KR102105622B1 - Colored composition - Google Patents

Abstract

[식에서, R^a1, R^a2, R^a3 및 R^a4는 서로 독립적으로 수소 원자, 브롬 원자 또는 1가의 치환기를 나타내고, 1개 이상은 브롬 원자를 나타냄]
로 나타내는 화합물을 포함하는 착색 조성물을 제공한다. The present invention includes a pigment and a resin, and the pigment is represented by the formula (P)

[Wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 independently of each other represent a hydrogen atom, a bromine atom or a monovalent substituent, and one or more represent a bromine atom]
It provides a coloring composition containing the compound represented by.

Description

Coloring composition {COLORED COMPOSITION}

The present invention relates to a coloring composition.

The coloring composition is used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels. As a red pigment used for such a coloring composition, C.I. which is a diketopyrrolopyrrole pigment. Pigment Red 254 (pigment containing a compound represented by the following formula) is widely known ["Latest Technology Trends in Color Filters-Constituent Materials, Structure, Evaluation and Overseas Trends-" p.25, 26 (by Kutata Taisei et al .; Information Agency (issued May 31, 2005)]

In order to achieve high contrast of the color filter, it is desired to develop a new colored photosensitive composition.

The present invention includes the following.

[1] It contains a pigment and a resin, and the pigment is a formula (P)

[Wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 independently of each other represent a hydrogen atom, a bromine atom or a monovalent substituent, and one or more represent a bromine atom]

Coloring composition containing the compound represented by.

[2] The colored composition according to [1], further comprising a dye.

[3] The colored composition according to [2], wherein the dye is a xanthene dye, an azo dye, or a metal complex dye.

[4] A color filter formed of the colored composition according to any one of [1] to [3].

[5] A display device comprising the color filter according to [4].

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring composition which can manufacture a high contrast color filter.

The coloring composition of the present invention contains a pigment (A1) and a resin (VIII).

Pigment (A1) contains the compound represented by Formula (P).

[Wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 independently of each other represent a hydrogen atom, a bromine atom or a monovalent substituent, and one or more represent a bromine atom]

^Examples of monovalent substituents on R ^a1 , R ^a2 , R ^a3 and R ^a4 are halogen atoms (except bromine atoms), cyno groups, -CF ₃ , -R ^a5 , -OR ^a5 , -SR ^a5 , -SOR ^a5 , -SO ₂ R ^a5 , -NR ^a6 COR ^a5 , -CONR ^a5 R ^a6 , -CONH ₂ .

R ^a5 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a naphthyl group, and -CH ₂ -contained in the alkyl group is substituted with -NR ^a7- , -O-, -S-, -SO- or -SO _2- It may be.

R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and -CH ₂ -contained in the alkyl group is substituted with -NR ^a7- , -O-, -S-, -SO- or -SO _2- do.

R ^a5 and R ^a6 may combine to form an alkanediyl group having 2 to 8 carbon atoms, and -CH ₂ -contained in the alkanediyl group is -NR ^a7- , -O-, -S-, -SO- Alternatively, it may be substituted with -SO _2- .

R ^a7 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, isobutyl group, sec-butyl group, and isopentyl group.

Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, and pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned.

Examples of the halogen atom (except for the bromine atom) include a fluorine atom, a chlorine atom, and an iodine atom, and preferably a chlorine atom.

Examples of -OR ^a5 include methoxy group, ethoxy group, propoxy group, butoxy, and pentyloxy group.

Examples of -SR ^a5 include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, and pentylsulfanyl group.

Examples of -SOR ^a5 include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, butylsulfinyl group, and pentylsulfinyl group.

Examples of -SO ₂ R ^a5 include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, and pentylsulfonyl group.

Examples of -NR ^a6 COR ^a5 include N-acetylamino group, N-propionylamino group, N-benzoylamino group, and N-methyl-N-acetylamino group.

Among -NR ^a6 COR ^a5 , examples of the group in which R ^a5 and R ^a6 form a ring include groups represented by the following formula.

Examples of -CONR ^a5 R ^a6 include N-methylaminocarbonyl group, N, N-dimethylaminocarbonyl group, and N, N-ethylmethylaminocarbonyl group.

Among the -CONR ^a5 R ^a6 , examples of the group in which R ^a5 and R ^a6 form a ring include groups represented by the following formula.

At least one of R ^a1 , R ^a2 , R ^a3 and R ^a4 is a bromine atom, preferably at least one of R ^a1 and R ^a2 is a bromine atom, R ^a1 is a bromine atom, and R ^a2 is a bromine atom Or it is preferable that it is a chlorine atom.

It is preferable that R ^a3 and R ^a4 are hydrogen atoms together.

As a compound represented by Formula (P), the compound represented by the following formula is mentioned, for example.

The pigment (A1) may be a pigment containing only the compound represented by the formula (P), or a pigment formed with a solid solution together with other pigments and these derivatives if necessary.

In the pigment (A1), the content of the compound represented by the formula (P) is preferably 1 to 100% by mass, more preferably 20 to 100% by mass.

Pigment (A1) is subjected to rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced, if necessary, grafting treatment to a pigment surface using a polymer compound, atomization treatment using a sulfuric acid atomization method, or removing impurities Washing treatment with an organic solvent, water, or the like, and removal treatment by an ion exchange method of ionic impurities may be performed. Moreover, it is preferable that the pigment (A1) has a uniform particle diameter.

The pigment (A1) can be formed into a pigment dispersion liquid in a form uniformly dispersed in a pigment dispersant solution by subjecting the pigment dispersant to a dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, trade names are KP (made by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperth (manufactured by Geneca Corporation), EFKA (manufactured by CIBA), Azisper [Ajinomoto Fine] Techno Co., Ltd.], Disperbyk (made by BIC Chemise), etc. are mentioned.

When a pigment dispersant is used, the amount of its use is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment (A1). When the amount of the pigment dispersant used is in the above range, there is a light weight in which a pigment dispersion liquid in a uniform dispersion state is obtained.

The coloring composition of the present invention may further contain pigments other than pigment (A1) (hereinafter referred to as "pigment (A2)").

Specific examples of the pigment (A2) include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists). Specifically, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 12, 128, 137, 138, 139 , Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Pigments such as Pigment Orange 13, 31, 34, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

C.I. Blue pigments such as 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, 38;

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

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

C.I. And black pigments such as Pigment Black 1 and 7.

Among these, yellow pigments, orange pigments, red pigments and violet pigments are preferred, yellow pigments, orange pigments and red pigments are more preferred, and C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Orange 38, 71 and C.I. Pigment Red 177, 242, and 254 are even more preferred. These pigments may be used alone or in combination of two or more.

It is preferable that the pigment (A2) is subjected to the dispersion treatment described above in the same manner as the pigment (A1).

The coloring composition of the present invention may further contain a dye (A3) together with a pigment (A1). The dye (A3) is not particularly limited, and a known dye can be used. For example, fat-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. It is preferable that the dye (A3) is an organic solvent-soluble dye.

As the dye (A3), for example, a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (Shikisensha).

Specifically, C.I. Solvent yellow 4 (hereinafter, C.I. solvent yellow is omitted and only numbers are described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 162;

C.I. Solvent red 45, 49, 125, 130;

C.I. Solvent orange 2, 7, 11, 15, 26, 56;

C.I. Solvent blue 35, 37, 59, 67;

C.I. And solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and the like.

In addition, C.I. As an acid dye, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

C.I. Acid violet 6B, 7, 9, 17, 19;

C.I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

In addition, C.I. As a direct dye, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C.I. Direct Red 79, 92, 93, 94, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 167, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. And dyes such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, and 82.

Moreover, C.I. As a modern dye, C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. And dyes such as modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

Further, as the dye (A3), azo dyes, metal complex dyes, anthraquinone salts, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes , Acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye and phthalocyanine dye, and azo dyes, metal complex dyes and xanthene dyes are preferred.

Among these, xanthene dye (A3a), metal complex dye (A3 '), metal complex dye (A3c) and metal complex dye (A3d) are preferable as the dye (A3).

The xanthene dye (A3a) is a dye containing a compound having a xanthene skeleton in a molecule. As the xanthene dye (A3a), for example, C.I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 8, C.I. Basic Red 10 (Rhodamine B), C.I. Solvent Red 218, C.I. Modern Red 27, C.I. And reactive red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in Japanese Patent Application Publication No. 2010-32999, and xanthene dyes described in Patent No. 4242760.

Among these, as the xanthene dye (A3a), a dye containing a compound represented by formula (1) (hereinafter referred to as "compound (1)") is preferable. When the compound (1) is used, the content of the compound (1) in the xanthene dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. In particular, it is preferable to use only compound (1) as xanthene dye (A3a).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

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 .

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 an integer of 2 or more, a plurality of R ^5s are the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may combine with each other to form a heterocyclic ring of 3 to 10 atom rings containing nitrogen atoms. .

R ¹¹ each independently 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]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ to R ⁴ include, for example, a phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group.

R ¹ groups are 6 to 10 carbon atoms indicated by 1 ~R ⁴ aromatic hydrocarbon, a hydrogen atom is a halogen atom which comprises the aromatic hydrocarbon ^{groups, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, It may be substituted with -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these substituent _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and -SO ₂ NR ⁹ R at least one member selected from the group consisting of ¹⁰ is preferred, and -SO ₃ ^- Z ⁺ and -SO ₂ or more selected from the group consisting of NR ⁹ R ¹⁰ is more preferred. Examples of Z ⁺ -SO ₃ ^{- -} -SO ₃ in this case is N ⁺ (R ¹¹⁾ ₄ are preferred. When R ¹ to R ⁴ are such groups, the colored composition containing the compound (1) is less likely to generate foreign matter and can form a color filter excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ to R ¹¹ are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and hexa Straight-chain alkyl groups such as a decyl group and an iconic group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; And cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

In addition, the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may have a hydrogen atom contained in the saturated hydrocarbon group substituted with -OH or a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is -O It may be substituted with-, -CO-, -NH- or -NR ^8- .

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the alkyl groups mentioned above.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by 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 .

As the ⁺ N (R ¹¹ ) _4, 4 R ¹¹ Among them, it is preferable that two or more are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total number of carbon atoms of the four R ¹¹ is more preferably dogs 20 to 80 are preferred, and 20 to 60. When R ¹¹ is such a group, the colored composition containing the compound (1) can form a color filter with few foreign substances.

m is preferably 1 to 4, and 1 or 2 is more preferable.

As the xanthene dye (A3a), a dye containing a compound represented by formula (2) (hereinafter referred to as "compound (2)") is more preferable. When the compound (2) is used, the content of the compound (2) in the xanthene dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more. In particular, it is preferable to use only compound (2) as xanthene dye (A3a).

[In formula (2), R ²¹ -R ²⁴ each independently represents a hydrogen atom, -R ^26, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ²⁵ is -SO ₃ ^- shows the Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

m1 represents the integer of 0-5. When m1 is an integer of 2 or more, a plurality of R ^{25 s} are the same or different.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

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

R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group]

As the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ²¹ to R ²⁴ , the same groups as those described above as the aromatic hydrocarbon group with R ¹ to R ⁴ can be exemplified. Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- or may be 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 and R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ has 6 to 10 carbon atoms and of 1-valent aromatic hydrocarbon group, hydrogen atom is contained the aromatic hydrocarbon groups -SO ₃ ^{-, -} It is preferable to be substituted with SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . An even more preferred 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 valence contained in the aromatic hydrocarbon group is -SO ₃ ^- Z1 ⁺ or -SO ₂ It is substituted with NHR ²⁶ . When R ²¹ to R ²⁴ are such groups, the colored composition containing the compound (2) can form a color filter excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁶ and R ²⁷ include the same groups as those described as saturated hydrocarbon groups with R ⁸ to R ¹¹ .

In R ²¹ to R ²⁴ , -R ²⁶ is preferably each independently a hydrogen atom, a methyl group, or an ethyl group. Further, in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ , R ²⁶ is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and a 2-ethylhexyl group is even more. desirable. When R ²⁶ is such a group, the coloring composition containing the compound (2) can form a color filter with less foreign matter.

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

To the ⁺ N (R ²⁷⁾ ₄ as the 4 R ²⁷ from, two or more carbon atoms of 5-20 monovalent saturated hydrocarbon group is preferred. Further, the total carbon number of R 4 is ²⁷ and 20 to 80 dogs preferred, more preferred 20 to 60 dogs. The coloring composition containing the compound (2) in which R ²⁷ is such a group can form a color filter with less occurrence of foreign matter.

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

As a compound (2), the compound represented by Formula (1-1)-Formula (1-22) is mentioned, for example. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and even more preferably a 2-ethylhexyl group. Among these, sulfonamides of CI acid red 289, quaternary ammonium salts of CI acid red 289, sulfonamides of CI acid violet 102 or quaternary ammonium salts of CI acid violet 102 are preferred. Examples of such a compound include compounds represented by formulas (1-1) to (1-1), formulas (1-111), and formulas (1-12).

Xanthene dyes (A3a) are commercially available xanthene dyes (e.g., `` Chugai Aminol Fast Pink RH / C '' manufactured by Tsugaikasei Co., Ltd., `` Rhodamin 6G '' manufactured by Taoka Chemical Industries, Ltd.) Can be used. In addition, commercially available xanthene dyes can be synthesized as a starting material, with reference to JP 2010-32999 A.

The metal complex dye (A3 ′) is a dye molecule comprising a group obtained by complexing with a metal atom in the molecule, and a dye complexed with a metal atom.

As said metal complex dye (A3 '), it is C.I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243, CI Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61, C.I. Solvent Blue 137, C.I. Solvent Brown 28, 42, 43, 44, 53, 62, 63, C.I. Acid Yellow 59, 121, C.I. Acid Orange 74, 162, C.I. And metal complex dyes described in Acid Red 211, Publication No. 2010-170117 and Publication No. 2011-59673. These metal complex dyes (A3 ') may be used alone or in combination of two or more.

Examples of the dye molecule (coordinator) include azo dyes, methine dyes, and azo dyes are preferred.

Examples of the metal atom include chromium, cobalt, and nickel, and chromium and cobalt are preferable.

Examples of the metal complex salt dye (A3 ′) include a 1: 1 metal complex salt dye having a metal atom to dye molecule bond ratio of 1: 1, and a 1: 2 metal complex salt dye with a ratio of 1: 2, and 1: 2. Type metal complex dyes are preferred.

The metal complex salt dye (A3 ′) is preferably a compound represented by formula (3) or a compound represented by formula (4).

[In the formula (3), R ³¹ to R ⁴⁸ are each independently a hydrogen atom, a halogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ⁵¹ , -SO ₃ ^- ,- COOR ⁵¹ or -SO ₂ R ⁵¹ .

R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.

R ⁵¹ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and -CH ₂ -contained in the hydrocarbon group may be substituted with -O- or -CO-.

A ^{1 to} A ⁴ each independently represent * -O-, * -O-CO-, and * -CO-O-.

* Indicates a binding hand with M.

M represents Cr or Co.

n represents the integer of 2-5.

D ⁺ represents a hydride, a monovalent metal cation, or a monovalent cation derived from a compound having a xanthene skeleton]

[In the formula (4), R ⁵² to R ⁶⁰ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ NHR ⁶² , -SO ₃ H or -SO ₂ CH ₃ Shows.

R ⁶¹ each independently represents a hydrogen atom, a methyl group or an ethyl group.

R ⁶² each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.

A ⁵ and A ⁶ each independently represent * -O-, * -O-CO-, * -CO-O-. * Indicates a binding hand with M1.

M1 represents Cr or Co.

n1 represents the integer of 0-2.

D1 ⁺ represents a hydride, a monovalent metal cation, or a monovalent cation derived from a compound having a xanthene skeleton]

Examples of monovalent saturated hydrocarbon groups having 1 to 8 carbon atoms represented by R ³¹ to R ⁴⁸ , R ⁵² to R ⁶⁰ and R ⁶² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups Straight-chain alkyl group; Isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2 And branched chain alkyl groups such as -ethylhexyl group and 1,1,5,5-tetramethylhexyl group.

Among R ³¹ to R ⁴⁸ , it is preferable that at least one is a nitro group. It is preferable that at least one of R ⁵² to R ⁶⁰ is a nitro group. Since it has a nitro group, it is preferable because the spectral concentration of the compound tends to increase.

R ⁴⁹ and R ⁵⁰ are preferably a methyl group.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ⁵¹ are monovalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 10 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and combinations thereof. And a group having 4 to 10 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; And branched chain alkyleries such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. A phenyl group, a naphthyl group, etc. are mentioned as a C6-C10 monovalent aromatic hydrocarbon group. Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the hydrocarbon group in which -CH ₂ -is substituted with -O- or -CO- include -R ⁷¹ -OR ⁷² , -R ⁷¹ -CO-OR ⁷² , and -R ⁷¹ -O-CO-R ⁷² . . R ⁷¹ is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ⁷² is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ⁷¹ are ethylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane- And 1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, and the like.

As -R ⁷¹ -OR ⁷² , methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo- 4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group, etc. are mentioned.

Examples of -R ⁷¹ -CO-OR ⁷² include methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group And a butoxycarbonylethyl group.

Examples of -R ⁷¹ -O-CO-R ⁷² include acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxyethyl group, butylcarbonyloxymethyl group, and butyl And carbonyloxyethyl groups.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ⁶² are methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1 -Ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopro And a foxxy-1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, and 3- (2-ethylhexyloxy) propyl group.

Examples of the monovalent metal cations represented by D ⁺ and D 1 ⁺ include lithium cations, sodium cations, and potassium cations. As the monovalent cation derived from a compound having a xanthene skeleton represented by D ^+, D1 ⁺ may be a cation represented by the formula (5). Since the brightness of the color filter formed from the coloring composition can be improved, monovalent cations derived from a compound having a xanthene skeleton are preferable as D ⁺ and D 1 ⁺ .

[In the formula (5), R ⁶³ to R ⁶⁷ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms]

Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶³ to R ⁶⁷ include those having 1 to 6 carbon atoms among those mentioned above as saturated hydrocarbon groups represented by R ³¹ to R ⁴⁸ .

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ⁶³ to R ⁶⁷ include, for example, a phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group.

As R ⁶³ to R ^67, each independently a hydrogen atom and an ethyl group are preferable.

As said metal complex dye (A3 '), the compound represented by Formula (6) is more preferable.

In the formula (6), R ^a41 ~R ^a58 are each independently a hydrogen atom, a halogen atom, having 1 to 8 carbon atoms of a monovalent aliphatic hydrocarbon group, a nitro group, a sulfo group, -SO ₂ R ⁷² or -SO ₂ NHR ^a34 Indicates.

R ^a34 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ⁷¹ -OR ⁷² , -R ⁷¹ -CO-OR ⁷² , -R ⁷¹ -O-CO-R ⁷² or an aralkyl group having 7 to 10 carbon atoms.

R ⁷¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ⁷² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a59 and R ^a60 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.

M ² represents Cr or Co.

R ^a21 to R ^a24 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are The hydroxyl group, -OR ⁷² , sulfo group, -SO ₃ Na, -SO ₃ K, or a halogen atom may be substituted.

R ^a25 and R ^a26 each independently represent a hydrogen atom or a methyl group.

R ^a27 represents an ethylene group, propane-1,3- ^diyl group or propane 1,2- ^diyl group.

R ^a28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents the integer of 1-4. When n is 2 or more, a plurality of R ^a27 may be the same or different from each other]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those for R ³¹ to R ⁴⁸ described above.

R ⁷¹ and R ⁷² have the same meaning as above.

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.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group and naphthyl group; And aralkyl groups such as benzyl group, diphenylmethyl group, phenylethyl group and 3-phenylpropyl group.

As a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-butylcyclohexyl group , 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group, and the like.

Tends high heat resistance, in ^a41 R ^a58 ~R, it is preferred that at least one nitro group.

In addition, R ^a41 ~R least one of 1 or more and R ^a46 ~R ^{a50 a45} of a sulfo group, -SO ₂ NHR ^a34 or -SO ₂ R ⁷² is preferably, and -SO ₂ R ⁷² is more preferably And -SO ₂ CH ₃ is even more preferable.

Since the color density is high, R ^a21 to R ^a24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group.

As R ^{a27, an} ethylene group and a propane-1,2- ^diyl group are preferable, and an ethylene group is more preferable.

As R ^{a28, a} hydrogen atom is preferable.

n is an integer of 1-4, an integer of 2-4 is preferable, 3 or 4 is more preferable, and 3 is still more preferable.

-(R ^a27 -O) _n -R ^a28 is a 2- (2-hydroxyethoxy) ethyl group and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group from the viewpoint of solubility in an organic solvent. It is preferable, and a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group is more preferable.

Examples of the metal complex dye (A3ｂ) include compounds represented by formulas (A3ｂ-1) to (A3ｂ-7). The compounds represented by formulas (A3ｂ-1) to (A3ｂ-5) correspond to compounds represented by formula (3), and the compounds represented by formula (A3ｂ-6) correspond to compounds represented by formula (4), The compound represented by formula (A3ｂ-7) corresponds to the compound represented by formula (6).

The content of the pigment (A1) is preferably 1% by mass or more and 100% by mass or less with respect to the total amount of the pigment (A1), the pigment (A2), and the dye (A3).

The total amount of the pigment (A1), the pigment (A2), and the dye (A3) is preferably 10 to 60% by mass, more preferably 20 to 45% by mass, based on the solid content of the colored composition. Here, solid content means the amount which excludes the solvent (E) from a coloring composition. The solid content can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

The said azo dye (A3c) is a dye of the structure represented by Formula (A3c-I).

In the formula (A3c-I), R ¹ to R ⁴ each independently represent a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group, or a carboxyl group.

R ⁵ to R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or It represents an N-substituted sulfamoyl group.

R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group]

Moreover, it is the said coloring photosensitive resin composition in which 1 or more of R <^5> -R <^12> is an N-substituted sulfamoyl group.

Further, the present invention is the colored photosensitive resin composition wherein at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² is an N-substituted sulfamoyl group.

Further, the present invention is the colored photosensitive resin composition wherein at least one of R ⁶ and R ⁷ and at least one of R ¹⁰ and R ¹¹ are N-substituted sulfamoyl groups.

In addition, the present invention is the N- substituted sulfamoyl group and a -SO ₃ NHR ¹⁵ group, R ¹⁵ is C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy C _{1 -10} saturated aliphatic hydrocarbon group which is substituted group, C _1-8 alkoxyl group, C _{6 -20} aryl groups, C _{7 -20} aralkyl group or C _{2 -10} represents an acyl group, the colored photosensitive resin composition is.

In addition, the present invention R ¹³ and R represents at least one of the ¹⁴ -CON (R ¹⁶⁾ R ¹⁷ group, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 - 8} is an alkoxy group which is substituted with a C _{1 -10} aliphatic saturated hydrocarbon group, C _{6 -20} aryl groups, C _{7 -20} aralkyl group or C _{2 -10} the colored photosensitive resin composition exhibiting an acyl group.

Preferred examples of the formula (A3c-I) include formulas (A3c-I-1) to formulas (A3c-I-10).

Moreover, as a preferable example of Formula (A3c-I), as represented by Formula (A3c-II), 1 or more of R ⁵ -R ⁸ and 1 or more of R ⁹ -R ¹² are -SO ₂ NHR ¹⁵ groups Also included are compounds in which the remaining six are hydrogen atoms.

Preferred examples of the formula (A3c-II) are formulas (A3c-II-1) to formulas (A3c-II-VII).

The compound R ⁵ ~R ¹² As the salt of (A3c-I) is a sulfonic acid salt in the case of a sulfo group, R ⁵ ~R ¹² can include a carboxylic acid salt in the case of the carboxyl group. In addition, although the cation forming the salt is not particularly limited, considering solubility in a solvent, alkali metal salts such as lithium salt, sodium salt and potassium salt; Ammonium salt; And organic amine salts such as ethanolamine salts and alkylamine salts. In particular, alkali metal salts (preferably sodium salts) are useful when incorporated in a polarizing film substrate. In addition, the organic amine salt is used when it is contained in a resin curable compound, and since it is a non-metal salt, it is also useful in fields where insulation is important.

The azo dye (A3d) is a dye having the structure represented by formula (A3d-I).

[In formula (A3d-I), Z represents an oxygen atom or a sulfur atom.

R ¹ ~R ⁴ is C ₁ which are each independently hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon group, a hydroxyl group, a C _{1 -10} aliphatic saturated hydrocarbon group, a C _{1 -8} alkoxy group which is substituted is substituted with _{- 10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy group is thio C _{1 -10} saturated aliphatic hydrocarbon group which is substituted, C _{6 -20} aryl groups, C _{7 -20} represents an aralkyl group, or a C _{2 -10} acyl.

R ⁵ ~R ¹² each independently represent a hydrogen atom, a halogen atom, a C _{1 -10} aliphatic saturated hydrocarbon group, a halogenated C _{1 -10} saturated aliphatic hydrocarbon group, a C _{1 -8} alkoxy group, a carboxyl group, a sulfo group, a sulfamoyl group or Represents an N-substituted sulfamoyl group]

Moreover, this invention is the said coloring photosensitive resin composition in which 1 or more of R <^5> -R <^12> is an N-substituted sulfamoyl group.

Moreover, this invention is the said coloring photosensitive resin composition in which 1 or more of R <^5> -R <^8> and 1 or more of R <^9> -R <^12> are N-substituted sulfamoyl groups.

In addition, the present invention is the colored photosensitive resin composition wherein at least one of R ⁵ and R ⁸ and at least one of R ⁹ and R ¹² are N-substituted sulfamoyl groups.

In addition, the present invention is the N- substituted sulfamoyl and a group -SO ₂ NHR ¹³ group, R ¹³ is C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy C _{1 -10} saturated aliphatic hydrocarbon group which is substituted group, C _6-20 aryl group, C _{7 -20} is an aralkyl group, or a C _{2 -10} the colored photosensitive resin composition exhibiting an acyl group.

As the compound (A3d-I), one type may be used alone, or two or more types may be used in combination.

When two or more of the compounds (A3d-I) are used in combination, the amount of dissolution in an organic solvent (fat-soluble) is greater than when one of these compounds is used alone. For this reason, it is also preferable to use a combination of two or more of compounds (A3d-I) as a dye for the liquid crystal display device from the viewpoint of oil solubility. As an example of a combination in which the usability is improved, a compound having two N-substituted sulfamoyl groups (A3d-I) [disulfonamide], a compound having one N-substituted sulfamoyl group and one sulfo group (A3d-) I) combination with [monosulfonamide]. Among these combinations, one of R ⁵ to R ⁸ and one of R ⁹ to R ¹² are N-substituted sulfamoyl groups, and the remainder is hydrogen atom disulfonamide and one of R ⁵ to R ^{8 is} N-substituted alcohol It is a pamoyl group, and one of R ⁹ to R ¹² is a sulfo group, and the rest is preferably combined with a monosulfonamide which is a hydrogen atom.

Among the compounds (A3d-I) having an N-substituted sulfamoyl group, at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² are -SO ₂ , as represented by formula (A3d-II). Preferred are NHR ¹³ groups, the rest being hydrogen atoms.

Preferred examples of the formula (A3d-I) include formulas (A3d-I-1) to formulas (A3d-I-13).

Preferred examples of the formula (A3d-II) are formulas (A3d-II-1) to formulas (A3d-II-7).

The compound R ⁵ ~R ¹² As the salt of (A3d-I) is a sulfonic acid salt in the case of a sulfo group, R ⁵ ~R ¹² can include a carboxylic acid salt in the case of the carboxyl group. In addition, the cation forming the salt is not particularly limited, but considering the solubility in a solvent, alkali metal salts such as lithium salt, sodium salt and potassium salt; Ammonium salt; And organic amine salts such as ethanolamine salts and alkylamine salts. In particular, alkali metal salts (preferably sodium salts) are useful when contained in a polarizing film substrate. In addition, the organic amine salt is useful when it is contained in a resin curable compound, and since it is a non-metal salt even more, it is also useful in fields where insulation is important.

The coloring composition of this invention contains resin. Although it does not specifically limit as resin (i), It is preferable that it is alkali-soluble resin. Examples of the resins include the following resins [# 1] to [# 6].

Resin [Ｋ1] At least one member selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms and ethylenically unsaturated bonds A copolymer with a monomer (i) having hereinafter (hereinafter referred to as "(i)").

Resin [X2] copolymerization of (a) and (i) with a monomer (c) copolymerizable with (a) (but different from (a) and (i)) (hereinafter referred to as "(c)") coalescence.

Resin [X3] Copolymer of (a) and (c).

Resin [X4] A resin obtained by reacting (VIII) with a copolymer of (A) and (C).

Resin [X5] A resin obtained by reacting (a) with a copolymer of (i) and (c).

Resin [X6] A resin obtained by reacting (a) with a copolymer of (i) and (c) and further reacting carboxylic anhydride.

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

Maleic acid, phthalic acid, citraconic acid, metaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing carboxyl groups such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-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] hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono-((meth) acryloyloxyalkyl) of polyvalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(i) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, one or more selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolan ring)) and Refers to a polymerizable compound having an ethylenically unsaturated bond. (iii) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In addition, in this specification, notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (iii), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(ｂ1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as "(2)", "(Ｂ2)", and a monomer (ｂ3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(ｂ3)").

(ｂ1) is, for example, a monomer having a structure in which an unsaturated aliphatic hydrocarbon group is ethoxylated (ｂ1-1) (hereinafter referred to as "(ｂ1-1)"), a monomer having a structure in which an unsaturated alicyclic hydrocarbon is ethoxylated (ｂ１-2) (hereinafter referred to as “(ｂ１-2)”).

(ｂ1-1) As glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycol Cydyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α -Methyl-p-vinylbenzylglycidyl 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. You can.

Examples of (# 1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [eg, ceroxide 2000; Daicel Chemical Industries Co., Ltd., 3,4-epoxycyclohexylmethyl (meth) acrylate [For example, cyclomer A400; Daicel Chemical Industries Co., Ltd., 3,4-epoxycyclohexylmethyl (meth) acrylate [For example, cyclomer M100; Daicel Chemical Industry Co., Ltd.], 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 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ¹ and X ² independently of each other represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S-, * -R ^c -NH-.

R ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents a bonding hand 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.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy are a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

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

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- group (* represents a bond with O), a * -CH ₂ CH ₂ -O- group, More preferably, a * -CH ₂ CH ₂ -O- group is mentioned.

Examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to (I-15). Preferably, formulas (I-1), formulas (I-3), formulas (I-5), formulas (I-7), formulas (I-９), formulas (I-11) to (I-15) ). More preferably, formulas (I-1), formulas (I-7), formulas (I-X) and formulas (I-15) are exemplified.

Examples of the compound represented by formula (II) include compounds represented by formulas (II-1) to (II-15). Preferably, formulas (II-1), formulas (II-3), formulas (II-5), formulas (II-7), formulas (II-９), formulas (II-11) to (II-15) ). More preferably, a formula (II-1), a formula (II-7), a formula (II-９), a formula (II-15) is mentioned.

The compound represented by formula (I) and the compound represented by formula (II) can be used independently, respectively. Further, they can be mixed in any ratio. When mixing, the mixing ratio thereof is molar ratio, preferably 5:95 to 95: 5 in formula (I): formula (II), more preferably 10:90 to 90:10, even more preferably 20: 80 to 80:20.

As the monomer (# 2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (# 2) As 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

As the monomer (ｂ3) having a tetrahydrofuryl and ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. (ｂ3) specifically, tetrahydrofurfuryl acrylate (for example, biscoat V # 150, Osaka Organic Chemical Industry Co., Ltd. product), tetrahydrofurfuryl methacrylate, etc. are mentioned.

It is preferable that (i) is (i) from the viewpoint of further improving the reliability, such as heat resistance and chemical resistance, of the obtained color filter. Moreover, (ｂ１-2) is more preferable from the viewpoint of excellent protective stability of the colored composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is called "dicyclopentanyl (meth) acrylate" as a common name in the art.) Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, the term "dicyclopentenyl ( Meta) acrylate), dicyclophene Tanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphth (Meth) acrylic acid esters such as butyl (meth) acrylate, 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] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl ) Bicyclo unsaturated compounds such as bicyclo [2.2.1] hepto-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

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

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hepto-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [# 1], the proportion of the structural unit derived from each is preferably within the following range among all the structural units constituting the resin [# 1].

structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%)

structural unit derived from (iii); 50 to 98 mol% (more preferably 55 to 90 mol%)

When the proportion of the structural unit of the resin [# 1] is in the above range, it tends to be excellent in storage stability, developability, and solvent resistance of the obtained pattern.

Resin [# 1] is described in, for example, the method described in the literature "Experiment of Polymer Synthesis" [Otsu Takayuki, published by the Chemical Industry Co., Ltd., first edition, published on March 1, 1972] and described in the document It can be prepared by referring to the cited literature.

Specifically, a method of mixing a predetermined amount of (a) and (iii), a polymerization initiator, a solvent, and the like in a reaction vessel, and stirring, heating, and warming in a deoxygenated atmosphere can be given. In addition, the polymerization initiator and solvent used herein are not particularly limited, and one of those commonly used in the art may be used. For example, as a polymerization initiator, an azo compound [2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile, etc.)] or an organic peroxide (such as benzoyl peroxide) Examples thereof include solvents in which respective monomers are dissolved, and a solvent (E) or the like described later can be used as the solvent for the colored composition.

Moreover, the obtained copolymer may use the solution after reaction as it is, the concentrated or diluted solution may be used, and the thing extracted as solid (powder) by methods, such as reprecipitation, may be used. In particular, by using the solvent (E) described later as a solvent during its polymerization, the solution after the reaction can be used still, and the manufacturing process can be simplified.

In the resin [# 2], the proportion of the structural unit derived from each is preferably within the following range among all the structural units constituting the resin [# 2].

Structural unit derived from (a): 4 to 45 mol% (more preferably 10 to 30 mol%)

Structural unit derived from (iii): 2 to 95 mol% (more preferably 5 to 80 mol%)

Structural unit derived from (c): 1 to 65 mol% (more preferably 5 to 60 mol%)

When the proportion of the structural unit of the resin [# 2] is in the above range, it tends to be excellent in storage stability, developability, solvent resistance of the resulting pattern, heat resistance and mechanical strength.

Resin [# 2] can be produced in the same manner as described for example as a method for producing resin [# 1].

Specifically, a method of mixing predetermined amounts of (a), (iii) and (c), a polymerization initiator and a solvent in a reaction vessel, and stirring, heating, and warming in a deoxygenated atmosphere can be given. The obtained copolymer may still use the solution after the reaction, a concentrated or diluted solution may be used, or an extract extracted as a solid (powder) by a method such as reprecipitation may be used.

In the resin [# 3], the proportion of the structural unit derived from each is preferably within the following range among all the structural units constituting the resin [# 3].

(a) 2 to 55 mol%, more preferably 10 to 50 mol%

(c) 45-98 mol%, more preferably 50-90 mol%

The resin [# 3] can be produced in the same manner as the method described as the structure method of the resin [# 1], for example.

Resin [# 4] is prepared by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms (i) to the carboxylic acid and / or carboxylic acid anhydride of (a). You can.

First, the copolymers of (a) and (c) are produced in the same manner as the method described as a method for producing the resin [# 1]. In this case, the proportion of the structural unit derived from each is preferably within the following range among all the structural units constituting the copolymer of (a) and (c).

(a) 5 to 50 mol%, more preferably 10 to 45 mol%

(c) 50-95 mol%, more preferably 55-90 mol%

Subsequently, a part of carboxylic acid derived from (a) and / or carboxylic acid anhydride in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms (b).

Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (iv), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with a cyclic ether [eg, Tris (dimethylaminomethyl) phenol, etc.] and a polymerization inhibitor (for example, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60 to 130 ° C for 1 to 10 hours to obtain a resin [# 4]. have.

The amount of (i) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (VIII) is difficult to remain, (VIII) used for the resin [VIII] is preferably (VIII), and more preferably (VIII-1).

The use amount of the reaction catalyst is preferably 0.001 to 5% by mass relative to the total amount of (a), (i) and (c). The use amount of the polymerization inhibitor is preferably 0.001 to 5% by mass relative to the total amount of (a), (i) and (c).

The reaction conditions such as the mixing method, reaction temperature, and time can be appropriately adjusted in consideration of the amount of heat generated by production facilities or polymerization. In addition, the mixing method and reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization in the same manner as the polymerization conditions.

As the first step, the resin [IX5] is obtained in the same manner as the method for producing the resin [X1] described above to obtain a copolymer of (X) and (C). As in the above, the obtained copolymer may use the solution after the reaction as it is, or may use a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation.

It is preferable that the ratio of the structural unit derived from (i) and (c) is in the following range with respect to the total mole number of all the structural units which comprise the said copolymer.

Structural unit derived from (iii): 5 to 95 mol% (more preferably 10 to 90 mol%)

Structural unit derived from (c): 5 to 95 mol% (more preferably 10 to 90 mol%)

Moreover, under the same conditions as the method for producing the resin [X4], the carboxylic ether derived from (VIII) of the copolymer of (VIII) and (C) is reacted with the carboxylic acid or carboxylic acid anhydride possessed by (A). By doing this, resin [IX5] can be obtained.

The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 moles per 100 moles (i). Since the reactivity of the cyclic ether is high and unreacted (VIII) is difficult to remain, (VIII) used in the resin [V5] is preferably (VIII), and more preferably (VIII-1).

Resin [Ｋ6] is a resin in which carboxylic acid anhydride is further reacted with resin [Ｋ5]. Carbonic anhydride is reacted with a hydroxy group generated by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride.

As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra And hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride).

As the resin (Ｂ), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid Resins such as copolymers [# 1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxycyclo [5.2 .1.0 ^2.6 ] resins such as decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [Ｋ２]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer [Ｋ3]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resins such as resins to which acrylate is added, resins to which glycidyl (meth) acrylate is added to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer [# 4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer of (meth) acrylic acid reacted with resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer [# 5]; And resins such as resins in which tetrahydrophthalic anhydride is further reacted with a resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. .

These resins may be used alone or in combination of two or more.

Among these, resin [# 1], resin [# 2] and resin [# 3] are preferable as the resin (i).

The weight average molecular weight of the resin in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the solubility in the developing solution of the unexposed portion is high, and the residual film ratio and hardness of the obtained pattern tend to be high.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (i) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin is preferably 50 to 180 mg-KOH / g, and more preferably 60 to 150 mg-KOH / g. Here, the acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (i) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the solid content of the coloring composition. When the content of the resin is in the above range, the solubility in the developing solution of the unexposed portion tends to be high.

It is preferable that the coloring composition of this invention contains a polymeric compound (C). It is preferable that the weight average molecular weight of a polymerizable compound (C) is 3,000 or less. The polymerizable compound (C) is not particularly limited as long as it is a compound capable of polymerizing with an active radical generated from the polymerization initiator (D) by irradiating light, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. .

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meta ) Acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, ethylene glycol modified pentaerythritol tetra (meth) ) Acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol te Tra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. You can. Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin in the colored composition.

It is preferable that the coloring composition of this invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals or acids by the action of light and / or heat, and initiates polymerization of the polymerizable compound (C), and a known polymerization initiator can be used. Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. These polymerization initiators may be used alone or in combination of two or more.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding hand.

As the O-acyloxime compound, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3, 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropan-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-day] -3-cyclopentylpropan-1-one-2-imine. You may use commercial items, such as a monocure OXE01, OXE02 (above, BASF company make), N-1919 (made by ADEKA company).

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

Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- And 1-butanone. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation).

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 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenol) propan-1-one, and α, α-diethoxyacetophenone and benzyl dimethyl ketal.

From the viewpoint of sensitivity, a compound having a partial structure represented by formula (d2) is preferable as the alkylphenone compound.

As the biimidazole compound, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373), 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, for example, Publication No. 48-38403, Publication No. 62-174204, etc.), 4,4', 5 And an imidazole compound in which the phenyl group at the 5'-position is substituted with a carboalkoxy group (for example, see JP-A No. 07-10913).

As the triazine compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- 1) 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) ether] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ether] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as an acylphosphine oxide compound.

Moreover, as a polymerization initiator (D), benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 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 campaquinone; And 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with a polymerization initiator (D1) [especially amines] mentioned later.

Moreover, you may use the acid generator which produces an acid by the action of light and / or heat as a polymerization initiator (D). As an acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl And onium salts such as iodonium hexafluoroantimonate, nitrobenzyl tosylates, and benzointosylates. The triazine compound can also be used as an acid generator.

The content of the polymerization initiator (D) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the solid content of the colored composition.

The colored composition of the present invention may contain a polymerization initiator (D1). When a polymerization initiator (D1) is included, it is usually used in combination with a polymerization initiator (D). The polymerization initiator (D1) is a compound or sensitizer used to accelerate polymerization of the polymerizable compound (C) in which polymerization is initiated by the polymerization initiator (D).

Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. These polymerization initiators may be used alone or in combination of two or more.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamine 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [common name, Mihiler ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone, etc. are mentioned, Of these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy And anthracene and 2-ethyl-9,10-dibutoxyanthracene.

As the thioxanthone compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- Propoxycity oxanthone and the like.

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfate And panyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When using a polymerization initiator (D1), its content is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles, per 1 mole of the polymerization initiator (D).

In addition, the total content of the polymerization initiator (D) and the polymerization initiator (D1) is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, even more preferably 10 to 1% of the solid content of the colored composition. 20% by mass.

The colored composition of the present invention may contain a thiol compound (T). Thiol compound (T) is a compound having -SH in a molecule.

As a compound having one -SH in the molecule, for example, 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzooxa Sol, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyridine, 4 -Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydride Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine Midine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sul Panyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2- All, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino- 5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3- Thiol, 3-sulfanyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4 -Thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2-sulfanyl-5-thiazolidon, 2-sul Panilthiazolin, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2- Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro With -2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2- And amino-6-purinthiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, and the like.

As a compound having two or more -SH in the molecule, hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate ), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3- Sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl butyloxy) butane, and the like.

The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is in this range, the sensitivity is increased and the developability tends to be improved.

The colored composition of the present invention may contain a silane compound (S). The silane compound (S) is a compound having a group represented by formula (S).

[In the formula (S), R ^s1 to R ^s3 independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 4 carbon atoms, and two or more are 1 to 4 carbon atoms. Represents an alkoxy group or an alkoxyalkoxy group having 2 to 4 carbon atoms]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, and butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and are preferably methoxy groups and ethoxy groups.

 Examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, methoxyethoxy group, and ethoxyethoxy group, and are preferably methoxyethoxy groups. .

Two of R ^s1 to R ^s3 are alkoxy groups having 1 to 4 carbon atoms, and preferably any one of R ^s1 to R ^s3 is an alkoxy group having 1 to 4 carbon atoms.

As the siran compound (S), methyl trimethoxy siran, methyl triethoxy siran, vinyl trichloro siran, vinyl trimethoxy siran, vinyl triethoxy siran, vinyl triacetoxy siran, (3 -Chloropropyl) trimethoxysiran, (3-chloropropyl) methyldimethoxysiran, (3-chloropropyl) methyldiethoxysiran, (3-glycidyloxypropyl) trimethoxysiran, ( 3-glycidyloxypropyl) triethoxysiran, (3-glycidyloxypropyl) methyldimethoxysiran, (3-sulfanylpropyl) trimethoxysiran, (3-methacryloyloxy Propyl) trimethoxysiran, (3-methacryloyloxypropyl) methyldimethoxysiran, [2- (3,4-epoxycyclohexyl) ethyl] trimethoxysiran, [N-2- ( N-vinylbenzylaminoethyl) -3-aminopropyl] trimethoxysiran hydrochloride, (triaminopropyl) trimethoxysiran, (3-aminopropyl) trimethoxysiran, (3-aminopropyl) tri Ethoxycyran, (3-aminopropyl) Methyl diethoxysiran, (3-aminopropyl) tris (2-methoxyethoxy) siran, [3- (2-aminoethyl) -3-aminopropyl] trimethoxysiran, [3- (2 -Aminoethyl) -3-aminopropyl] methyldimethoxysiran, (3-ureidopropyl) trimethoxysiran, (3-ureidopropyl) triethoxysiran, (N-aminoethyl-3- Aminopropyl) trimethoxysiran, (N-aminoethyl-3-aminopropyl) dimethoxysiran, (N-methyl-3-aminopropyl) trimethoxysiran, (N-phenyl-3-aminopropyl) ) Trimethoxysiran etc. are mentioned.

The content of the silane compound (S) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to the solid content of the colored composition. When the content of the silane compound (S) is in this range, pattern peeling tends to be small at the time of development.

It is preferable that the coloring composition of this invention contains a solvent (E). The solvent (E) is not particularly limited, but a solvent commonly used in the art may be used. For example, ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), esters It can be selected from ketone solvents other than solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid And butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenitol, methyl anisole, etc. Can be mentioned.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, 3-ethoxypropionic acid ethyl, 2-methoxypropionic acid methyl, 2-methoxypropionic acid ethyl, 2-methoxypropionic acid propyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether Acetate, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monoe There may be mentioned ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane And cyclohexanone, isophorone, and the like.

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

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

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

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C or higher and 180 ° C or lower in 1 atm from the viewpoint of coatability and dryness is preferable. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanol, N, N-dimethylformamide, cyclohexanone, etc. are preferable, and propylene glycol monomethyl ether acetate, propylene Glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionic acid ethyl and the like are more preferable.

When using 2 or more types of solvents, you may use together with the solvent whose boiling point is 170 degreeC or more and 250 degreeC or less in 1 atm, and the solvent whose boiling point is 120 degreeC or more and less than 170 degreeC. At this time, the content of the solvent having a boiling point of 170 ° C or more and 250 ° C or less in 1 atm is preferably 0.1% by mass or more and 10% by mass or less relative to the solvent (E). By using such a solvent, a coloring composition tends to be excellent in coatability.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, with respect to the colored composition. In other words, the solid content of the coloring composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, flatness at the time of application becomes good, and when forming a color filter, the color density is not insufficient, so the display characteristics tend to be good.

The colored composition of the present invention may contain a surfactant. Examples of the surfactant include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 [Tore-Dow Corning Co., Ltd.], KP321, KP322, KP323 , KP324, KP326, KP340, KP341 [manufactured by Shin-Etsu Chemical Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Momentive, Performance, Materials and Japan joint ventures] And the like.

As said fluorine type surfactant, surfactant etc. which have a fluoro carbon chain are mentioned. Specifically, Floyd (brand name) FC430, Floyd FC431 (Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183 , Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 [made by Mitsubishi Material Electronic Chemical Co., Ltd.] , Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megapack (trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (made by DIC Corporation), etc. are mentioned.

These surfactants may be used alone or in combination of two or more.

The content of the surfactant (i) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, even more preferably 0.01% by mass or more and 0.05% by mass with respect to the coloring composition. % Or less. However, the content of the pigment dispersant is not included in the content of the surfactant (i). When the content of the surfactant (Ｆ) is in the above range, the flatness of the coating film can be improved.

The coloring composition of the present invention may contain additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, if necessary.

The coloring composition of this invention can be manufactured as follows, for example.

First, it is preferable to mix the pigment (A1) with the solvent (E) and disperse it using a disperser until the average particle diameter of the pigment is about 0.2 µm or less. At this time, part or all of the pigment dispersant and the resin may be blended as necessary. When the coloring composition of the present invention contains the pigment (A2), the pigment (A1) and the pigment (A2) may be mixed after being dispersed, or may be dispersed together after mixing both. When the dye composition (A3) is included in the coloring composition of this invention, you may disperse | distribute like pigment (A1) and / or pigment (A2). Examples of the disperser include a paint shaker, a sand grinder, a beads mill, a ball mill, a roll mill, a stone mill, a jet mill, And a homogenizer.

When performing dispersion treatment using a paint shaker, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to 2 mm. The temperature at which the dispersion treatment is performed is preferably 0 to 100 ° C or higher, and more preferably 20 to 80 ° C or higher. In addition, as the time for performing the dispersion treatment, usually 1 to 20 hours, preferably about 1 to 10 hours, may be mentioned, but may be appropriately adjusted depending on the composition of the pigment dispersion liquid and the size of the apparatus of the paint shaker.

A desired coloring composition can be obtained by mixing a predetermined amount of the pigment dispersion thus obtained, the remainder of the resin (i), the remainder of the solvent (E), and other components included in the coloring composition. It is preferable to filter a coloring composition with a filter of about 0.5-10 micrometers in diameter as needed.

As a method of forming a pattern using the coloring composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among these, photolithography is preferred.

The photolithography method is a method of obtaining a pattern by applying the coloring composition to a substrate, drying it, exposing it with a photomask, and developing it.

Examples of the substrate include glass, metal, plastic, and the like, and may be in the form of a plate or a film. In addition, structures such as color filters, various insulating or conductive films, and driving circuits may be formed on the substrate.

Application to the substrate is, for example, spin coater, slit & spin coater, slit coater (also called die coater, curtain flow coater, spinless coater) , It can be carried out using a coating device such as inkjet.

As a method of drying the film applied to the substrate, for example, methods such as heat drying, self-heat drying, air drying and reduced pressure drying are exemplified. You may perform combining several methods. The drying temperature is preferably 10 to 120 ° C, and more preferably 25 to 100 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. The drying under reduced pressure is preferably carried out under a pressure of 50 to 150 MPa in a temperature range of 20 to 25 ° C. By drying, volatile components such as a solvent contained in the coloring composition are removed.

The film thickness of the coated film after drying is not particularly limited, and can be appropriately adjusted depending on the material used, application, and the like, for example, 0.1 to 20 μm, and preferably 1 to 6 μm.

The dried coating film is exposed by inserting a photomask to form a desired pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape is used depending on the intended use.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength, or a band pass filter that extracts light near 436 nm, near 408 nm, and around 365 nm using this wavelength range is used. It may be selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use a device such as a mask aligner, a stepper, etc. so that the entire surface of the exposure surface can be irradiated with uniformly parallel light or the alignment of the mask and the substrate can be accurately performed.

After exposure, a pattern can be obtained by contacting a developer to dissolve and develop a predetermined portion, for example, an unexposed portion. An organic solvent may be used as the developer, but it is difficult to dissolve or swell the exposed portion of the coating film with the developer, and an aqueous solution of a basic compound is preferred in order to obtain a pattern of good shape.

The developing method may be any of paddle method, dipping method, spray method and the like. Moreover, the substrate may be tilted at an arbitrary angle during development.

After development, it is preferable to wash with water.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, Inorganic basic compounds such as potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia; Tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, And organic basic compounds such as ethanolamine. Among these, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferred.

The concentration of the inorganic and organic basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The aqueous solution of the basic compound may contain a surfactant.

As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine;

Anionic surfactants such as sodium lauryl alcohol sulfate ester, sodium oleyl alcohol sulfate ester, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonic acid;

And cationic surfactants such as stearylamine hydrochloride and lauryl trimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, particularly preferably 0.1 to 5% by mass.

Furthermore, a post bake may be performed as necessary. It is preferable to perform post-baking in the range of 150-250 degreeC and 1-240 minutes, for example.

The pattern obtained as described above with the colored composition of the present invention is useful as a color filter. The color filter can be used in a form known to equipment related to various colored images, such as a display device (for example, a liquid crystal display device, an organic EL device), a solid-state imaging device, and electronic paper.

Example

The present invention will be described more specifically by taking the following examples. "%" And "part" in the example are mass% and mass parts, unless otherwise specified.

Synthesis Example 1

Sodium tert-amyl alcohol was synthesized by reacting 174 g of tert-amyl alcohol with 22.2 g of metallic sodium under a nitrogen atmosphere at 130 ° C. This was heated to 60 ° C, 91.0 g of 4-bromobenzonitrile, 71.05 g of succinic acid di-tert-amyl ester, and 108.9 g of tert-amyl alcohol were added and stirred for 2 hours so that the solution temperature was 85 ° C or lower. The suspension was further stirred for 18 hours or more, and then added to a mixture of 200 g of methanol cooled to -10 ° C, 1000 g of water, and 49.21 g of sulfuric acid. After the suspension was added, the mixture was kept at 0 ° C and stirred for 5 hours to complete the reaction, and then the solid content was filtered. The solid content was alternately washed with methanol and water, and repeatedly washed until the coloration of the filtrate disappeared and the precipitation of salt disappeared. Thereafter, the solid content was dried in a vacuum dryer at 80 ° C. for 18 hours to obtain the desired red pigment 1. The amount obtained was 107 g.

Synthesis Example 2

15 parts of a mixture of a compound represented by formula (A1-1a) and a compound represented by formula (A1-1-1) (trade name Chugai Aminol Fast Pink R) in a flask equipped with a cooling tube and a stirring device, chloroform 150 parts and 8.9 parts of N, N-dimethylformamide were added, and 10.9 parts of thionyl chloride was added dropwise while stirring at 20 ° C or lower. After completion of the dropwise addition, the temperature was raised to 50 ° C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20 ° C. The reaction solution after cooling was kept dropping to 20 ° C or less under stirring, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to react. Subsequently, the obtained reaction mixture was removed by evaporation of a solvent using a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. This mixture was added while stirring in a mixed solution of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated as a result, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye 1 (a mixture of compounds represented by formulas (A1-1-1) to (A1-1-1)). 11.3 parts were obtained.

Synthesis Example 3

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 6.1 parts of an aqueous 35% sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by dissolving and dissolving 19.4 parts of 35% hydrochloric acid little by little to obtain a suspension containing a diazonium salt. Subsequently, an aqueous solution in which 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added, and excess sodium nitrite was quenched.

Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C. to obtain 11.7 parts (yield 87%) of the compound represented by formula (VII-1).

10 parts of the compound represented by formula (ｐ-1) is dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved in 12 parts of ammonium chromium (II) sulfate (made by Wako Pure Chemical Industries, Ltd.) 3.1 parts After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the red-orange solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts (63%) of the compound represented by formula (VII-1).

The structure of the compound represented by formula (VII-1) was identified using a mass spectrometer JMS-700 (manufactured by Nippon Electronics Co., Ltd.).

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

(Mass Spec.) Ionization mode ^{= ESI -: m / z =} 882.1 [M-Na +] -

Exact Mass: 905.1

Rhodamine B (Tokyo Kasei Industry Co., Ltd.) 18 parts, anhydrous chloroform (Kanto Chemical Co., Ltd.) 170 parts, campasulfonic acid [Aldrich Co., Ltd.] 1.0 parts, 4- (N, N-dimethylamino) 1.4 parts of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred for about 30 minutes. Thereafter, 47 parts of anhydrous chloroform was added to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride [manufactured by Wako Pure Chemical Industries, Ltd.], and the solution previously dissolved was slowly added, followed by room temperature. It was stirred for about 2 hours. After performing the separation operation twice in 150 parts of 1N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts of 10% saline. Subsequently, after adding 43 parts of anhydrous magnesium sulfate and stirring for about 30 minutes, the desiccant was filtered and the solvent was evaporated to remove to obtain 20.6 parts of the compound represented by formula (VII-1) (yield 90%).

The structure of the compound represented by formula (VII-1) was identified using a mass spectrometer JMS-700 (manufactured by Nippon Electronics Co., Ltd.).

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

(Mass Spec.) Ionization mode ^{= ESI +: m / z =} 575.3 [M-Cl -] +

Exact Mass: 610.3

The solution (s3) was adjusted by adding 4030 parts of methanol to 253 parts of the compound represented by formula (VII-1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by formula (VII-1) to adjust the solution (T3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 ° C to obtain 263 parts of compound (dye 2) represented by formula (A2Ａ-7) (yield 65%). .

The structure of the compound represented by formula (A2ｂ-7) was determined by elemental analysis. As an analytical instrument, an ICP emission analysis device (ICPS-8100; manufactured by Shimadzu Corporation) was used.

Synthesis Example 4

After adding 100 parts of water to 10 parts of 2,2'-benzidine disulfonic acid represented by formula (a-1) (containing 30% of water), the mixture was adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice cooling. 5.6 parts of sodium nitrite was added and stirred for 30 minutes. 14.8 parts of 35% hydrochloric acid was added little by little to make a brown solution, followed by stirring for 2 hours. An aqueous solution in which 3.8 parts of amide sulfuric acid was dissolved in 38.3 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

After adding 47.9 parts of water to 9.6 parts of 1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyrid-2-one represented by formula (c-1), under ice-cooling, 30% aqueous sodium hydroxide solution PH was adjusted to 8-9.

The following operation was performed under ice cooling. After stirring the pyridone alkaline aqueous solution to a colorless solution, the suspension containing the diazonium salt was added dropwise with a pump while adjusting the pH to 8-9 with a 30% sodium hydroxide aqueous solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 15.7 parts of the azo compound represented by formula (A3c-I-1).

The structure of the azo compound (A3c-I-1) was determined by ¹ H-NMR and ¹³ C-NMR analysis. ECA-500 (manufactured by Nippon Electronics Co., Ltd.) was used as the analysis instrument.

To a flask equipped with a cooling tube and a stirring device, 5 parts of azo compound (A3c-I-1), 50 parts of chloroform and 2.1 parts of N, N-dimethylformamide were added, while stirring, while maintaining 20 DEG C or lower, titanium chloride 6 parts of o'Neill was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20 ° C. While stirring, the reaction solution after cooling was kept at 20 ° C or lower, and a mixture of 4 parts of 1,5-dimethylhexylamine and 14 parts of triethylamine was added dropwise. Thereafter, the last solution was stirred and reacted at the same temperature. Subsequently, the obtained reaction mixture was removed by evaporation of a solvent using a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. This mixture was added with stirring in a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.6 parts (yield 56%) of the azo compound represented by formula (A3c-II-1) (dye 3).

Synthesis Example 5

After adding 300 parts of water to 30 parts of 2,2'-benzidine disulfonic acid represented by formula (a-1) (containing 30% of water), the mixture was adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice cooling. 12.6 parts of sodium nitrite was added and stirred for 30 minutes. 38.1 parts of 35% hydrochloric acid was added little by little to form a brown solution, and then stirred for 2 hours. An aqueous solution in which 5.3 parts of amide sulfuric acid was dissolved in 57.4 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

After adding 372 parts of water to 18.6 parts of N, N'-dimethylbarbituric acid represented by the formula (c-2), it was adjusted to pH 8-9 with ice-cooled 30% aqueous sodium hydroxide solution.

The following operation was performed under ice cooling. After stirring the aqueous alkali solution of barbituric acid to a colorless solution, a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8-9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 14.6 parts of an azo compound represented by formula (A3d-I-1).

The structure of the azo compound (A3d-I-1) was determined by ¹ H-NMR and ¹³ C-NMR analysis. As the analysis instrument, ECA-500 (manufactured by Nippon Electronics Co., Ltd.) was used.

The azo compound represented by formula (A3d-II-1) was prepared as follows. 10 parts of azo compound (A3c-I-1), 100 parts of chloroform, and 4.2 parts of N, N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and while stirring, the temperature was maintained at 20 ° C or lower, and 7 parts of O'Neill was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20 ° C. While stirring, the reaction solution after cooling was added dropwise to a mixture of 5 parts of 1,5-dimethylhexylamine and 15 parts of triethylamine while maintaining the temperature at 20 ° C or lower. Thereafter, the mixture was stirred at the same temperature for 5 hours to react. Subsequently, the obtained reaction mixture was removed by evaporation of a solvent using a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. This mixture was added while stirring in a mixture of 58 parts of acetic acid and 600 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 10.9 parts (yield 82%) of an azo compound (A3d-II-1; dye 4).

Synthesis Example 6

133 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping rod, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 ° C, and dicyclopentanyl methacrylate [FA-513M; Nihon Kasei Industrial Co., Ltd.] 22.0 g (0.10 mol), benzyl methacrylate 82.8 g (0.47 mol), methacrylic acid 37.0 g (0.43 mol), 2,2'-azobisisobutyronitrile 3.6 g and The mixture consisting of 164 g of propylene glycol monomethyl ether acetate was added dropwise into the flask over 2 hours using a dropping rod, and after completion of dropping, the mixture was further stirred at 100 ° C for 5 hours.

After completion of the stirring, air was introduced into the flask through a gas introduction pipe, and the atmosphere in the flask was replaced with air, followed by 21.5 g (0.15 mol) of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol, and 0.145 of hydroquinone. g was put into the flask, and the reaction was continued at 110 ° C for 6 hours to obtain a resin 1 solution having a weight average molecular weight (Mw): 9000, molecular weight distribution: 1.7, solid content 37.8 mass%, and solid acid value of 97 mgKOH / g.

Synthesis Example 7

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping rod, and a gas introduction tube, nitrogen was flowed at 0.02 L / min into a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Subsequently, 36 parts of acrylic acid; And 4,5-epoxycyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate {ie monomer (I-1)} and 3,4-epoxycyclo [5.2.1.0 ^2,6 ] decane A mixture of -8-yl acrylate {i.e., monomer (II-1)} {molar ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 264 parts; propylene glycol monomethyl A monomer solution was prepared by dissolving in 140 parts of ether acetate. The monomer lysate was added dropwise to the flask maintained at a temperature of 70 ° C. over 4 hours using a dropping rod. On the other hand, a polymerization initiator solution in which 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was used over a period of 4 hours using a separate dropping rod. It was dripped into the flask. After the dropping of the polymerization initiator solution was completed, the mixture was maintained at 70 ° C. for 4 hours, and then cooled to room temperature, followed by weight average molecular weight (Mw): 9000, molecular weight distribution: 2.0, solid content 33%, solid content acid value 90 mg-KOH / g solution of resin 2 was obtained.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of the resin obtained in the above synthesis example was carried out under the following conditions using the GPC method.

Device ; HLC-8120GPC [manufactured by Tosoh Corporation]

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Test subject solids concentration; 0.001 to 0.01 mass%

Injection volume; 50 μl

Detector; RI

Standard materials for calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 [manufactured by Tosoh Corporation]

Example 1

[Preparation of coloring composition]

Pigment: 70 parts of pigment 1,

28 parts of pigment dispersant, and

462 parts of propylene glycol monomethyl ether acetate

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Resin: Resin 1 (solid content equivalent) 65 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

And

Solvent: 267 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition.

[Production of patterns]

After the coloring composition was applied on a 2-inch glass substrate (Eagle XG; manufactured by Corning) by spin coating, it was pre-baked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the coloring composition and the photo mast made of quartz glass having a pattern was set to 100 µm, and an exposure machine [TME-150RSK; Topcon Co., Ltd. product, and irradiated with light at an exposure amount of 150 mJ / cm 2 (based on 365 nm) under an atmospheric atmosphere. In addition, a mask formed with a line and space pattern of 100 µm was used as the photo mask. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then post-baked at 220 ° C for 20 minutes in an oven. It was carried out to obtain a pattern.

[Foreign body evaluation]

About the obtained pattern, surface shape optical microscope [magnification 100 times; VF-7510; Keyence Co., Ltd.]. It was set as (circle) when a foreign substance was not recognized within the observation field, and as x when a foreign substance was confirmed. Table 1 shows the results.

[Measurement of film thickness]

About the obtained pattern, the film thickness measuring apparatus [DEKTAK3; The film thickness was measured using Japan Vacuum Technology Co., Ltd.]. Table 1 shows the results.

[Chromaticity evaluation]

About the obtained pattern, a colorimetric machine [OSP-SP-200; The spectroscopy was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and brightness Y were measured in the XYZ colorimeter of the CIE using the characteristic coefficients of the C light source. Table 1 shows the results.

[Contrast evaluation]

A coating film was obtained by performing the same operation as in the production of a pattern, except that a photomask was not used during exposure. About the obtained coating film, a contrast system [CT-1; Tsubosaka Electric Co., Ltd., color chrominance meter BM-5A; Topcon, a light source; F-10, polarizing film; Contrast was measured using a Tsubosaka Electric Co., Ltd. product with a blank value of 30000. If the contrast is high in the coating film, it can be said that the contrast is also high in the pattern. Table 1 shows the results.

Example 2

[Preparation of coloring composition]

Pigment: 36 parts of pigment 1,

14 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 238 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Pigment: C.I. Pigment Red 242 36 copies,

18 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 194 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Resin: Resin 1 (solid content equivalent) 65 copies

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

And

Solvent: 319 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Example 3

[Preparation of coloring composition]

Pigment: 35 parts of pigment 1,

14 parts of pigment dispersant, and

234 parts of propylene glycol monomethyl ether acetate

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Pigment: C.I. Pigment Red 177 35 copies,

16 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 191 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Resin: Resin 1 (solid content equivalent) 65 copies

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

And

Solvent: 314 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Example 4

[Preparation of coloring composition]

Pigment: 53 parts of pigment 1,

21 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 353 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Dye: 13 parts of dye 1,

Resin: Resin 1 (solid content conversion) 16 copies,

Resin: Resin 2 (solid content equivalent) 49 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

And

Solvent: 343 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Example 5

[Preparation of coloring composition]

Pigment: 53 parts of pigment 1,

21 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 353 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Dye: 13 parts of dye 2,

Resin: Resin 1 (solid content conversion) 16 copies,

Resin: Resin 2 (solid content equivalent) 49 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

Solvent: 252 parts of ethyl lactate,

And

Solvent: 91 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Example 6

[Preparation of coloring composition]

Pigment: 53 parts of pigment 1,

21 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 353 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Dye: 13 parts of dye 3,

Resin: Resin 1 (solid content conversion) 16 copies,

Resin: Resin 2 (solid content equivalent) 49 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

Solvent: 252 parts of ethyl lactate,

And

Solvent: 91 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Example 7

[Preparation of coloring composition]

Pigment: 53 parts of pigment 1,

21 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 353 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Dye: 13 parts of dye 4,

Resin: Resin 1 (solid content conversion) 16 copies,

Resin: Resin 2 (solid content equivalent) 49 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

Solvent: 252 parts of ethyl lactate,

And

Solvent: 91 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same operation as in Example 1 was performed on the colored composition to obtain a high contrast color filter.

Comparative Example 1

[Preparation of coloring composition]

Pigment: C.I. Pigment Red 254 72 copies,

33 parts of pigment dispersant, and

Propylene glycol monomethyl ether acetate 391 parts

And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,

Resin: Resin 1 (solid content equivalent) 65 parts,

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.] 35 copies,

Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Mongacure OXE01; manufactured by BASF; O-acyloxime compound),

Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Mongacure 369; manufactured by BASF; alkylphenone compound) 6 parts,

Polymerization initiator: 2 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound),

Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone [EAB-F; Hodogaya Chemical Industry Co., Ltd. Part 2,

Surfactant: Polyether-modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 copies,

And

Solvent: 368 parts of propylene glycol monomethyl ether acetate

Was mixed to obtain a colored composition. The same evaluation as in Example 1 was performed for the colored composition. Table 1 shows the results.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring composition which can manufacture a high contrast color filter.

Claims (9)

Pigments, xanthene dyes or azo dyes and resins,
The xanthene dye and azo dye do not include dye molecules containing a group capable of complexing with a metal atom in the molecule, and dyes complexed with a metal atom,
The pigment is the formula (P)

[In formula (P), R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represent a hydrogen atom, a bromine atom or a monovalent substituent, and at least one represents a bromine atom]
Contains a compound represented by,
The xanthene dye is represented by formula (1)

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
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 .
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 an integer of 2 or more, a plurality of R ^5s are the same or different.
a represents the integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may combine with each other to form a heterocyclic ring of 3 to 10 atom rings containing nitrogen atoms. .
R ¹¹ each independently 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]
It is a compound represented by,
The azo dye is represented by the formula (A3c-I)

In the formula (A3c-I), R ¹ to R ⁴ each independently represent a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group, or a carboxyl group.
R ⁵ to R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or It represents an N-substituted sulfamoyl group.
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group]
Or formula (A3d-I)

[In formula (A3d-I), Z represents an oxygen atom or a sulfur atom.
R ¹ ~R ⁴ are each independently a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group, a hydroxyl group is a C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group which is substituted with substituted C _{1- 10} saturated aliphatic hydrocarbon group, C _1-8 thioalkoxy group substituted C _1-10 saturated aliphatic hydrocarbon group, C _6-20 aryl group, C _7-20 aralkyl group, or C _2-10 acyl group.
R ⁵ to R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or Represents an N-substituted sulfamoyl group]
The coloring composition which is a compound represented by. delete delete delete delete delete delete A color filter formed by the coloring composition according to claim 1. A display device comprising the color filter according to claim 8.