JP2018203844A - Colored resin composition - Google Patents

Abstract

To provide a colored resin composition capable of forming a color filter excellent in contrast and heat resistance.SOLUTION: There is provided a resin composition containing a coloring agent and a resin, in which the coloring agent contains a compound represented by the formula (I), and the compound is a compound having absorbance maximum wavelength in 500 to less than 700 nm. A ring Tis a substituted/unsubstituted C6 to 20 aromatic hydrocarbon ring or a substituted/unsubstituted heteroaromatic ring; a ring Tis a nitrogen-containing heteroaromatic ring containing Nin constituting atoms of a substituted/unsubstituted ring; Land Lare each independently a substituted/unsubstituted C1 to 8 bivalent hydrocarbon group.SELECTED DRAWING: None

Description

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

  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 such a colored resin composition, a composition containing a compound represented by the formula (x) as a colorant is known (Patent Document 1).

Japanese Patent Laying-Open No. 2015-98589

  However, the color filters formed from the above-described colored resin compositions known in the past may not sufficiently satisfy the contrast, or may not withstand the heat during post-baking and may change color greatly. Therefore, the present invention provides a colored resin composition capable of forming a color filter excellent in contrast and heat resistance.

［式（Ｉ）中、
環Ｔ^１は、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素環または置換基を有していてもよい芳香族複素環を表す。
環Ｔ^２は、置換基を有していてもよい環の構成原子にＮ^＋を含む含窒素芳香族複素環を表す。
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。
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］ さらに、重合性化合物及び重合開始剤を含む［１］記載の着色樹脂組成物。
［３］ ［１］または［２］記載の着色樹脂組成物から形成されるカラーフィルタ。
［４］ ［３］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 colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by formula (I), and the compound is a compound having an absorption maximum wavelength at 500 nm or more and less than 700 nm.

[In the formula (I),
Ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.
Ring T ² represents a nitrogen-containing aromatic heterocyclic ring containing N ⁺ as a constituent atom of the ring which may have a substituent.
L ¹ and L ² each independently represent a C 1-8 divalent hydrocarbon group which may have a substituent.
M ^{n +} represents an arbitrary cation.
n represents an integer of 1 to 5. ]
[2] The colored resin composition according to [1], further comprising a polymerizable compound and a polymerization initiator.
[3] A color filter formed from the colored resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

  ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition which can form the color filter excellent in contrast and heat resistance is provided.

<Colored resin composition>
The colored resin composition of the present invention includes a colorant (A) and a resin (B). The colorant (A) has an absorption maximum wavelength at 500 nm or more and less than 700 nm, and is represented by the formula (I). Compounds.
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 a compound represented by the formula (I) (hereinafter may be referred to as compound (I)) as the colorant (A). Compound (I) has an absorption maximum wavelength at 500 nm or more and less than 700 nm.
Formula (I) is an example of a resonance structure, and the compound represented by formula (I) is defined as including all structures having a resonance relationship with formula (I).

[In the formula (I),
Ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.
Ring T ² represents a nitrogen-containing aromatic heterocyclic ring containing N ⁺ as a constituent atom of the ring which may have a substituent.
L ¹ and L ² each independently represent a C 1-8 divalent hydrocarbon group which may have a substituent.
M ^{n +} represents an arbitrary cation.
n represents an integer of 1 to 5. ]

Compound (I) is a colorant exhibiting green to red having an absorption maximum wavelength at 500 nm or more and less than 700 nm. The absorption maximum wavelength of the compound (I) can be confirmed by measuring the absorption spectrum of the compound (I), and the compound (I) is preferably 530 nm or more, more preferably 580 nm or more, still more preferably 600 nm or more, preferably It is desirable to have an absorption maximum wavelength at 690 nm or less.
In the present invention, the absorption maximum wavelength of compound (I) is measured with a spectrophotometer, and a solution in which compound (I) is dissolved in a measurement solvent can be used as a measurement sample. Examples of the measurement solvent include N-methylpyrrolidone, N, N dimethylformamide, dimethyl sulfoxide and the like.

Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by ring T ¹ include aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, and cymene; pentalene, indene, naphthalene, azulene, heptalene , Biphenylene, as-indacene, s-indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, tetracene, etc .; It is done. Carbon number of this aromatic hydrocarbon ring becomes like this. Preferably it is 6-16, More preferably, it is 6-10.

The aromatic heterocyclic ring represented by the ring T ¹ includes at least one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as a constituent element of the ring. The aromatic heterocycle may be monocyclic or polycyclic. Carbon number of this aromatic heterocyclic ring becomes like this. Preferably it is 3-30, More preferably, it is 3-20, More preferably, it is 3-15. The aromatic heterocycle represented by the ring T ¹ is more preferably a nitrogen-containing aromatic heterocycle containing a nitrogen atom as a ring component and the nitrogen atom being> N-.

Ring T ¹ is bonded to L ¹ and a carbon atom, respectively, by removing a hydrogen atom bonded to any atom constituting the ring among the above rings.

Examples of the nitrogen-containing aromatic heterocycle in the ring T ¹ include rings represented by the formula (T ¹ -A) and the formula (T ¹ -B).

Wherein ^(T 1 -A) and formula ^(T 1 -B),
X ¹ represents —C (R ^a3 ) (R ^a4 ) —, —N (R ^a5 ) —, —O—, or —S—, and preferably —C (R ^a3 ) (R ^a4 ) —. .
R ^a3 , R ^a4 and R ^a5 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
Ring T ⁵ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.
i is 1 or 2. ]

The nitrogen-containing aromatic heterocycle containing N ⁺ as a constituent atom of the ring represented by the ring T ² includes a nitrogen atom as a constituent element of the ring, and the nitrogen atom is> N ⁺ <. It is a ring. More preferably, the nitrogen-containing aromatic heterocyclic ring containing N ⁺ as a constituent atom of the ring represented by the ring T ² contains> C═N ⁺ <as a constituent element of the ring.

Ring T ² is bonded to L ² and a carbon atom, respectively, by removing a hydrogen atom bonded to any atom constituting the ring among the rings.

Examples of the nitrogen-containing aromatic heterocycle in the ring T ² include rings represented by the formula (T ² -A) and the formula (T ² -B).

Wherein ^(T 2 -A) and formula ^(T 2 -B),
X ² represents —C (R ^a6 ) (R ^a7 ) —, —N (R ^a8 ) —, —O—, or —S—, and preferably —C (R ^a6 ) (R ^a7 ) —. .
R ^a6 , R ^a7 and R ^a8 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.
Ring T ⁶ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.
j is 0 or 1. ]

The C1-C8 aliphatic hydrocarbon group represented by R ^{a3 to} R ^a8 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 aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. Carbon number of this aliphatic hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-5, More preferably, it is 1-4.
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. Carbon number of this cyclic aliphatic hydrocarbon group becomes like this. Preferably it is 3-8, More preferably, it is 3-6.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{a3 to} R ^a8 is preferably independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. , A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is still more preferable.

Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by ring T ⁵ and ring T ⁶ include aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, and cymene; pentalene, indene, naphthalene , Azulene, heptalene, biphenylene, as-indacene, s-indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, acanthrylene, triphenylene, pyrene, chrysene, tetracene, etc. And the like. Carbon number of this aromatic hydrocarbon ring becomes like this. Preferably it is 6-16, More preferably, it is 6-10.
Ring T ⁵ and ring T ⁶ are each independently preferably benzene, naphthalene, phenalene or anthracene, more preferably benzene or naphthalene.
Ring T ⁵ and ring T ⁶ may be the same or different.

Aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring T ^1, an aromatic heterocyclic ring represented by ring T ^1, nitrogen-containing aromatic containing N ⁺ to constituent atoms of the ring for ring T ² The aromatic heterocyclic ring having 6 to 20 carbon atoms represented by the heterocyclic ring and rings T ⁵ and T ⁶ may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; nitro group; cyano group; —N (R ^a1 ) (R ^a2 ) group; hydroxy group; methoxy group, ethoxy group, etc. An alkoxy group having 1 to 6 carbon atoms; a sulfanyl group; an alkylsulfanyl group having 1 to 6 carbon atoms such as a methylsulfanyl group and an ethylsulfanyl group; a carboxy group; a carbamoyl group; and a carbon number 1 to 1 such as a methoxycarbonyl group and an ethoxycarbonyl group 6 alkoxycarbonyl groups; sulfo groups; sulfamoyl groups; alkoxysulfonyl groups having 1 to 6 carbon atoms such as methoxysulfonyl groups and ethoxysulfonyl groups;
R ^a1 and R ^a2 in the —N (R ^a1 ) (R ^a2 ) group each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The aliphatic hydrocarbon group having 1 to 8 carbon atoms 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 aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. Carbon number of this aliphatic hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-5, More preferably, it is 1-4.
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. Carbon number of this cyclic aliphatic hydrocarbon group becomes like this. Preferably it is 3-8, More preferably, it is 3-6.

Ring T ¹ and ring T ² may be the same or different.

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. Yes, a C1-C8 bivalent aliphatic hydrocarbon group or a C6-C8 bivalent 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 includes methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5. -Alkanediyl groups 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, 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 groups represented by formulas (L-a1) to (L-a6).

  Examples of the divalent aromatic monocyclic hydrocarbon group include an o-phenylene group, an m-phenylene group, a p-phenylene group, and groups represented by the formulas (L-b1) to (L-b6). It is 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, more preferably 1 to 8 carbon atoms. A divalent chain hydrocarbon group, more preferably an alkanediyl group having 1 to 8 carbon atoms, and particularly preferably a linear alkanediyl group having 1 to 8 carbon atoms.
Moreover, carbon number of this bivalent hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-4.

The divalent hydrocarbon group having 1 to 8 carbon atoms in L ¹ and L ² may have a substituent, such as a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or 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 methylsulfanyl group and ethylsulfanyl 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; And the like.
More preferably, 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. L ¹ and L ² may be the same or different, but are preferably the same.

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 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 and copper ion; typical metals such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion and bismuth ion Ion; etc. are mentioned.
Examples of the substituted or unsubstituted ammonium ion represented by M ^{n +} include quaternary ammonium ions such as tetraalkylammonium ions.
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 still 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.

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

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

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

[In formula (II), L ¹ , L ² , M ^{n +} , and n are the same as above.
Ring T ³ represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent.
Ring T ⁴ represents a nitrogen-containing aromatic heterocyclic ring containing N ⁺ as a constituent atom of the ring which may have a substituent. ]

The nitrogen-containing aromatic heterocycle represented by the ring T ³ is a nitrogen-containing aromatic heterocycle containing a nitrogen atom as a ring component, wherein the nitrogen atom is> N—, and has the formula (T ³ -A) or ring is preferably represented by the formula ^(T 3 -B).
The nitrogen-containing aromatic heterocycle containing N ⁺ as a constituent atom of the ring represented by ring T ⁴ contains a nitrogen atom as a ring constituent element, and the nitrogen atom is> N ⁺ < And a ring represented by the formula (T ⁴ -A) or the formula (T ⁴ -B) is preferable.
Rings T ³ and T ⁴ may be the same or different.

Expression ^(T 3 -A), formula ^(T 3 -B), wherein ^(T 4 -A) and formula ^{(T 4 -B), X 1} , X 2, ring ^{T 5,} ring ^{T 6,} the Is the same.
* L means a bond to L ¹ or L ² and * C means a bond to a carbon atom. ]

Ring T ¹ and ring T ³ are more preferably rings represented by formula (R ³ -1) to formula (R ³ -6), and more preferably formula (R ³ -1) to formula (R ³ -3). Is a ring represented by Ring T ² and ring T ⁴ are more preferably rings represented by formula (R ⁴ -1) to formula (R ⁴ -6), and more preferably formula (R ⁴ -1) to formula (R ⁴ -3). Is a ring represented by

  Compound (I) and compound (II) are more preferably a compound represented by formula (III) (hereinafter sometimes referred to as compound (III)).

[In formula (III), ring T ⁵ , ring T ⁶ , L ¹ , L ² , M ^{n +} and n are the same as defined above. ]

Examples of the compound (I) include compounds represented by the formula (I-1) to the formula (I-63) shown in Table 1.
Compound (I) is
Preferably, it is a compound represented by formula (I-1) to formula (I-42),
More preferably, it is a compound represented by formula (I-1) to formula (I-12), a compound represented by formula (I-22) to formula (I-33),
More preferred are compounds represented by formula (I-22) to formula (I-33).

In Table 1, ring ^{T 1} represents a ring represented by the formula ^(R 3 -a1) ~ formula ^(R 3 -a3), Ring ^{T 2} are the formula ^(R 4 -a1) ~ formula ^(R 4 -a3) Represents a ring represented by Wherein ^(R 3 -a1) ~ formula ^(R 3 -a3) and the formula ^(R 4 -a1) ~ formula ^(R 4 -a3), * L and * C are as defined above.

In Table 1, L ¹ and L ² represent a divalent hydrocarbon group represented by Formula (L-1) to Formula (L-7). In formula (L-1) to formula (L-7), * n means a bond with a nitrogen atom, and * s means a bond with a sulfur atom.

L ¹ and L ² are the same, and ring T ¹ and ring T ² are represented by the formula (I) that is the same except that> N—CH <⇔> N ⁺ = C <in each ring. A compound (however, M ^{n +} = H ⁺ ) can be produced by reacting a compound represented by the formula (pt1) with a compound represented by the formula (pt2). In this reaction, the amount of the compound represented by the formula (pt1) is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt2).
The compound represented by formula (I) (where M ^{n +} ≠ H ⁺ ) is a compound represented by formula (I) (where M ^{n +} = H ⁺ ) and a halide containing an n-valent metal ion. (Preferably chloride), acetate, phosphate, sulfate, silicate or cyanide can be used for the reaction.

[In Formula (pt1) and Formula (I), Ring T ¹ , Ring T ² , L ¹ , L ² , 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 5 to 80 parts by mass with respect to 100 parts by mass of the resin (B). More preferably.

  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, and further preferably 1 to 50% by mass with respect to the total amount of the solid content. %.
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).
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 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 the solid content.

  The colored resin composition of the present invention may contain a polymerizable compound (C) and a polymerization initiator (D). Hereinafter, the colored resin composition containing the polymerizable compound (C) and the polymerization initiator (D) may be referred to as “colored curable resin composition”.

<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-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morpholino-1- ( 4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis (trichloromethyl) ) -6-Piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoy Diphenyl phosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole.

  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.

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

<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 assistant (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.

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

<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, heptanone, 4-methyl-2-pentanone and 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, 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 resin composition of the present invention. . In other words, the total amount of the solid content of the colored 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 when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

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

<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, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  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 (I) as a colorant, a color filter particularly excellent in contrast and 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.

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

[Synthesis Example 1]
3.5 parts of the compound represented by the formula (1-1), 0.57 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione, 201 parts of 1-butanol and 134 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 16 hours while removing the water produced using a Dean-Stark tube. Crystals formed after cooling were filtered, washed twice with 80 parts of hexane, and the crystals were dried under reduced pressure at 60 ° C. to obtain 3.3 parts of a compound represented by the formula (I-10).

  5.9 mg of the compound represented by formula (I-10) was dissolved in N-methylpyrrolidone to make a volume of 50 ml, 2 ml of it was diluted with N-methylpyrrolidone to make a volume of 100 ml, and a spectrophotometer (V -650; manufactured by JASCO Corporation, quartz cell, optical path length: 1 cm), the absorption spectrum was measured. This compound showed an absorbance of 5.0 (arbitrary unit) at λmax = 656 nm.

[Synthesis Example 2]
7.7 parts of the compound represented by the formula (I-10) was added to 100 parts of water to prepare a solution (aqueous solution 1) in which the compound represented by the compound (I-10) was dissolved. Separately, a solution (aqueous solution 2) in which 4.9 parts of barium chloride dihydrate was dissolved in 40 parts of water was prepared, and the aqueous solution 2 was dropped into the aqueous solution 1 at 40 ° C. over 2 hours, and then for 4 hours. Stir. 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 15 parts of a compound represented by the formula (I-31).

  A compound represented by formula (I-31) (7.5 mg) was dissolved in N-methylpyrrolidone to a volume of 50 ml, 2 ml of it was diluted with N-methylpyrrolidone to a volume of 100 ml, and a spectrophotometer (V -650; manufactured by JASCO Corporation, quartz cell, optical path length: 1 cm), the absorption spectrum was measured. This compound showed an absorbance of 3.8 (arbitrary unit) at λmax = 656 nm.

[Resin synthesis example 1]
An appropriate amount of nitrogen was passed through 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. 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 solution in which 289 parts of a mixture of decan-9-yl acrylate (trade name “E-DCPA”, manufactured by Daicel Corporation) was dissolved in 125 parts of propylene glycol monomethyl ether acetate was added using a dropping pump. For about 5 hours. On the other hand, a solution obtained by dissolving 33 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over another 6 hours using another dropping pump. did. After the completion of dropping, the mixture was held 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. 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 gel permeation chromatography (GPC method) under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
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.

Example 1
[Preparation of Colored Resin Composition (P-1)]
10 parts of a compound represented by the formula (I-10), 4 parts of a solid content of a dispersing agent BYK-LP N6919 (manufactured by BYK) (60% propylene glycol monomethyl ether acetate solution), and a resin (B-2) solution After weighing 5 parts of solids 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. Thus, a colored resin composition (P-1) was produced.

Example 2
[Preparation of colored resin composition (P-2)]
A colored resin composition (P-2) was produced in the same manner as in Example 1, except that the compound represented by the formula (I-10) was replaced with the compound represented by the formula (I-31).

Example 3 to Example 4
[Preparation of colored curable resin composition]
Each component was mixed so that it might become a composition shown in Table 2, and the colored curable resin composition was obtained.

Comparative Example 1
A colored curable resin composition was obtained in the same manner as in Example 3 except that the colored resin composition (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 2, each component represents the following compound.
Colorant (A-1): Compound represented by formula (x)

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 (registered trademark) OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate

<Preparation of color filter (colored coating film)>
A colored curable 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 composition layer. After allowing to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. The colored composition layer after the light irradiation is immersed 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 200 ° C. in an oven. Was post-baked for 120 minutes to obtain a color filter (colored coating film).

<Heat resistance evaluation>
In the production of the color filter, the xy chromaticity coordinates (x, y) and Y are measured before and after post-baking, and the color difference is measured by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). ΔEab * was calculated and the results are shown in Table 3. ΔEab * means that the smaller the color change, the smaller the color change.

<Contrast evaluation>
About the color filters obtained in Examples 3 to 4 and Comparative Example 1, contrast meter (CT-1; Keyakizaka Electric Co., Ltd., color and color difference meter BM-5A; Topcon Co., light source; F-10, polarizing film; Contrast was measured using a blank value of 30000 using the product of Aisaka Electric Co., Ltd. The results are shown in Table 3.

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

Claims (4)

Including colorants and resins,
A colored resin composition, wherein the colorant comprises a compound represented by formula (I), and the compound is a compound having an absorption maximum wavelength at 500 nm or more and less than 700 nm.

[In the formula (I),
Ring T ¹ represents an optionally substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic ring.
Ring T ² represents a nitrogen-containing aromatic heterocyclic ring containing N ⁺ as a constituent atom of the ring which may have a substituent.
L ¹ and L ² each independently represent a C 1-8 divalent hydrocarbon group which may have a substituent.
M ^{n +} represents an arbitrary cation.
n represents an integer of 1 to 5. ]   Furthermore, the colored resin composition of Claim 1 containing a polymeric compound and a polymerization initiator.   A color filter formed from the colored resin composition according to claim 1.   A display device comprising the color filter according to claim 3.