KR102023781B1 - Colorant dispersion - Google Patents

Abstract

The present invention is a colorant dispersion in which a colorant is dispersed in a solvent by a dispersant, wherein the colorant contains xanthene dye and does not substantially contain a pigment, and the content of xanthene dye is 40% by mass or more relative to the total amount of the colorant. The colorant dispersion liquid which is 100 mass% or less, a dispersing agent has an amine group, and whose amine value of a dispersing agent is 0-55 mgKOH / g, the color filter formed from this colored dispersion, and the display apparatus containing this color filter are provided.

Description

Colorant Dispersion {COLORANT DISPERSION}

The present invention relates to colorant dispersions and the like.

Colored curable compositions are used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display. And as such a colored curable composition, after disperse | distributing a pigment to a solvent, the colored curable composition manufactured by further mixing xanthene dye is used (JP2010-32999-A (Example 1)).

The brightness of the color filter obtained from said colored curable composition was not necessarily satisfactory enough.

The present invention includes the following inventions.

[1] A colorant dispersion wherein the colorant is dispersed in a solvent by a dispersant,

The colorant comprises a xanthene dye, substantially free of pigments,

Content of xanthene dye is 40 mass% or more and 100 mass% or less with respect to the total amount of a coloring agent,

A colorant dispersion wherein the dispersant has an amine group and the amine number of the dispersant is 0 to 55 mgKOH / g.

[2] The colorant dispersion according to [1], wherein the amine number of the dispersant is 2 to 40 mgKOH / g.

[3] The solvent described in [1] or [2], wherein the solvent contains propylene glycol monomethyl ether acetate and the content of propylene glycol monomethyl ether acetate is 40% by mass to 99% by mass with respect to the total amount of the solvent. Colorant dispersion.

[4] The colorant dispersion liquid according to any one of [1] to [3], further containing a resin.

[5] A colored curable composition comprising the colorant dispersion, the polymerizable compound and the polymerization initiator according to any one of [1] to [4].

[6] a pigment composition further prepared separately from the colorant dispersion,

The colored curable composition as described in [5] in which a pigment composition contains at least 1 sort (s) chosen from the group which consists of a pigment, a solvent, a pigment dispersing agent, and resin.

[7] A color filter formed of the colored curable composition according to [5] or [6].

[8] A display device comprising the color filter described in [7].

A high-brightness color filter can be obtained from the colored curable composition prepared with the coloring agent dispersion liquid of this invention.

1. Colorant Dispersion

In the coloring agent dispersion of this invention, a coloring agent (A) is disperse | distributed in the solvent (B) with a dispersing agent (D), and a coloring agent (A) contains xanthene dye (A1), and does not contain a pigment substantially. In addition, as for a coloring agent (A), content of xanthene dye (A1) is 40 mass% or more and 100 mass% or less with respect to the total amount of a coloring agent. In addition, the said dispersing agent (D) has an amine group, and an amine number is 0-55 mgKOH / g. The coloring agent (A) contains xanthene dye (A1), and substantially does not contain a pigment, and also uses the coloring agent dispersion liquid whose content of xanthene dye was 40 mass% or more and 100 mass% or less with respect to the total amount of a coloring agent. When the colored curable composition is prepared, a colored curable composition capable of producing a high brightness color filter can be obtained. In addition, contrast is also increased.

Hereinafter, each component is demonstrated in detail. In addition, in this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless a special understanding is requested | required.

1-1. Colorant (A)

Colorant (A) comprises xanthene dye (A1) and is substantially free of pigments. Content of xanthene dye (A1) is 40 mass% or more with respect to the total amount of a coloring agent (A), Preferably it is 60 mass% or more. The coloring agent (A) may further contain dyes (sometimes referred to as "other dyes (A3)") other than xanthene dyes (A1).

If a coloring agent (A) is the said structure, the color filter obtained from the colored curable composition manufactured with the coloring agent dispersion liquid of this invention is high in brightness.

1-1-1. Xanthene Dye (A1)

Xanthene dye (A1) is a dye containing the compound which has a xanthene frame | skeleton in a molecule | numerator. As xanthene dye (A1), it is C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and described by numbers only. Others are the same), 52, 87, 92, 94, 289, 388, and C.I. Acid violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive red 36 (rose bengal B), sulforhodamine G, the xanthene dye of JP2010-32999-A, the xanthene dye of JP4492760-B, etc. are mentioned.

Among these, as xanthene dye (A1), the dye containing the compound represented by Formula (1a) (hereinafter may be called "compound (1a)") is preferable. Compound (1a) may be a tautomer thereof. When using compound (1a), content of compound (1a) in xanthene dye (A1) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only compound (1a) as xanthene dye (A1).

[In formula (1a), R <^1> -R <^4> may independently independently represent a hydrogen atom and a C1-C20 monovalent saturated hydrocarbon group which may have a substituent, or a C6-C10 monovalent aromatic hydrocarbon group which may have a substituent. And -CH ₂ -contained in this saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^11- . R ¹ and R ² may be bonded to form a ring with an adjacent nitrogen atom, or R ³ and R ⁴ may be bonded to form a ring with an adjacent nitrogen atom.

R ⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is shown.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is two or more, some R <^5> may be same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, The hydrogen atom contained in this saturated hydrocarbon group may be substituted by the halogen atom.

R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and -CH ₂ -contained in this saturated aliphatic hydrocarbon group is -O-, -CO-,- It may be substituted by NH- or -NR ^8-, or R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle together with an adjacent nitrogen atom.

R ¹¹ represents a hydrogen atom, a C 1-20 monovalent saturated hydrocarbon group or a C 7-10 aralkyl group.

As a C1-C20 monovalent saturated hydrocarbon group in R <^1> -R <^4> , for example, a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, hexa Linear alkyl groups such as decyl group and icosyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C2-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

The hydrogen atom contained in the said saturated hydrocarbon group in R <^1> -R <^4> may be substituted by the C6-C10 aromatic hydrocarbon group or halogen atom, for example.

Examples of the C6-C10 monovalent aromatic hydrocarbon group in R ¹ to R ⁴ include a phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

Examples of the group even if they have a saturated hydrocarbon group or the aromatic hydrocarbon substituents, halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these, as the substituent _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ more preferably is Do. As -SO ₃ ^- Z ^+, -SO _3- ⁺ N (R ¹¹ ) ₄ is preferable. If R <^1> -R <^4> is these groups, from the colored curable composition prepared with the coloring agent dispersion liquid of this invention containing compound (1a), a color filter with little generation | occurrence | production of a foreign material and excellent in heat resistance can be formed.

As a ring which R <^1> and R <^2> combines and forms with the adjacent nitrogen atom, and the ring which R <^3> and R <^4> combines and forms with the adjacent nitrogen atom is mentioned, for example.

As a C1-C20 monovalent saturated hydrocarbon group in R <^8> -R <^11> , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, dodec Linear alkyl groups such as actual groups, hexadecyl groups, and icosyl groups; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

The C1-C20 monovalent saturated hydrocarbon group in R ⁹ and R ¹⁰ may have a substituent. As this substituent, a hydroxyl group and a halogen atom are mentioned.

As -OR <^8> , a methoxy group, an ethoxy group, a propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and an icosyloxy group are mentioned, for example.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and icosyloxysulfonyl group.

As —SO ₂ NR ⁹ R ¹⁰ , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups, such as a sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, and N- (1,1,2,2- tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. N-2 substituted sulfamoyl group, etc. are mentioned.

R ⁵ is ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or SO ₂ NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H or SO ₂ NHR ⁹ is more preferable.

1-4 are preferable and, as for m, 1 or 2 is more preferable.

As a C1-C6 alkyl group in R <^6> and R <^7> , a C1-C6 thing is mentioned among the alkyl groups mentioned above.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

At least two of four R ¹¹ in ⁺ N (R ¹¹ ) ₄ are preferably a C 5-20 monovalent saturated hydrocarbon group. Moreover, it is preferable that it is 20-80, and, as for the total carbon number of four R <^11> , it is more preferable that it is 20-60. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), and if R ¹¹ is these groups, a color filter containing few foreign substances is prepared from the colored curable composition prepared with the colorant dispersion of the present invention containing the compound (1a). Can be formed.

As compound (1a), the compound (Hereinafter, it may be called "compound (2a)") represented by Formula (2a) is preferable. Compound (2a) may be a tautomer thereof.

In the formula ^{(2a), R 21 ~ R} 24 each independently represents hydrogen, -R ^26, or even have a substituent a monovalent aromatic hydrocarbon having a carbon number of 6-10. R ²¹ and R ²² may be bonded to each other to form a ring with an adjacent nitrogen atom, or R ²³ and R ²⁴ may be bonded to each other to form a ring together with an adjacent nitrogen atom.

R ²⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z 1 ^+, or —SO ₂ NHR ²⁶ .

m1 represents the integer of 0-5. When m1 is two or more, some R <^25> may be same or different.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R <^26> represents a C1-C20 monovalent saturated hydrocarbon group.

Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four R ^{27 's} may be the same or different.

R ²⁷ represents a C 1-20 monovalent saturated hydrocarbon group or benzyl group.]

As a C6-C10 monovalent aromatic hydrocarbon group in R <^21> -R <^24> , the group similar to what was mentioned as an aromatic hydrocarbon group of said R <^1> -R <^4> is mentioned. Hydrogen atoms contained groups are aromatic hydrocarbon is -SO ₃ ^- good even if they are substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

As the combination of R ²¹ ~ R ^24, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ and the carbon number of 6 to 10 aromatic hydrocarbon 1 valence group, the hydrogen atom of the aromatic hydrocarbon groups which contain -SO ₃ ^-, It is preferred that it is substituted with -SO ₃ H, -SO ₃ ^- Z 1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- Z 1 ⁺ or -SO ₂ is substituted with NHR ²⁶ . If R <^21> -R <^24> is these groups, the color filter excellent in heat resistance can be formed from the colored curable composition prepared with the coloring agent dispersion liquid of this invention containing compound (2a).

As a ring which R <^21> and R <^22> couple | bonds and forms with the adjacent nitrogen atom, and the ring which R <^23> and R <^24> couple | bonds and forms with the adjacent nitrogen atom, R <^1> and R <^2> couple | bonds and adjoins a nitrogen atom And the like with a ring formed together. Especially, aliphatic heterocycle is preferable. As this aliphatic heterocycle, the following are mentioned, for example.

As a C1-C20 monovalent saturated hydrocarbon group in R <^26> and R <^27> , the group similar to what was mentioned as a saturated hydrocarbon group in R <^8> -R <^11> is mentioned.

When R ²¹ to R ²⁴ are —R ²⁶ , —R ²⁶ is preferably each independently a methyl group or an ethyl group. Also, -SO ₃ R ²⁶ and -SO ₂ R ²⁶ as in the NHR ^26, a branched chain alkyl group having 3 to 20 carbon atoms are preferred, the branched chain alkyl group having a carbon number of 6 to 12 more preferred, and 2-ethylhexyl More preferred. If R <^26> is these groups, the color filter with little generation | occurrence | production of a foreign material can be formed from the coloring curable composition of this invention containing compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

At least two of four R ²⁷ in ⁺ N (R ²⁷ ) ₄ is preferably a C 5-20 monovalent saturated hydrocarbon group. Moreover, it is preferable that it is 20-80, and, as for the total carbon number of four R <^27> , it is more preferable that it is 20-60. In the case where ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), and if R ²⁷ is these groups, a color with less occurrence of foreign substances from the colored curable composition prepared with the colorant dispersion of the present invention containing the compound (2a) A filter can be formed.

1-4 are preferable and, as for m1, 1 or 2 is more preferable.

In addition, as compound (1a), it is represented by said formula (2a), and R <^21> -R <^24> is respectively independently a C1-C20, especially a C1-C10 monovalent saturated hydrocarbon group, or Formula (3a). Also preferable are compounds (hereinafter sometimes referred to as "compound (3a)"). Compound (3a) may be a tautomer thereof.

[In formula (3a), R <^31> and R <^32> represents a C1-C10 monovalent saturated hydrocarbon group each independently, and the hydrogen atom contained in this saturated hydrocarbon group is substituted by C6-C10 aromatic hydrocarbon group or a halogen atom, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ -in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ^11- . You may be.

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ³¹ and R ³³ may be bonded to form a ring together with an adjacent nitrogen atom and a carbon atom on a benzene ring, or R ³² and R ³⁴ may be combined to form a ring together with an adjacent nitrogen atom and a carbon atom on a benzene ring. good.

p and q respectively independently represent the integer of 0-5. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different.

R ¹¹ has the same meaning as described above.]

As a C1-C10 monovalent saturated hydrocarbon group in R <^31> and R <^32> , the C1-C10 group is mentioned among the things in R <^8> .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be used as a substituent include the same groups as those in R ¹ .

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, and a propoxy group are mentioned, for example.

It is preferable that R <^31> and R <^32> are a C1-C3 monovalent saturated hydrocarbon group each independently.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group and isopropylsulfanyl group.

As a C1-C4 alkylsulfonyl group in R <^33> and R <^34> , a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group are mentioned.

It is preferable that R <^33> and R <^34> are respectively independently a C1-C4 alkyl group, and it is more preferable that both are methyl groups.

It is preferable that p and q are the integers of 0-2 each independently, and it is preferable that it is 0 or 1.

As compound (1a), the compound represented, for example by Formula (1-1)-Formula (1-63) is mentioned. In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group.

Among the said compounds, the compound represented by Formula (1-1)-formula (1-23) or Formula (1-37)-formula (1-63) corresponds to compound (2a), and is a formula (1-24) The compound represented by any one of formulas (1-36) corresponds to compound (3a).

Among these, C.I. Sulfonamides of acid red 289, C.I. Quaternary ammonium salt of acid red 289, C.I. Sulfonamides of acid violet 102 or C.I. Preferred are quaternary ammonium salts of acid violet 102. As such a compound, the compound etc. which are represented by Formula (1-1)-formula (1-8), Formula (1-11), or Formula (1-12), etc. are mentioned, for example.

Moreover, the compound represented by either of Formula (1-24)-Formula (1-33) is also preferable at the point which is excellent in the dispersibility to an organic solvent.

Xanthene dye (A1) is a commercially available xanthene dye (for example, "Chugai Amino Fast Pink RH / C" by Jugai Chemical Co., Ltd., "Rhodamin 6G" by Taoka Chemical Co., Ltd.). It is available. In addition, commercially available xanthene dyes may be synthesized with reference to JP2010-32999-A as a starting material.

1-1-2. Other dyes (A3)

The other dye (A3) is not particularly limited as long as it is a dye other than xanthene dye (A1), and is an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye. Dyes such as, for example, the dye in the color index (Published by The Society of Dyers and Colorists), ie CI The compound classified as having a color other than a pigment, and the well-known dye described in the dyeing note (Shiki Sensha) are mentioned. Furthermore, according to the chemical structure, azo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, Coumarin dyes, quinoline dyes, nitro dyes and the like.

1-2. Solvent (B)

Solvent (B) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule, a ketone solvent (a solvent containing -CO- in a molecule and no -COO-), an alcoholic solvent (containing OH in a molecule, -O- , -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate and ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, propylene glycol diacetate, 1,3-butylene glycol diacetate, and the like. .

As an ether solvent, For example, ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Cyclic ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Phenol ethers such as anisole, phentol and methyl anisole; 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, etc. are mentioned.

As an ether ester solvent, For example, ethylene glycol monoalkyl ether acetates, such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate; Methyl methoxy acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, 3-methoxy propionate, 3-methoxy propionate, 3-ethoxy propionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2 Ethyl ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and the like.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among the solvents mentioned above, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or 4-hydroxy-4-methyl-2-pentanone is preferable.

In particular, the solvent containing an ether ester solvent is preferable. In this case, it is preferable that content of an ether ester solvent is 40 mass% or more and 100 mass% or less with respect to the total amount of a solvent (B), and it is more preferable that they are 40 mass% or more and 99 mass% or less from a point of dispersion stability. Preferably the minimum of the said content of ether ester solvent is 60 mass%, More preferably, it is 70 mass%.

The ether ester solvent is preferably at least one selected from the group consisting of ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, and diethylene glycol monoalkyl ether acetates, and more preferably propylene glycol mono Methyl ether acetate.

When the solvent (B) is a mixed solvent, the solvent to be combined with the ether ester solvent is preferably at least one selected from the group consisting of an ether solvent and a ketone solvent, more preferably propylene glycol monomethyl ether and 4- It is at least 1 sort (s) chosen from the group which consists of hydroxy-4-methyl- 2-pentanone.

If the solvent (B) is such a solvent, since a high brightness color filter can be manufactured from the colored curable composition prepared with the coloring agent dispersion liquid of this invention, it is preferable.

As solvent (B), it is preferable that the solubility (23 degreeC) of a coloring agent (A) is 5 mass% or less solvent, and it is more preferable that it is a solvent whose solubility (23 degreeC) of a coloring agent (A) is 0.3-3 mass%. . The solvent (B) in which the solubility of xanthene dye (A1) falls within the above range is particularly preferable.

It is preferable that the coloring agent dispersion liquid of this invention contains a dispersing agent (D), and further contains resin (C).

1-3. Dispersant (D)

As a dispersing agent (D), it is used for the dispersing of a coloring agent, and if it has an amine group and an amine value is 0-55 mgKOH / g (preferably 2-40 mgKOH / g), it will not specifically limit, For example, a polymeric dispersing agent is mentioned.

Examples of the polymer dispersant include an acrylic dispersant and a urethane dispersant.

Examples of the acrylic dispersant include an acrylic block copolymer. Examples of the acrylic block copolymer include a colorant adsorption block further comprising an acid group as a colorant adsorber in a colorant adsorption block including a basic group as a colorant adsorber (also called a dye adsorber); Preference is given to using block copolymers having blocks which do not contain a colorant adsorber.

As said colorant adsorber, what is comprised by using the monomer which has an acidic group with the monomer which has a basic group as a colorant adsorption block which further contains an acidic group in the colorant adsorption block containing a basic group is mentioned.

As a monomer which has the said basic group, it is a monomer which has a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group,

Specifically N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, diethylacrylamide, dimethylaminopropyl methacrylamide, A monomer having a glycidyl group such as acryloyl morpholine, vinylimidazole, 2-vinylpyridine, an amino group and a caprolactone skeleton, and glycidyl (meth) acrylate, and one secondary amino group in the molecule Reactant with a compound having, (meth) acryloylalkylisocyanate compound with 4- (2-aminomethyl) -pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-hydroxyethyl) pyridine, 1 -(2-aminoethyl) -piperazine, 2-amino-6-methoxybenzothiazole, 1- (2-hydroxyethylimidazole), N, N- diallyl melamine, N, N-dimethyl- The reactant with 1, 3- propanediamine, etc. are mentioned.

As a monomer which has the said acidic group, it is a monomer which has a carboxy group, a sulfonic acid group, and a phosphoric acid group, Specifically, as a monomer which has a carboxy group, unsaturated monocarboxylic acid compounds, such as acrylic acid, methacrylic acid, and crotonic acid, maleic acid, fumaric acid, itaconic acid 2-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, styrenesulfonic acid as monomers having sulfonic acid groups such as unsaturated dicarboxylic acid compounds such as these and half esters thereof Acid phosphonyl (meth) acrylate, an acid phosphonyl ethyl (meth) acrylate, etc. are mentioned as a monomer which has a phosphoric acid group etc.

As a component of the block which does not contain the said coloring agent adsorption group, Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, vinyltoluene, and benzyl chloride, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acryl Unsaturated carboxylic acid aryl alkyl esters, such as an unsaturated carboxylic acid alkyl ester, such as a rate, benzyl (meth) acrylate, a polycaprolactone containing monomer, a polyalkylene glycol monoester type monomer, etc. can be illustrated.

The acrylic block copolymer can be obtained by living anion polymerization or the like, and a conventionally known polymerization method can be used.

The amine titer of the said acrylic block copolymer is 0-55 mgKOH / g normally, Preferably it is 0-50 mgKOH / g, More preferably, it is 2-40 mgKOH / g. On the other hand, the amine number means the amine value per 1 g of the solid content of the acrylic block copolymer, using a 0.1 mol / L aqueous hydrochloric acid solution, potentiometric titration method (e.g. COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK-900) ) And the value converted into equivalents of potassium hydroxide after the measurement by Hiranumasan Co., Ltd.).

As a commercial item of the said acryl-type block copolymer, "Disperbyk (registered trademark) -112 (amine value 36 mgKOH / g)" by "Bekchem Japan Japan", "Disperbyk (registered trademark) -2000 (amine value 4 mgKOH / g)", `` Disperbyk-2001 (amine value 29 mgKOH / g) '', `` Disperbyk (registered trademark) -2020 (amine value 38 mgKOH / g) '', `` Disperbyk (registered trademark) -2050 (amine value 30 mgKOH / g) '', `` Disperbyk ( Registered trademark) -2070 (amine value 20 mgKOH / g) ”.

As said urethane type dispersing agent, what is obtained by making the isocyanate group of a polyisocyanate compound react the compound of the number average molecular weight 300-10,000 which has one or more hydroxyl groups in a molecule | numerator, and the basic group containing compound which has a functional group which can react with an isocyanate group in a molecule | numerator can be used. . As a method of obtaining such a urethane type dispersing agent, the method described in JPS60-166318-A, etc. can be used.

As a polyisocyanate compound which comprises the said urethane type dispersing agent, the isocyanate compound which has 2 or more isocyanate groups is mentioned, For example, 2, 4- tolylene diisocyanate, a dimer of 2, 4- tolylene diisocyanate, 2, 6- tolylene di Isocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate Aromatic diisocyanate compounds such as; Hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanate methylene) cyclohexane, etc. Aliphatic and alicyclic polyisocyanates; Polyisocyanates having isocyanuric groups based on the above diisocyanates (polyisocyanates having isocyanuric groups formed by trimming the diisocyanate), and polyisocyanates and diisocyanate compounds obtained by reacting diisocyanates with polyols. The polyisocyanate etc. which are obtained by reaction are mentioned. Among the above polyisocyanate compounds, polyisocyanates having isocyanuric groups based on diisocyanates such as tolylene diisocyanate and isophorone diisocyanate are preferable.

As a compound which has one or more hydroxyl groups in the molecule | numerator which comprises the said urethane type dispersing agent, a polyether compound, a polyester compound, etc. are mentioned, for example.

As said polyether compound, For example, Polyalkylene glycol, such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol; Alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol And ethylene oxide modified products, propylene oxide modified products, butylene oxide modified materials, tetrahydrofuran modified products, and the like of low molecular weight monools such as methanol and ethanol.

Examples of the polyester compound include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, ditrimethylol propane, dipenta (Epsilon) -caprolactone modified substance, (gamma) -butyrolactone modified substance, (delta) -valerolactone modified substance, methylvalerolactone modified substance of alkylene glycols, such as erythritol, and low molecular weight monools, such as methanol and ethanol; Aliphatic polyester polyols which are esterified products of aliphatic dicarboxylic acids such as adipic acid and dimer acid and polyols such as neopentyl glycol and methylpentanediol; Polyester polyols such as aromatic polyester polyols which are esterified products of aromatic dicarboxylic acids such as terephthalic acid and polyols such as neopentyl glycol; Polyhydric hydroxy group compounds such as polycarbonate polyol, acryl polyol, polytetramethylenehexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid Esterified products with dicarboxylic acids such as; Polyhydric hydroxy group containing compounds, such as monoglyceride obtained by transesterification reaction of polyhydric hydroxy group containing compounds, such as glycerin, and fatty acid ester, etc. are mentioned. Among the compounds having at least one hydroxyl group in the molecule, ε-caprolactone adducts of alcohols are preferable.

The number average molecular weight of the compound which has one or more hydroxyl groups in the said molecule | numerator is 300-10,000, Preferably it is 300-6,000. In addition, a number average molecular weight and a weight average molecular weight can be measured by a column chromatography method.

Although it does not specifically limit as a basic group containing compound which has a functional group which can react with an isocyanate group in the molecule | numerator which comprises the said urethane type dispersing agent, It consists of polyol, polythiol, and amines which have N, N-di substituted amino group or heterocyclic nitrogen atom. It is preferable that it is at least 1 type of compound chosen from the group. As these compounds, the compound used by the well-known conventional art in the technical field of a dispersing agent can be used. These compounds have an active hydrogen atom of Zerewitinoff and at least one nitrogen atom-containing basic group.

Such compounds include, for example, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,4-butanediamine, 2-dimethylaminoethanol, 1- (2-aminoethyl) -pipe Lazine, 2- (1-pyrrolidyl) -ethylamine, 4-amino-2-methoxypyrimidine, 4- (2-aminoethyl) -pyridine, 1- (2-hydroxyethyl) -piperazine, 4- (2-hydroxyethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzoimidazole, 2-amino-6-methoxybenzothiazole, N, N-diallyl-melamine, 3 -Amino-1,2,4-triazole, 1- (2-hydroxyethyl) -imidazole, 3-mercapto-1,2,4-triazole, etc. are mentioned. Among them, amines having a heterocyclic nitrogen atom are preferable.

Reaction in the synthesis | combination of the said urethane type dispersing agent is not specifically limited, It can carry out by a conventionally well-known method. Moreover, the amine titer of the said urethane type dispersing agent is also 0-55 mgKOH / g, Preferably it is 5-40 mgKOH / g.

Moreover, as a commercial product of the said urethane-type dispersing agent, Disperbyk-161 (Amine value 11 mgKOH / g, the product made by Vikchem Co., Ltd.), Disperbyk-162 (Amine value 13 mgKOH / g Vikchemy make), Disperbyk-167 (Amine value 13 mgKOH / g) , Vikchem Co., Ltd., Disperbyk-182 (amine value 13 mgKOH / g, Vikchem Co., Ltd.), etc. are mentioned.

As the dispersant, the acrylic dispersant is preferable.

1-4. Resin (C)

Although resin (C) is not specifically limited, It is preferable that it is alkali-soluble resin. As resin (C), the following resin [K1]-resin [K6], etc. are mentioned.

At least one selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and Copolymer with monomer (b) (hereinafter sometimes referred to as "(b)") having an ethylenically unsaturated bond;

With the resin [K2] (a) and (b) and the monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter may be referred to as "(c)"). Copolymers;

Copolymer of resin [K3] (a) and (c);

Resin [K4] Resin obtained by making (b) react with the copolymer of (a) and (c);

Resin obtained by making (a) react with the copolymer of resin [K5] (b) and (c);

Resin [K6] Resin obtained by making (a) react with the copolymer of (b) and (c), and making carboxylic anhydride further react.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity, or the solubility of the resin obtained to aqueous alkali solution.

(b) means the polymerizable compound which has an ethylenically unsaturated bond with a C2-C4 cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter " (b2) ", and the monomer (b3) (Hereinafter, it may be called" (b3) ") which have a tetrahydrofuryl group and ethylenically unsaturated bond, etc. are mentioned.

As (b1), for example, a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and the alicyclic unsaturated hydrocarbon is epoxy And monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a ized structure.

As (b1-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta)-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc. Can be.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide® 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl Methyl (meth) acrylate (e.g., cyclomer® A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., cyclomer M100; dicel Co., Ltd.) Production), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[In Formula (I) and Formula (II), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ^a and X ^b represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

As an alkyl group in which the hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^<a> and R <^b> , Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1 And a 6-diyl group.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond and *- CH ₂ CH ₂ —O— (* indicates the number of bonds with O).

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-a formula (I-15) are mentioned. Preferably formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) The compound represented by) is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9), or Formula (I-15) is mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-formula (II-15) are mentioned. Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) The compound represented by) is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination with the compound represented by the formula (I) and the compound represented by the formula (II). When using these together, the content rate of the compound represented by Formula (I) and the compound represented by Formula (II) becomes like this. Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90: 10, More preferably, it is 20: 80-80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3- methacryloyl oxymethyl oxetane, 3-methyl-3- acroyloxy methyl oxetane, 3-ethyl-3- methacryloyl oxymethyl oxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yuki Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which can improve reliability, such as heat resistance and chemical-resistance, of the color filter obtained. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of a colored curable composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methyl Cyclohexyl (meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is referred to as "dicyclopentanyl (meth) acrylate" as a common name. It may also be referred to as "tricyclodecyl (meth) acrylate.", Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field as the conventional name, "dicyclo Is called "pentenyl (meth) acrylate.", Di Cyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene monomers such as styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, and p-methoxy styrene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride and vinylidene chloride; Amide monomers such as acrylamide and methacrylamide; Vinyl acetate; And diene monomers such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and heat resistance. Do.

In resin [K1], the ratio of the structural unit derived from each is in all the structural units which comprise resin [K1],

structural unit derived from (a); 2 ~ 60 mol%

structural unit derived from (b); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency which is excellent in the storage stability of a colored curable composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Osaka Yuki, First Publication, First Edition, March 1, 1972, issued by Chemical Co., Ltd.) and references cited in this document. It can manufacture.

Specifically, the method of putting in predetermined amount (a) and (b), a polymerization initiator, a solvent, etc. in a reaction container, replacing oxygen with nitrogen, for example, making it into a deoxidation atmosphere, and heating and keeping stirring while stirring is mentioned. have. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide etc.) are mentioned as a polymerization initiator. What is necessary is just to melt | dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. In particular, when the polymerization is carried out, the solution after the reaction can be used as it is for the preparation of the colored curable composition of the present invention by using the solvent contained in the colored curable composition of the present invention as a solvent, thereby producing the colored curable composition of the present invention. The process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K2],

structural unit derived from (a); 2 ~ 45 mol%

structural unit derived from (b); 2 ~ 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5-40 mol%

structural unit derived from (b); 5 ~ 80 mol%

structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of resin [K2] exists in the above-mentioned range, there exists a tendency which is excellent in the storage stability of a colored curable composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the color filter obtained.

Resin [K2] can be manufactured by the same method as the method described as a manufacturing method of resin [K1], for example.

In resin [K3], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K3],

structural unit derived from (a); 2 ~ 60 mol%

structural unit derived from (c); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (c); It is more preferable that it is 50-90 mol%.

Resin [K3] can be manufactured by a method similar to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] is obtained by obtaining the copolymer of (a) and (c) and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has can do.

First, the copolymer of (a) and (c) is manufactured by the method similar to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was illustrated by resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask was replaced by nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether (e.g. tris (dimethyl Aminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) and the like can be placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to produce a resin [K4].

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of the colored curable composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become favorable. Since the reactivity of cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c).

Reaction conditions, such as an input method, reaction temperature, and time, can be appropriately adjusted in consideration of the amount of heat generated by a production facility or polymerization. On the other hand, in the same manner as the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

Resin [K5] is a 1st step and is obtained by the same method as the manufacturing method of resin [K1] mentioned above, and obtains the copolymer of (b) and (c). In the same manner as described above, the obtained copolymer may be used as it is, a concentrated or diluted solution may be used, or one obtained as a solid (powder) may be used by a method such as reprecipitation.

The ratio of the structural unit derived from (b) and (c) is respectively with respect to the total number of moles of all the structural units which comprise the said copolymer.

structural unit derived from (b); 5 ~ 95 mol%

structural unit derived from (c); It is preferable that it is 5-95 mol%,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (c); It is more preferable that it is 10-90 mol%.

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the conditions similar to the manufacturing method of resin [K4] Resin [K5] can be obtained by making it react.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin obtained by making carboxylic anhydride further react with resin [K5].

The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (C) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decylacrylate / (meth Resins such as acrylic acid copolymers; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decylacrylate / (meth) acrylic acid / styrene Resins such as monomer copolymers and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymers; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, is mentioned. .

Especially, as resin (C), resin [K1] and resin [K2] are preferable.

The weight average molecular weight of polystyrene conversion of resin (C) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (C) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (C) becomes like this. Preferably it is 50-170 mgKOH / g, More preferably, it is 60-150 mgKOH / g, More preferably, it is 70-135 mgKOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, a potassium hydroxide solution.

1-5. Process for preparing colorant dispersion

In the manufacturing method of the coloring composition of this invention, a coloring agent (A) is disperse | distributed to a solvent (B) with a dispersing agent (D), and resin (C) is further disperse-processed in the said solvent (B) as needed. , Colorant dispersion can be prepared.

Dispersion processing means mixing until particle | grains, such as a coloring agent (A) and resin (C), become a dispersed state. By this dispersion treatment, the particles are pulverized small. In addition, a dispersed state means the state which the particle | grains floated in the solvent (B) in the liquid mixture.

As for content of the coloring agent (A) in the coloring agent dispersion liquid of this invention, 2 mass% or more is preferable with respect to the total amount of a coloring agent dispersion liquid, More preferably, it is 5 mass% or more, 30 mass% or less is preferable, and 20 mass% or less More preferred.

Moreover, as for content of a solvent (B), 60 mass% or more is preferable with respect to the total amount of a coloring agent dispersion liquid, More preferably, it is 75 mass% or more, 93 mass% or less is preferable, 90 mass% or less is more preferable, More preferably, it is 85 mass% or less.

When the colorant dispersion contains a resin (C), the content of the resin (C) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 15% by mass or less, based on the total amount of the colorant dispersion. More preferably, it is 7 mass% or less. When content of resin (C) exists in the said range, there exists a tendency for a dispersed state to become stable.

As for content of the dispersing agent (D) in a coloring agent dispersion liquid, 1 mass% or more is preferable with respect to the total amount of a coloring agent dispersion liquid, More preferably, it is 2 mass% or more, 20 mass% or less is preferable, More preferably, it is 10 mass% or less to be. When content of a dispersing agent (D) exists in the said range, there exists a tendency for a dispersed state to become stable.

As for the temperature at the time of disperse | distributing the said coloring agent (A) to the solvent (B), and at the time of disperse | distributing the said mixture, 120 degrees C or less is preferable, More preferably, it is 70 degrees C or less. Although the minimum of temperature at the time of dispersing is not specifically limited, Usually, it is 20 degreeC.

0.5 hour or more is preferable, dispersion time is 2 hours or more preferably, 48 hours or less are preferable, and 20 hours or less are more preferable.

As a device used for dispersion, a roll mill, a high speed stirring apparatus, a bead mill, a ball mill, a sand mill, a paint conditioner, an ultrasonic dispersion machine, a high pressure dispersion machine, etc. are mentioned, for example.

It is preferable to filter the obtained coloring agent dispersion liquid with the filter of about 1.0-5.0 micrometers of pore diameters.

2. Colored Curable Composition

The colored curable composition of this invention contains a polymeric compound (E) and a polymerization initiator (F) in addition to the coloring agent dispersion liquid mentioned above.

2-1. Polymerizable Compound (E)

The polymerizable compound (E) is a compound which can be polymerized by an active radical and an acid generated from a polymerization initiator (F) described later, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. ) Acrylic acid ester compound is mentioned.

Especially, as a polymeric compound (E), the polymeric compound which has three or more ethylenically unsaturated bonds (preferably 4-10, More preferably, 5-8) is preferable, Furthermore, three or more (preferably The ester of the alcohol (for example, pentaerythritol, its condensate, or modified product thereof) which has an OH group of 4-10, More preferably, 5-8) and (meth) acrylic acid is preferable. Examples of such a polymerizable compound include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and tripentaerythritol hepta. (Meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (Meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (Meth) acrylate, caprolactone modified dipene Taerythritol hexa (meth) acrylate etc. are mentioned. Especially, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned preferably.

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

It is preferable that content of a polymeric compound (E) is 7-65 mass% with respect to solid content of a colored curable composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of the said polymeric compound (E) exists in the said range, hardening arises enough, the residual film ratio in image development improves, it becomes difficult to undercut into a colored patterned coating film, and since adhesiveness tends to become favorable, it is preferable. Do.

2-2. Polymerization initiator (F)

As said polymerization initiator (F), if it is a compound which can generate an active radical, an acid, etc. by the action of light or heat, and can start superposition | polymerization, it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (F), the compound which generate | occur | produces an active radical by the effect of light is preferable, and an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

As a compound which has the partial structure represented by a formula (d2), for example, 2-methyl- 2-morpholino-1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1- (4) -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane- 1-one etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oligomers of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

In view of the sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferable, and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1- More preferred is one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercially available products, such as Irgacure 819 (made by BASF Corporation).

The oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond number.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2 , 4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- 3-cyclopentyl propane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation). Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2- Preferred are imines and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imines. If it is these oxime compounds, when preparing the colored curable composition of this invention as a blue colored curable composition, there exists a tendency for the brightness of the color filter obtained to become high.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see eg JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -Tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), the phenyl group at the 4,4'5,5'-position already substituted by a carboalkoxy group And a dazole compound (for example, see JPH07-10913-A and the like). Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As the polymerization initiator (F), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (F1) (especially amines) mentioned later.

As an acid generator which generate | occur | produces an acid by light, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium, for example p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium onium salts such as p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates, benzointosylates and the like.

Content of a polymerization initiator (F) is resin (C) in the colored curable composition of this invention (when resin (C ') mentioned later is included, resin (C') shall also be included) and a polymeric compound (E) Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of, More preferably, it is 1-20 mass parts. When content of a photoinitiator exists in the said range, it will become high sensitivity, shortening an exposure time, and improving productivity.

The colored curable composition of this invention may further contain at least 1 sort (s) chosen from the group which consists of a polymerization start adjuvant (F1) and a leveling agent (G).

2-3. Polymerization Initiator (F1)

The colored curable composition of this invention may further contain the polymerization start adjuvant (F1). A polymerization start adjuvant (F1) is a compound or sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator, and is used normally in combination with polymerization initiator (F).

As polymerization start adjuvant (F1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercially available products, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxide Citioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetate, methylphenylsulfanyl acetate, ethylphenylsulfanyl acetate, methylethylphenylsulfanyl acetate, dimethylphenylsulfanyl acetate, methoxyphenylsulfanyl acetate, dimethoxyphenylsulfanyl acetate, Chlorophenylsulfanyl acetate, dichlorophenylsulfanyl acetate, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When using a polymerization start adjuvant (F1), the usage-amount is resin (C) in the colored curable composition of this invention (when resin (C ') mentioned later is included, resin (C') is also included) and superposition | polymerization Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts with respect to 100 mass parts of total amounts of a sex compound (E). If the amount of the polymerization initiation assistant (F1) is within this range, the pattern can be formed with higher sensitivity, and the pattern productivity tends to be improved.

2-4. Leveling agent (G)

Examples of the leveling agent (G) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, dore silicon (brand name) DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper 8400 (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, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like. .

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Florade (registered trademark) FC430, East FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Park (registered trademark) F142D, East F171, East F172, East F173, East F177, East F183, East F554, East R30 , RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishima Terry Alden Shigasei Co., Ltd.), sufflon (registered trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Co., Ltd.), etc. are mentioned.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Park (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F 443 (manufactured by DIC Corporation), and the like.

The content of the leveling agent (G) is preferably 0.001% by mass or more and 0.2% by mass or less with respect to the total amount of the colored curable composition of the present invention, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass. 0.05 mass% or more. In addition, content of the pigment dispersant (D ') mentioned later is not included in this content. If content of a leveling agent (G) exists in the said range, flatness of a color filter can be made favorable.

2-5. Resin (C ')

When the coloring agent dispersion liquid of this invention does not contain resin, it is preferable to add resin ("resin (C ')") when preparing colored curable composition. Moreover, when a coloring agent dispersion liquid contains resin (C), you may add resin (C ') further when preparing colored curable composition. The same thing as resin (C) is mentioned as resin (C ') used when preparing colored curable composition. Resin (C ') may be the same as resin (C), but may be a different kind.

The total content of the resin (C) and the resin (C ') is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 13 to 55% by mass relative to the total amount of solids. . When content of resin exists in the said range, there exists a tendency for the resolution of a coloring pattern and the residual film rate of a coloring pattern to improve.

It is preferable that the colored curable composition of this invention further contains at least 1 sort (s) chosen from the group which consists of a solvent (B ') and a coloring agent (A').

2-6. Solvent (B ')

As a solvent (henceforth "a solvent (B ')") used when preparing colored curable composition, the same thing as a solvent (B) is mentioned.

Preferably, from the point of applicability | paintability and dryness, the boiling point in 1 atm is an organic solvent of 120 degreeC or more and 180 degrees C or less, More preferably, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3 Ethyl ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4 -Hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, and the like, more preferably propylene glycol monomethyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, Diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

The total content of the solvent (B) and the solvent (B ') in the colored curable composition is preferably 40 to 95 mass%, and more preferably 45 to 92 mass%, based on the total amount of the colored curable composition. In other words, solid content of a colored curable composition becomes like this. Preferably it is 5-60 mass%, More preferably, it is 8-55 mass%. When content of a solvent exists in the above-mentioned range, flatness at the time of application | coating becomes favorable, and since a color density does not run short when a color filter is formed, there exists a tendency for display characteristic to become favorable.

2-7. Colorant (A ')

As a coloring agent (A ') used when preparing colored curable composition, the same thing as a coloring agent (A), and a pigment (A2) are mentioned.

The total content of the coloring agent (A) and the coloring agent (A ') is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, still more preferably 10 to 50% by mass, based on the solid content of the colored curable composition. %to be. When content of a coloring agent exists in the said range, since the color density at the time of setting it as a color filter can be sufficient, and a resin and a polymeric compound can be contained in a composition, a color filter with sufficient mechanical strength can be formed. Here, solid content of a colored curable composition means the total amount of the component except the solvent in the colored curable composition of this invention. Solid content and content of each component with respect to it can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

2-8. Pigment composition

When the colored curable composition of this invention contains a pigment (A2), it is preferable to prepare a pigment composition separately from the said coloring agent dispersion liquid, and to use for preparation of the colored curable composition of this invention. It is preferable that a pigment composition contains a pigment (A2) and a solvent (B "). The pigment (A2) mixes previously with a solvent (B"), and it beads until the average particle diameter of a pigment becomes about 0.2 micrometer or less. It is preferable to disperse | distribute using a wheat etc. Solvent (B ") is a part or all of solvent (B ').

It is preferable that the pigment composition further contains at least 1 sort (s) chosen from the group which consists of resin (C ") and a pigment dispersant (D '). Resin (C") is a part or all part of resin (C'). Pigment (A2) is uniformly dispersed in a solution by containing at least one selected from the group consisting of a resin (C ") and a pigment dispersant (D ') and dispersing the pigment (A2).

2-8-1. Pigment (A2)

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include organic pigments and inorganic pigments, and compounds classified as pigments in the color index (Published by The Society of Dyers and Colourists). Can be.

As the organic pigment, for example, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ;

C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments, such as pigment green 7, 36, and 58, etc. are mentioned.

Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, 15: 6 are preferred, and C.I. Pigment Blue 15: 6 is more preferable.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Can be mentioned.

The pigment (A2) described above may be optionally treated with rosin, surface treatment using a pigment derivative or dispersant having an acidic group or a basic group introduced therein, graft treatment on the surface of the pigment with a polymer compound, atomization treatment by sulfate atomization, or the like, Alternatively, a washing treatment with an organic solvent or water for removing impurities, or a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. Moreover, it is preferable that pigment (A2) is uniform particle size.

In addition, when using a pigment (A2), content of the pigment (A2) becomes like this. Preferably it is 1-99 mass% with respect to the total amount of a coloring agent (A) and a coloring agent (A '), More preferably, it is 50-99 mass% More preferably, it is 70-99 mass%.

2-8-2. Pigment Dispersant (D ')

As the pigment dispersant (D '), in addition to the same as the dispersant (D) mentioned above, a synergistic dispersant can be used.

Examples of the synergistic dispersant (pigment derivative type dispersant) include phthalocyanine derivatives. Examples of commercially available products of the synergistic dispersant include "Sulpas (registered trademark) 5000 (copperphthalocyanine derivative)" manufactured by Lubriz Corporation.

In the case of containing the synergistic dispersant, the content thereof is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and 20 parts by mass or less based on 100 parts by mass of the pigment. Is preferable, More preferably, it is 10 mass parts or less, More preferably, it is 8 mass parts or less.

When using the said polymeric dispersing agent and a synergistic dispersing agent together as a pigment dispersing agent (D '), 70/30-99/1 are preferable, and, as for these mass ratio (polymeric dispersing agent / synergistic dispersing agent), More preferably, 80 / 20-97/3, More preferably, it is 85/15-95/5.

The usage-amount of a pigment dispersant (D ') is 100 mass parts or less per 100 mass parts of pigments (A2), More preferably, they are 5 mass parts or more and 50 mass parts or less.

The total content of the dispersant (D) and the pigment dispersant (D ') is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, based on the total amount of the colored curable composition. 20 mass% or less is preferable, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

When the usage-amount of a pigment dispersant (D ') exists in the said range, the dispersion state of a pigment will be favorable.

5 mass% or more is preferable with respect to the total amount of a pigment composition, More preferably, it is 10 mass% or more, 30 mass% or less is preferable, and, as for content of the pigment (A2) in a pigment composition, 20 mass% or less is more preferable. .

As for content of the solvent (B ") in a pigment composition, 60 mass% or more is preferable with respect to the total amount of a pigment composition, More preferably, it is 75 mass% or more, 90 mass% or less is preferable, More preferably, 85 mass% It is as follows.

When containing resin (C "), 1 mass% or more of content of resin (C") in a pigment composition is preferable with respect to the total amount of a pigment composition, More preferably, it is 2 mass% or more, and 15 mass% or less Preferably, it is 7 mass% or less.

When it contains a pigment dispersant (D '), 1 mass% or more is preferable with respect to the total amount of a pigment composition, and, as for content of the pigment dispersant (D') in a pigment composition, More preferably, it is 2 mass% or more, 20 mass% The following is preferable, More preferably, it is 10 mass% or less.

2-9. Other ingredients

The colored curable composition of this invention uses various additives (henceforth "other components") known in the said technical field, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a light stabilizer, a chain transfer agent, as needed. It may be included.

2-10. Method for producing colored curable composition

The colored curable composition of this invention is the coloring agent dispersion liquid, polymeric compound (E), and polymerization initiator (F) of this invention, and the polymerization start adjuvant (F1), leveling agent (G), pigment composition which are used as needed, and It can prepare by mixing other components.

When a coloring agent dispersion does not contain resin (C), it is preferable to add resin (C ') when preparing colored curable composition. When a coloring agent dispersion liquid contains resin (C), you may add resin (C ') further when preparing colored curable composition.

When preparing a colored curable composition, you may add a coloring agent (A ') and / or a solvent (B') further.

It is preferable to filter the colored curable composition prepared by mixing as mentioned above with the filter of about 0.01-10 micrometers of pore diameters.

3. Manufacturing method of color filter

As a method of manufacturing the colored patterned coating film of a color filter with the colored curable composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithographic method is a method of applying the colored curable composition to a substrate, drying to form a composition layer, exposing the composition layer through a photomask, and developing it. In the photolithography method, the colored coating film which is the hardened | cured material of the said composition layer can be formed by not using a photomask and / or developing at the time of exposure.

The film thickness of the produced color filter is not specifically limited, According to the objective, a use, etc., it can adjust suitably, For example, it is 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and the soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, silicon, aluminum on the said board | substrate, Silver and the thing which formed the silver / copper / palladium alloy thin film etc. are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed by a well-known or usual apparatus and conditions. For example, it can produce as follows.

First, a coloring curable composition is apply | coated on a board | substrate, and it heat-drys (prebakes) and / or drys under reduced pressure, removes and dries volatile components, such as a solvent, and obtains a smooth composition layer.

As a coating method, a spin coat method, the slit coat method, the slit & spin coat method, etc. are mentioned.

30-120 degreeC is preferable and, as for the temperature at the time of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The film thickness of a composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Subsequently, the composition layer is exposed through a photomask for forming a desired colored patterned coating film. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm may be selectively selected using a bandpass filter that extracts these wavelength ranges. May be extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses such as a mask aligner and a stepper because the entire light exposure surface can be uniformly irradiated with parallel light or can be accurately aligned with the photomask and the substrate.

The coloring pattern is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. The unexposed part of a composition layer melt | dissolves in a developing solution and is removed by image development. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method and a spray method. In addition, during development, the substrate may be tilted at an arbitrary angle.

It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake to the obtained colored patterned coating film. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

The colored patterned coating film and the colored coating film thus obtained are useful as color filters because they have high brightness, and the color filters are used for display devices (e.g., liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a filter.

Example

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to the following Example, It is also possible to change suitably and to implement in the range which may be suitable for the said and later meaning, These are All are included in the technical scope of the present invention. In the examples, "%" and "parts" are% by mass and parts by mass unless otherwise specified.

In the following synthesis examples, the compound was identified by mass spectrometry (LC; Form Agilent 1200, MASS; Form Agilent LC / MSD).

Synthesis Example 1

20 parts of compounds represented by Formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions, and the resulting solution was stirred at 110 ° C for 6 hours. After cooling the obtained reaction liquid to room temperature, it added in the liquid mixture of 800 parts of water and 50 parts of 35 weight% hydrochloric acid, and stirred at room temperature for 1 hour, and crystal precipitated. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of the compound represented by the formula (1-24). Yield 80%.

Identification of the compound represented by formula (1-24)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 603.4

Exact Mass: 602.2

Synthesis Example 2

A compound represented by the formula (1-32) was obtained in the same manner as in Synthesis example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by formula (1-32)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 659.9

Exact Mass: 658.9

Synthesis Example 3

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of the compound represented by formula (A0-1) and a compound represented by formula (A0-2) (manufactured by Jugai Chemical Co., Ltd.), 150 parts of chloroform and N, 8.9 parts of N-dimethylformamide was added, and 10.9 parts of thionyl chlorides were added dropwise while maintaining the temperature at 20 ° C. or lower under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. The mixture liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamines was dripped, keeping the reaction solution after cooling at 20 degrees C or less under stirring. Then, it stirred and reacted for 5 hours at the same temperature. Subsequently, after distilling off the solvent by the rotary evaporator, the reaction mixture obtained was added with a small amount of methanol and stirred vigorously. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of dye A1 (a mixture of compounds represented by formulas (A1-1) to (A1-8)).

Synthesis Example 4

50.0 parts of compounds represented by the formula (1x) and 350 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 18.1 parts of diethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to the mixture at 20 ° C. It dripped at the temperature not exceeding, and stirred at 20 degreeC for 3 hours. The reaction solution was poured into 2100 parts of 10% hydrochloric acid. The obtained precipitate was obtained as a residue of suction filtration, washed with 373 parts of ion-exchanged water, and dried to obtain 23.6 parts of the compound represented by the formula (1y). Yield 43%.

Identification of the compound represented by formula (1y)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 442.1

Exact Mass: 441.1

Synthesis Example 5

5.0 parts of compounds represented by formula (1y) and 35 parts of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and dipropylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 3.4 was added to the mixture. The part was dripped at the temperature which does not exceed 20 degreeC, the temperature was raised to 80 degreeC, and it stirred for 3 hours. After cooling the reaction liquid to room temperature, 3.4 parts of concentrated hydrochloric acid was added, and the obtained mixture was poured into 315 parts of saturated saline. The obtained precipitate was obtained as a residue of suction filtration, washed with 630 parts of ion-exchanged water, and dried to obtain 3.9 parts of the compound represented by the formula (1-51). Yield 69%.

Identification of the compound represented by formula (1-51)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 507.7

Exact Mass: 506.7

Synthesis Example 6

10.0 parts of compounds represented by the formula (1x) and 40 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and 7.2 parts of diethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise to the mixture. It heated up at 65 degreeC and stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into 280 parts of 0.5% saline solution. The obtained precipitate was obtained as a residue of suction filtration, washed with 200 parts of ion-exchanged water, dried, and 8.0 parts of the compound represented by the formula (1-55) were obtained. Yield 68%.

Identification of the compound represented by formula (1-55)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 479.3

Exact Mass: 478.2

Synthesis Example 7

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace with a nitrogen atmosphere, 300 parts of diethylene glycol ethylmethyl ether was added, and heated to 85 ° C while stirring. Then 54 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9- A solution obtained by dissolving 306 parts of a mixture of monoacrylate (containing a molar ratio of 50:50) and 24 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 316 parts of diethylene glycol ethylmethyl ether was dissolved in 5 parts. It dripped in the flask over time. After completion of the dropwise addition, the mixture was held at 85 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer solution. This copolymer is referred to as resin C1. Solid content of the resin C1 solution measured by 37.0 weight% and the Brookfield viscometer (23 degreeC) was 88 mPa * s. As for the weight average molecular weight of resin C1, the acid value of 7.5x10 <^3> , solid content conversion was 91 mg-KOH / g, and molecular weight distribution was 1.93. Resin C1 has the following structural units.

Synthesis Example 8

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace with a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. 54 parts acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylic A mixed solution prepared by dissolving 225 parts of the mixture (rate: 50:50 in molar ratio) and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 4 hours.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2, 2- azobis (2, 4- dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. After completion of dropwise addition of the initiator solution, the mixture was held at 85 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer solution. This copolymer is referred to as resin C2. Solid content of resin C2 solution measured by 37.5% and the Brookfield viscometer (23 degreeC) was 246 mPa * s. As for the weight average molecular weight of resin C2, the acid value of 1.06x10 <^4> and solid content conversion was 115 mg-KOH / g, and molecular weight distribution was 2.01. Resin C2 has the following structural units.

Synthesis Example 9

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate (FA-513M by Hitachi Chemical Co., Ltd.) of a tricyclodecane skeleton, and propylene The solution which added 3.6 g of 2,2'- azobisisobutyronitrile was dripped at the mixture which consists of 136 g of glycol monomethyl ether acetates, and stirring was further continued at 100 degreeC.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, 35.5 g [0.25 mol of glycidyl methacrylate ((50 mol% based on the carboxyl group of methacrylic acid used in this reaction)]], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC, and the resin C3 solution whose solid acid value was 79 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 30,000.

Synthesis Example 10

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Subsequently, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50 parts. It was dissolved in 440 parts and 140 parts of propylene glycol monomethyl ether acetate, and the solution was prepared, and this solution was dripped at the flask kept at 70 degreeC over 4 hours using the dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetates is dripped in the flask over 4 hours using the other dropping funnel. did. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9073, the molecular weight distribution was 2.16, the solid content 34.8%, and the solution acid value was 28 mgKOH /. Resin C4 solution which was g (acid value of solid content conversion: 81 mgKOH / g) was obtained.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device; K2479 (manufactured by Shimadzu Seisakusho Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detectors; RI

Calibration standards; 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 of polystyrene conversion obtained above was made into molecular weight distribution.

Example 1

(Preparation of Colorant Dispersion 1)

Xanthene dyes (a1); 9.60 parts of compounds represented by formula (1-32)

Solvent (B); Propylene glycol monomethyl ether acetate 58.21 parts

Solvent (B); Propylene glycol monomethyl ether 5.76 parts

Resin (C); Resin C2 (solid content conversion) 3.17 parts

Dispersant (D); Acrylic dispersant (Disperbyk (R) 2000; manufactured by Vikchemy; Amine number 4 mgKOH / g) 3.70 parts

And 360 parts of 0.2 mm diameter zirconia beads were thrown into the mayonnaise bottle of capacity 140 ml, it knead | mixed at 60 degreeC for 10 hours with the paint conditioner, and the dispersion process was carried out. Thereafter, zirconia beads were removed to obtain a dispersion. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 1 was obtained.

On the other hand, about the compound represented by Formula (1-32), the solubility in the propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether solvent (content ratio is 9/1 by mass basis) at 23 degreeC was 3%. .

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 1 28 parts

Polymerizable compound (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure® OXE01; manufactured by BASF; O-acyl oxime compound) 5 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure® 907; manufactured by BASF; alkylphenone compound) 2 parts

Polymerization initiation aid (F1); 10 parts of 2,4-diethyl thioxanthone (KAYACURE® DETX; Nihon Kayaku Co., Ltd .; thioxanthone compound)

Leveling agent (G): 0.2 parts of polyether-modified silicone oil (Toray Silicon SH8400; Toray Dow Corning Co., Ltd. product)

Resin (C '): 99 parts of Resin C1 solution

Solvent (B '): 456 parts of propylene glycol monomethyl ether acetate

Solvent (B '): 186 parts of propylene glycol monomethyl ether

Pigment Composition 1 258 parts

However, the pigment composition 1 was prepared as follows.

(Preparation of Pigment Composition 1)

Pigment (A2); C.I. Pigment Blue 15: 6

Solvent (B "); propylene glycol monomethyl ether acetate 58.21 parts

Solvent (B "); propylene glycol monomethyl ether 5.76 parts

Resin (C "); Resin C2 (solid content conversion) 3.17 parts

Pigment dispersants (D '); 0.38 parts of copper phthalocyanine derivatives (solspars 5000; Lubrizol)

Pigment dispersants (D '); Acrylic dispersant (Disperbyk (registered trademark) 2000; manufactured by Beek Chemical Co., Ltd.) 3.26 parts

Was mixed and the pigment composition 1 was obtained by fully disperse | distributing a pigment using the bead mill.

Comparative Example 1

Pigment: C.I. Pigment Blue 15: 6

5 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 137 parts

Are mixed, the pigment is sufficiently dispersed using a bead mill, and then

Colorant: 3.5 parts of dye A1 (formula (A1-1) to formula (A1-8))

Resin: 157 parts of resin C3 solution

Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nihon Kayaku Co., Ltd.)

50 copies

Polymerization initiator: 15 parts of OXE-01 (manufactured by Chivas Specialty Chemicals)

Solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone

Was mixed to obtain a colored curable composition.

Comparative Example 2

Pigment: C.I. Pigment Blue Part 15: 6

Dye: Dye A1 (formula (A1-1)-formula (A1-8)) 1.8 parts

Dispersant 1: Acrylic dispersant (Disperbyk®-116; manufactured by Vikchemy; amine number 65 mgKOH / g) 18.1 parts

Dispersant 2: Copper phthalocyanine derivative (solspars 5000, product of Abyssia)

0.4 part

Solvent 1: Propylene glycol monomethyl ether acetate 47.9 parts

The components of were sequentially added to the beaker and all the components were mixed. Then, the dispersion process was performed for 5 hours with the paint shaker using the zirconia bead of 0.65 mm (phi). The obtained homogeneous dispersion was filtered to remove beads, thereby obtaining Pigment Composition 2.

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Pigment Composition 2 223 parts

Resin: 133 parts of Resin C3 solution

Polymerizable compound: (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); 15 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE01; manufactured by BASF; O-acyl oxime compound)

Leveling agent (G): 0.1 part of polyether modified silicone oil (Toray silicon SH8400; Toray Dow Corning Co., Ltd. product)

Solvent (B '): 425 parts of propylene glycol monomethyl ether acetate

Comparative Example 3

(Preparation of colorant dispersion 2)

Xanthene dyes (a1); 9.60 parts of compounds represented by formula (1-32)

Solvent (B); Propylene glycol monomethyl ether acetate 58.21 parts

Solvent (B); Propylene glycol monomethyl ether 5.76 parts

Resin (C); Resin C2 (solid content conversion) 3.17 parts

Dispersant (D); Acrylic dispersant (Disperbyk (R) -116; amine number 65 mgKOH / g, manufactured by Vikchem Co., Ltd.) 3.26 parts

And 360 parts of 0.2 mm diameter zirconia beads were thrown into the mayonnaise bottle of capacity 140 ml, it knead | mixed at 60 degreeC for 10 hours with the paint conditioner, and the dispersion process was carried out. Thereafter, zirconia beads were removed to obtain a dispersion. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 2 was obtained.

On the other hand, about the compound represented by Formula (1-32), the solubility in the propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether solvent (content ratio is 9/1 by mass basis) at 23 degreeC was 3%. .

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 2 28 parts

Polymerizable compound (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure® OXE01; manufactured by BASF; O-acyl oxime compound) 5 parts

Polymerization initiator (F); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure® 907; manufactured by BASF; alkylphenone compound) 2 parts

Polymerization initiation aid (F1); 10 parts of 2,4-diethyl thioxanthone (KAYACURE® DETX; Nihon Kayaku Co., Ltd .; thioxanthone compound)

Leveling agent (G): 0.2 parts of polyether-modified silicone oil (Toray Silicon SH8400; Toray Dow Corning Co., Ltd. product)

Resin (C '): 99 parts of Resin C1 solution

Solvent (B '): 456 parts of propylene glycol monomethyl ether acetate

Solvent (B '): 186 parts of propylene glycol monomethyl ether

Pigment Composition 1 258 parts

<Production of colored pattern>

After apply | coating a colored curable composition by the spin coat method on the square glass substrate (Eagle XG; Corning Corporation make) one side is 2 inches, it prebaked at 100 degreeC for 3 minutes, and obtained the coloring composition layer. After cooling, the interval between the colored composition layer on the substrate and the quartz glass photomask was set to 100 µm, and the exposure amount (365 mJ / cm 2) under an atmospheric atmosphere was performed using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) (365 nm reference). As a photomask, the thing in which the 100 micrometer line & space pattern was formed was used. The colored composition layer after exposure was immersed and developed for 25 seconds at 25 ° C. for 70 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate. After washing with water, it was post-baked at 230 ° C. for 20 minutes in an oven to color. A pattern was obtained.

<Measurement of film thickness>

The film thickness of the obtained coloring pattern was measured using the film thickness measuring apparatus (DEKTAK3; the Nihon Shinkugi Jutsu Co., Ltd. product). The results are shown in Table 1.

<Color evaluation>

About the obtained coloring pattern, spectroscopic measurement was carried out using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) in the XYZ colorimeter of the CIE using the characteristic function of the C light source. ) And the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

<Contrast Evaluation>

Except not using a photomask and developing, the same operation as formation of a coloring pattern was performed and the coloring coating film on a glass substrate was produced. About the obtained colored coating film, contrast was measured using the contrast system (CT-1; Tsubasaka Denki Co., Ltd., chromatic color difference meter BM-5A; Topcon Co., Ltd. light source; F-10) with a blank value of 30000. What sandwiched the colored coating film on a glass substrate with the polarizing film (POLAX-38S; Lukeo Co., Ltd.) was used as the measurement sample. The results are shown in Table 1. When the contrast of a colored coating film is high, it is a high contrast similarly also in the coloring pattern obtained using the same colored curable composition.

Example 2

A colored composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (1-32) is changed to the compound represented by the formula (1-24) (xanthene dye (a2)). A colored curable composition is obtained in the same manner as in Example 1 except using this coloring composition. In the same manner as in Example 1, a high-brightness color filter is obtained from the colored curable composition in the same manner as in Example 1.

Example 3

(Preparation of colorant dispersion 3)

Xanthene dyes (a3); 4.80 parts of the compound represented by formula (1-55)

Solvent (B); Propylene glycol monomethyl ether acetate 69.54 parts

Solvent (B); 4-hydroxy-4-methyl-2-pentanone 2.64 parts

Resin (C); Resin C2 (solid content conversion) 1.44 parts

Dispersant (D); Acrylic dispersant Disperbyk (registered trademark) 2000 (manufactured by Vikchem, Inc .; amine number 4 mgKOH / g) 1.58 parts

And 360 parts of 0.2 mm diameter zirconia beads were thrown into the mayonnaise bottle of capacity 140 ml, it knead | mixed at 60 degreeC for 10 hours with the paint conditioner, and the dispersion process was carried out. Thereafter, zirconia beads were removed to obtain a dispersion. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 3 was obtained.

On the other hand, with respect to the compound represented by the formula (1-55), the propylene glycol monomethyl ether acetate / 4-hydroxy-4-methyl-2-pentanone solvent at 23 ° C. (content ratio is 9 / by mass) The solubility in 1) was 1%.

Example 4

(Preparation of colorant dispersion 4)

Xanthene dyes (a3); 4.00 parts of the compound represented by formula (1-55)

Xanthene dyes (a4); 4.00 parts of the compound represented by formula (1-51)

Solvent (B); Propylene glycol monomethyl ether acetate 68.56 parts

Solvent (B); 4-hydroxy-4-methyl-2-pentanone2.40

Resin (C); Resin C2 (solid content conversion) 2.40 parts

Dispersant (D); Acrylic dispersant Disperbyk (registered trademark) 2000 (manufactured by Vikchem, Inc .; amine number 4 mgKOH / g) 1.58 parts

And 360 parts of 0.2 mm diameter zirconia beads were thrown into the mayonnaise bottle of capacity 140 ml, it knead | mixed at 60 degreeC for 10 hours with the paint conditioner, and the dispersion process was carried out. Thereafter, zirconia beads were removed to obtain a dispersion. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 4 was obtained.

Example 5

(Preparation of colorant dispersion 5)

Xanthene dyes (a4); 8.00 parts of compounds represented by formula (1-51)

Solvent (B); Propylene glycol monomethyl ether acetate 62.55 parts

Solvent (B); Propylene glycol monomethyl ether 4.41 parts

Resin (C); Resin C2 (solid content conversion) 2.40 parts

Dispersant (D); Acrylic dispersant Disperbyk (registered trademark) 2000 (manufactured by Vikchem, Inc .; amine number 4 mgKOH / g) 2.64 parts

And 360 parts of 0.2 mm diameter zirconia beads were thrown into the mayonnaise bottle of capacity 140 ml, it knead | mixed at 60 degreeC for 10 hours with the paint conditioner, and the dispersion process was carried out. Thereafter, zirconia beads were removed to obtain a dispersion. This dispersion liquid was filtered with the membrane filter of 1.0 micrometer of pore diameters, and the coloring agent dispersion liquid 5 was obtained.

On the other hand, regarding the compound represented by Formula (1-51), the solubility in the propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether solvent (content ratio is 9/1 by mass basis) at 23 degreeC was 1.5%. .

Example 6

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Colorant Dispersion 397 parts

Polymerizable compound (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE01; manufactured by BASF; O-acyl oxime compound) 13 parts

Leveling agent (G): 0.1 part of polyether modified silicone oil (Toray silicon SH8400; Toray Dow Corning Co., Ltd. product)

Resin (C '): 50 parts of Resin C4 solution

Solvent (B '): 622 parts of propylene glycol monomethyl ether acetate

Solvent (B '): 22 parts of 4-hydroxy-4-methyl-2-pentanone

Pigment Composition 3 479 parts

Example 7

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Colorant dispersion 4 57 parts

Polymerizable compound (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE01; manufactured by BASF; O-acyl oxime compound) 13 parts

Leveling agent (G): 0.1 part of polyether modified silicone oil (Toray silicon SH8400; Toray Dow Corning Co., Ltd. product)

Resin (C '): 50 parts of Resin C4 solution

Solvent (B '): 438 parts of propylene glycol monomethyl ether acetate

Solvent (B '): 246 parts of propylene glycol monomethyl ether

Pigment Composition 3 483 parts

Example 8

(Preparation of a colored curable composition)

The following components were mixed and the colored curable composition was obtained.

Colorant Dispersion 5 75 parts

Polymerizable compound (E): 50 parts of dipentaerythritol hexaacrylate ((KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (F); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE01; manufactured by BASF; O-acyl oxime compound) 13 parts

Leveling agent (G): 0.1 part of polyether modified silicone oil (Toray silicon SH8400; Toray Dow Corning Co., Ltd. product)

Resin (C '): 50 parts of Resin C4 solution

Solvent (B '): 456 parts of propylene glycol monomethyl ether acetate

Solvent (B '): 226 parts of propylene glycol monomethyl ether

Pigment Composition 3 482 parts

However, Pigment Composition 3 was prepared as follows.

(Preparation of Pigment Composition 3)

Pigment (A2): C.I. Pigment Red 254 Part 8.86

Solvent (B "): 58.24 parts of propylene glycol monomethyl ether acetates

Solvent (B "): 5.76 parts of propylene glycol monomethyl ethers

Resin (C "): 3.30 parts of Resin (C2) (solid content conversion)

Pigment Dispersant (D '): 3.84 parts of Acrylic Dispersant

Was mixed and the pigment composition 3 was obtained by fully disperse | distributing a pigment using the bead mill.

About the colored curable composition obtained in Examples 6-8, colored pattern preparation, film thickness measurement, chromaticity evaluation, and contrast evaluation were performed similarly to the colored curable composition of Example 1 and Comparative Examples 1-3. The results are shown in Table 2.

Although dye A1 (formula (A1-1)-(A1-8)) and the pigment composition 3 were mixed as the comparative example 4, it was not a comparable chromaticity and it was impossible to color.

The colored curable composition which can form a high brightness color filter from the coloring agent dispersion liquid of this invention can be obtained.

Claims (8)

As a coloring agent dispersion liquid in which a coloring agent is disperse | distributed in a solvent with a dispersing agent,
The colorant comprises a xanthene dye represented by the following formula (1a) and does not substantially contain a pigment,
Content of xanthene dye is 40 mass% or more and 100 mass% or less with respect to the total amount of a coloring agent,
Colorant dispersions in which the dispersant has an amine group and the amine number of the dispersant is 0-55 mgKOH / g:

[In formula (1a), R <^1> -R <^4> may independently independently represent a hydrogen atom and a C1-C20 monovalent saturated hydrocarbon group which may have a substituent, or a C6-C10 monovalent aromatic hydrocarbon group which may have a substituent. And -CH ₂ -contained in this saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^11- . R ¹ and R ² may be bonded to form a ring with an adjacent nitrogen atom, or R ³ and R ⁴ may be bonded to form a ring with an adjacent nitrogen atom.
R ⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is shown.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents the integer of 0-5. When m is two or more, some R <^5> may be same or different.
a represents the integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, The hydrogen atom contained in this saturated hydrocarbon group may be substituted by the halogen atom.
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and -CH ₂ -contained in this saturated aliphatic hydrocarbon group is -O-, -CO-,- It may be substituted by NH- or -NR ^8-, or R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle together with an adjacent nitrogen atom.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] The colorant dispersion according to claim 1, wherein the amine number of the dispersant is 2 to 40 mgKOH / g. The colorant dispersion liquid according to claim 1 or 2, wherein the solvent contains propylene glycol monomethyl ether acetate, and the content of propylene glycol monomethyl ether acetate is 40% by mass to 99% by mass with respect to the total amount of the solvent. The colorant dispersion according to claim 1 or 2, further comprising a resin. The colored curable composition containing the coloring agent dispersion liquid of Claim 1 or 2, a polymeric compound, and a polymerization initiator. The method of claim 5, further comprising a pigment composition prepared separately from the colorant dispersion,
The colored curable composition in which a pigment composition contains at least 1 sort (s) chosen from the group which consists of a pigment, a solvent, a pigment dispersing agent, and resin. The color filter formed with the colored curable composition of Claim 5. A display device comprising the color filter according to claim 7.