｒ¹²のうち少なくとも一つは、−ＣＯ₂ ^-を置換基として有する炭素数１〜２０の炭化水素基である。
Ｑⁿ⁺は、ｎ価の金属イオンを表す。
ｎは、２以上の整数を表す。
ｂは、Ｑⁿ⁺の個数を表す。
Ｒ¹〜Ｒ¹²に含まれる負電荷の合計をｋ個としたとき、ａは（ｎ×ｂ）／ｋである。］
［２］ 着色剤及び樹脂を含み、着色剤が、［１］記載の式（Ｉ）で表される化合物を含む着色樹脂組成物。
［３］ さらに、重合性化合物及び重合開始剤を含む［２］記載の着色樹脂組成物。
［４］ ［２］又は［３］記載の着色樹脂組成物から形成されるカラーフィルタ。
［５］ ［４］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] A compound represented by the formula (I).

[In the formula (I),
R ^{1 to} R ⁸ are each independently a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted substituent having 1 to 20 carbon atoms. Represents an alkoxy group.
R ^{9 to} R ¹² each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{9 to} R ¹² is substituted with —CO ₂ ^— . It is a C1-C20 hydrocarbon group which has as a group.
Q ^{n +} represents an n-valent metal ion.
n represents an integer of 2 or more.
b represents the number of Q ^{n +} .
When the total number of negative charges contained in R ^{1 to} R ¹² is k, a is (n × b) / k. ]
[2] A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the formula (I) described in [1].
[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.
[4] A color filter formed from the colored resin composition according to [2] or [3].
[5] A display device including the color filter according to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the novel compound which can form the color filter excellent in heat resistance is provided.

<Compound>
The compound according to the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). Hereinafter, the present invention will be described in detail using Formula (I). In Compound (I), the resonance structure of Formula (I) and each group in Formula (I) are each represented by a carbon-carbon single bond or carbon- A compound obtained by rotating around a bond axis of a nitrogen single bond is also included.

[In the formula (I),
R ^{1 to} R ⁸ are each independently a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted substituent having 1 to 20 carbon atoms. Represents an alkoxy group.
R ^{9 to} R ¹² each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{9 to} R ¹² is substituted with —CO ₂ ^— . It is a C1-C20 hydrocarbon group which has as a group.
Q ^{n +} represents an n-valent metal ion.
n represents an integer of 2 or more.
b represents the number of Q ^{n +} .
When the total number of negative charges contained in R ^{1 to} R ¹² is k, a is (n × b) / k. ]

The alkyl group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁸ may be linear, branched or cyclic. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, A decyl group, a heptadecyl group, an undecyl group, etc. are mentioned. Cyclic alkyl groups include cyclopropyl group, 1-methylcyclopropyl group, cyclopentyl group, cyclohexyl group, 1,2-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 4-cyclohexylcyclohexyl. Groups and the like.
Examples of the substituent of the alkyl group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁸ include a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; —NR ^a R ^b (R ^a and R ^b are Each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; a carbon number such as a methoxycarbonyl group or an ethoxycarbonyl group 1-10 alkoxycarbonyl groups; and the like.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁸ include a group in which —O— is bonded to the bond of the alkyl group having 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group , 2-ethylhexyloxy group and the like.
Examples of the substituent of the alkoxy group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁸ include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a hydroxy group; —NR ^c R ^d (R ^c and R ^d are Each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; a carbon number such as a methoxycarbonyl group or an ethoxycarbonyl group Examples include 1 to 10 alkoxycarbonyl groups.

Of R ^{1 to} R ⁸ , R ^{1 to} R ⁴ are particularly preferably hydrogen atoms. R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 alkoxy groups are preferable, and a hydrogen atom or a hydroxy group is more preferable.

Of R ^{1 to} R ⁸ (preferably R ^{5 to} R ⁸ ), 2 to 4 are preferably each independently a hydroxy group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ to R ^12, and aromatic hydrocarbon groups aliphatic hydrocarbon group or a C6-20 having 1 to 20 carbon atoms are exemplified.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and is preferably saturated. In addition, the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched.

Examples of the linear or branched aliphatic hydrocarbon having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, 1- Linear aliphatic hydrocarbon groups such as propenyl group, 2-propenyl group (allyl group); branched chain aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, etc. Can be mentioned. Carbon number of this aliphatic hydrocarbon group becomes like this. Preferably it is 1-15, More preferably, it is 1-10.
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. Carbon number of this cyclic aliphatic hydrocarbon group becomes like this. Preferably it is 3-8, More preferably, it is 3-6.

  The methylene group contained in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be replaced with -O-. Examples of the group in which the methylene group contained in the aliphatic hydrocarbon group is replaced with -O- include groups represented by the following formulae. In the following formula, * represents a bond.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, xylyl group, trimethylphenyl group, dipropylphenyl group, di (2,2-dimethylpropyl) phenyl group, and naphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is more preferably 6 to 16, further preferably 6 to 12, and still more preferably 6 to 9.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{9 to} R ¹² may have a substituent, such as —CO ₂ ⁻ ; carboxy group; —SO ₃ ⁻ ; ¹ Z ² (Z ¹ and Z ² each independently represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom); a halogen such as a fluorine atom, a chlorine atom, or iodine Atoms: alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; hydroxy groups; sulfamoyl groups; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group;

In the substituent -CONZ ¹ Z ² , the hydrocarbon group having 1 to 10 carbon atoms represented by Z ¹ and Z ² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. A hydrocarbon group etc. are illustrated.
The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be either saturated or unsaturated. The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or cyclic.
Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms include the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{9 to} R ¹² . Of these, those having 1 to 10 carbon atoms are exemplified.

In the substituent -CONZ ¹ Z ² , the hydrocarbon group having 1 to 10 carbon atoms represented by Z ¹ and Z ² may have a substituent, such as a fluorine atom, a chlorine atom, A halogen atom such as iodine; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; It is done.

At least one of R ^{9 to} R ¹² is a hydrocarbon group having 1 to 20 carbon atoms having —CO ₂ ^— as a substituent. The hydrocarbon group having 1 to 20 carbon atoms having —CO ₂ ^— as a substituent preferably has —CO ₂ ^— , preferably 1 to 2, more preferably 1. The —CO ₂ ^— is preferably bonded to at least the terminal of a hydrocarbon group having 1 to 20 carbon atoms having —CO ₂ ^— as a substituent. Such -CO ₂ ^- Examples of the hydrocarbon group having 1 to 20 carbon atoms having as the substituent, for example, groups represented by the following formula. In the following formula, * represents a bond.

At least one of R ^{9 to} R ¹² is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferably a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group or di (2,2-dimethylpropyl). A phenyl group, more preferably a 2,4-dimethylphenyl group or a 2,4,6-trimethylphenyl group.

In Compound (I), R ⁹ and R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms having —CO ₂ ^— as a substituent, and R ¹⁰ and R ¹¹ are each independently substituted. It is desirable that it is a C6-C20 aromatic hydrocarbon group which may have a group.

Examples of ^n- valent metal ions represented by Q ^{n +} include alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, and cobalt ions. Transition metal ions such as nickel ion and copper ion; typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion and bismuth ion; Q ^{n +} is preferably an alkaline earth metal ion, more preferably a barium ion.

  n is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and even more preferably 2.

Compound (I) is electrically neutral, and a is (n × b) / k when the total number of negative charges contained in R ^{1 to} R ¹² is k.
Note that b is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
Further, k is the value of —CO ₂ ^— contained in the formula (I) when the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{9 to} R ¹² does not have —SO ₃ ^— as a substituent. A total is mentioned, Preferably it is 1-5 pieces, More preferably, it is 2-4 pieces, More preferably, it is two pieces.

Examples of compound (I) include compounds represented by formulas (I-1) to (I-108) shown in Tables 1 and 2.
Compound (I) is
Preferably, it is a compound represented by formula (I-1) to formula (I-54),
More preferably, it is a compound represented by formula (I-1) to formula (I-18),
More preferred are compounds represented by formula (I-1) to formula (I-3).

  In Tables 1 and 2, ph1 to ph6 represent groups represented by the following formulas (* means a bond).

  In Tables 1 and 2, ca1 to ca6 represent groups represented by the following formulas (* means a bond).

The compound represented by the formula (I) includes a compound represented by the formula (pt4), a halide (preferably chloride) containing an n-valent metal ion, acetate, phosphate, sulfate, silicic acid. It can be produced by reacting with a salt or cyanide.
The compound represented by the formula (pt4) is produced by reacting the compound represented by the formula (pt1), the compound represented by the formula (pt2), and the compound represented by the formula (pt3). it can. In this reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt3). Preferably there is.

[In the formula (I), R ^{1 to} R ¹² are the same as above.
In formula (pt1) to formula (pt2) and formula (pt4), R ^{9a to} R ^12a each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁹ at least one of to R ¹² is a hydrocarbon group having 1 to 20 carbon atoms having as the substituent a -CO ₂ H. ]

<Colored resin composition>
The colored resin composition of the present invention contains a colorant (A) and a resin (B), and the colorant (A) contains a compound represented by the formula (I).
The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).
The colored resin composition of the present invention may further contain a polymerization initiation assistant (D1), a solvent (E), and a leveling agent (F).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colored resin composition of the present invention contains compound (I) as the colorant (A). The content of the compound (I) is preferably 0.1 to 150 parts by weight, more preferably 0.5 to 100 parts by weight, with respect to 100 parts by weight of the resin (B). More preferably, it is part by mass.
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 in the total amount of the colorant (A).

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

  The dye (A1) is not particularly limited, and a known dye can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as those having a hue other than pigment in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). It is done. According to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye (however, compound (I) And acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a 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. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI 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 CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 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 with respect to the total solid content of the colored resin composition, Preferably it is 1-50 mass%.
Here, the “total amount of solids” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored 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, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter “(a)”. More preferred is a resin having a structural unit derived from The resin (B) is a structural unit derived from a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), A structural unit derived from the monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”), and the 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.

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

(B) is preferably a monomer having a C2-C4 cyclic ether structure (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. .
In the present 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 can be mentioned. Glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( (Meth) 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. -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 preferable.

  A resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to a copolymer of (a) and (c) or 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 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 further 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 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 necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example. .

The content of the resin (B) is preferably 30 to 99.9% by mass, more preferably 50 to 99.5% by mass, and still more preferably based on the total solid content of the colored resin composition. Is 70-99 mass%.
When the colored resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D), the content of the resin (B) is preferably relative to the total solid content of the colored resin composition. It is 7-65 mass%, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%.

<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. Is a (meth) acrylic acid ester compound.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of 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 ( And (meth) acrylate.

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

  When the polymerizable compound (C) is included, 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 the solid content. More preferably, it is 17-55 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 or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- (4-phenyl) Sulfanylphenyl) -3-cyclohexylpropan-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 T, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (2-chlorophenyl) -4, Examples include 4 ', 5,5'-tetraphenylbiimidazole.

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

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (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 Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone , N-phenylglycine and the like.

  When using these polymerization initiation assistants (D1), the content thereof 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). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) 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-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

As a solvent,
Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (in the molecule -COO- Containing -O- free solvent);
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 -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 (in the molecule -COO- And a solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), 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 -O-, -CO- and -COO-);
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone;
As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

  When the solvent (E) is included, the content of the solvent (E) is preferably 60 to 95 mass%, more preferably 65 to 92 mass%, based on the total amount of the colored resin composition of the present invention. . In other words, the total solid content of the colored resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

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

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

  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 0.002 to the total amount of the colored resin composition. 0.1% by mass. Note that 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 resin composition of the present invention contains additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as necessary. But you can.

<Method for producing colored resin composition>
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation assistant (D1), a solvent used as necessary. It can be prepared by mixing (E), the leveling agent (F) and other components.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable.

  When the colored resin composition contains the compound represented by the formula (I), a color filter particularly excellent in heat resistance can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

(Synthesis Example 1)
100 parts of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 55 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), potassium hydroxide (Wako Pure Chemical Industries, Ltd.) 51 parts), tetrabutylammonium bromide (Tokyo Chemical Industry Co., Ltd.) 1.5 parts, bis (tri-t-butylphosphine) palladium (Aldrich Co., Ltd.) 2.3 parts, water 100 parts and toluene 1000 parts (manufactured by Kanto Chemical Co., Inc.) were mixed and heated at 90 ° C. with stirring for 1 hour. After completion of the reaction, the organic layer was separated with water and ethyl acetate, and the organic layer was separated. And the organic layer was dried with magnesium sulfate, the solvent was distilled off by the evaporator, and 113 parts of compounds represented by Formula (1-1) were obtained.

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 258.2
Exact Mass: +257.1

(Synthesis Example 2)
70 parts of the compound represented by the formula (1-1), 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 53 parts, and 700 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) are mixed. And heated at 100 ° C. with stirring for 16 hours. After completion of the reaction, the solvent was distilled off, 700 parts of hexane (manufactured by Kanto Chemical Co., Inc.) was added to the obtained crude product, and the mixture was stirred for 2 hours to separate the solid by the formula (1-2). 90 parts of the compound represented were obtained.

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 372.2
Exact Mass: +371.1

(Synthesis Example 3)
34 parts of the compound represented by the formula (1-2) are dissolved in 340 parts of dichloromethane (manufactured by Kanto Chemical Co., Inc.), cooled to 0 ° C., and 92 parts of boron tribromide (manufactured by Tokyo Chemical Industry Co., Ltd.). Was dripped. After completion of the dropwise addition, the mixture was heated to 10 ° C. and stirred for 3 hours, and then water was added to extract the organic layer. The crude product A contained 44% of the compound represented by the formula (1-3) and 53% of the compound represented by the formula (1-3-1).

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 344.2
Exact Mass: +343.1 Formula (1-3)
Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 330.2
Exact Mass: +329.1 Formula (1-3-1)

(Synthesis Example 4)
89 parts of the crude product A was dissolved in 370 parts of methanol (manufactured by Kanto Chemical Co., Inc.), cooled to 0 ° C., and then 51 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at room temperature for 23 hours, and after completion of the reaction, water was added and the solvent was distilled off. The resulting crude product was separated and purified by silica gel column chromatography, and the compound represented by formula (1-3) 53 parts were obtained.

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 344.2
Exact Mass: +343.1

(Synthesis Example 5)
After 53 parts of the compound represented by the formula (1-3) are dissolved in 530 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C., 460 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) are added. The solution was added dropwise, and stirred at 20 ° C. for 5 hours after the completion of dropping. After completion of the reaction, water was added, the solvent was distilled off, and the crude product obtained was separated and purified by column chromatography to obtain 25 parts of the compound represented by the formula (1-4).

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 330.3
Exact Mass: +329.2

  4 parts of a compound represented by the formula (1-4), 2.5 parts of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), tetrahydrofuran ( 20 parts of Kanto Chemical Co., Ltd.) was added and stirred at room temperature of 23 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography to obtain 1.7 parts of a compound represented by the formula (1-5).

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 316.1
Exact Mass: +315.2

(Synthesis Example 6)
1.7 parts of the compound represented by the formula (1-5) and 0.3 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were added to toluene (Kanto Chemical). (Made by Co., Ltd.) 65 parts and n-butanol (Kanto Chemical Co., Ltd.) 17 parts were dissolved and heated at 120 ° C. with stirring for 2 hours. After completion of the reaction, the solvent was distilled off and the resulting crude product was separated and purified by silica gel column chromatography to obtain 0.85 part of the compound represented by formula (1-6).

Identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 709.3
Exact Mass: +708.3

Example 1
An aqueous solution 1 was prepared by adding 1.0 part of the compound represented by the formula (1-6) to 25 parts of a 0.8% aqueous sodium hydroxide solution and dissolving it. Separately, a solution (aqueous solution 2) in which 1.7 parts of barium chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 parts of water was prepared. After slow addition, the mixture was stirred for 30 minutes. After completion of the reaction, the solid obtained by suction filtration was rinsed with water and acetone. The washed solid was dried under reduced pressure at 60 ° C. for 12 hours to obtain 1.2 parts of a compound represented by the formula (1-7).

(Resin synthesis example 1)
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxy tricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 225 parts of a decane-9-yl acrylate (mixing ratio is 1: 1), 81 parts of vinyltoluene (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 a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping of the initiator solution, the inside of the flask was held at 85 ° C. for 4 hours, and then cooled to room temperature, and a copolymer (resin (B) having a B-type viscosity (23 ° C.) of 246 mPa · s and a solid content of 37.5% was obtained. B-1) A solution was obtained. The resulting copolymer had a weight average molecular weight Mw of 10600, a dispersity of 2.01, and a solid content acid value of 115 mg-KOH / g. Resin (B-1) has the following structural units.

(Resin synthesis example 2)
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 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 289 parts of a mixture of decane-9-yl acrylate (mixing ratio is 1: 1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the flask was kept at 80 ° C. for 4 hours, and then cooled to room temperature. A B-type viscosity (23 ° C.) of 125 mPa · s and a solid content of 35.1% copolymer (resin (B-2)) ) A solution was obtained. The resulting copolymer had a weight average molecular weight Mw of 9,200, a dispersity of 2.08, and a solid content acid value of 77 mg-KOH / g. Resin (B-2) has the following structural units.

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the 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
Reference 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 weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as the dispersity.

Preparation of Dispersion (P-1) 5 parts of the compound represented by formula (1-7), 5 parts of dispersant, 4 parts of resin (B-1) (solid content), propylene glycol monomethyl ether acetate 76 And 10 parts of diacetone alcohol are mixed, 300 parts of 0.2 μm-diameter zirconia beads are added thereto, shaken for 3 hours using a paint conditioner (manufactured by LAU), the zirconia beads are removed, and a dispersion ( P-1) was produced.

In Table 3, each component represents the following compound.
Colorant (A-1): Compound represented by Formula (1-7) Resin (B-1): Resin (B-1) (in terms of solid content)
Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-2): Diacetone alcohol Dispersant (G-1): Acrylic dispersant

[Example 2, Comparative Example 1]
[Preparation of colored resin composition]
Each component was mixed so that it might become a composition shown in Table 4, and the colored resin composition was obtained.

樹脂（Ｂ−２）：樹脂（Ｂ−２）（固形分換算）
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
溶剤（Ｅ−３）：クロロホルム
レベリング剤（Ｆ−１）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製「トーレシリコーンＳＨ８４００」） In Table 4, each component represents the following compound.
Colorant (Ax): Compound represented by formula (x)

Resin (B-2): Resin (B-2) (solid content conversion)
Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-3): Chloroform Leveling agent (F-1): Polyether-modified silicone oil ("Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

<Preparation 1 of color filter (colored coating film)>
A colored resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to obtain a colored coating film.

<Measurement of chromaticity>
The chromaticity of the colored coating film is determined based on the spectrum measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) and the characteristic function of the C light source. The coordinates (x, y) and the stimulus value Y were obtained.

<Heat resistance evaluation>
The obtained colored coating film was heated in an oven at 230 ° C. for 2 hours. The chromaticity was measured before and after heating, and the color difference ΔEab * was calculated from the measured value by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The results are shown in Table 5. ΔEab * means that the smaller the color change, the smaller the color change. Moreover, if the heat resistance of a colored coating film is favorable, it can be said that the heat resistance of the coloring pattern produced from the same colored resin composition is also favorable.

[Example 3]
[Preparation of colored resin composition]
Each component was mixed so that it might become a composition shown in Table 6, and the colored resin composition was obtained.

In Table 6, each component represents the following compound.
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; Changzhou powerful electronic new material ( Made by Co., Ltd.)
Other symbols represent the same as above.

<Preparation 2 of color filter (colored coating film) and heat resistance evaluation>
A colored resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After standing to cool, light is applied to the colored composition layer formed on the substrate using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere. Irradiated. After light irradiation, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored coating film.
The chromaticity was measured before and after post-baking, and the color difference ΔEab * was calculated from the measured value by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The results are shown in Table 7.

  According to the compound of the present invention, a color filter having excellent heat resistance can be formed.

Claims (5)

A compound represented by formula (I).

[In the formula (I),
R ^{1 to} R ⁸ are each independently a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted substituent having 1 to 20 carbon atoms. Represents an alkoxy group.
R ^{9 to} R ¹² each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{9 to} R ¹² is substituted with —CO ₂ ^— . It is a C1-C20 hydrocarbon group which has as a group.
Q ^{n +} represents an n-valent metal ion.
n represents an integer of 2 or more.
b represents the number of Q ^{n +} .
When the total number of negative charges contained in R ^{1 to} R ¹² is k, a is (n × b) / k. ]   A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by formula (I) according to claim 1.   Furthermore, the coloring resin composition of Claim 2 containing a polymeric compound and a polymerization initiator.   A color filter formed from the colored resin composition according to claim 2.   A display device comprising the color filter according to claim 4.