TWI496840B - Dye composition - Google Patents

Description

Dye composition

This invention relates to a dye composition.

Since the beginning, in order to form a thin and fine colored pattern having desired spectral characteristics, for example, various azo dyes and A pigment or the like (for example, Patent Document 1, Patent Document 2, etc.).

In recent years, the industry expects color filters to be more highly contrasted.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 7-134207

[Patent Document 2] Japanese Patent Laid-Open No. 7-146402

The present invention has been developed in view of the above problems, and an object thereof is to provide a dye composition capable of producing a color filter having higher contrast.

That is, the present invention provides the following [1] to [18].

[1] A dye composition comprising a compound represented by the formula (1) and a compound represented by the formula (2):

(In the formulae (1) and (2), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K or -SO ₃ H, and one of R ¹ to R ¹⁵ represents -SO ₃ ^- , and R ¹⁶ represents a saturated hydrocarbon group having a carbon number of 1 to 10, the saturated hydrocarbon group The hydrogen atom contained in the hydrogen atom may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹⁷ -, R ¹⁷ represents a hydrogen atom or a saturated hydrocarbon group having a carbon number of 1 to 10, and R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H , -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , R ²¹ ~R ³⁵ One of the groups represents -SO ₃ ^- , and at least one of R ²¹ to R ³⁵ represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , and R ¹⁸ and R ¹⁹ independently represent a carbon number of 1 An alkyl group of ~10, a cycloalkyl group having a carbon number of 3 to 30, an aromatic hydrocarbon group having a carbon number of 6 to 10, or an aromatic heterocyclic group having a carbon number of 5 to 10, or Bonding to each other to form a heterocyclic ring having a carbon number of 2 to 10, The alkyl group and the hydrogen atom contained in the cycloalkyl group may be substituted by a halogen atom, a hydroxyl group or a phenyl group, and the alkyl group and the -CH ₂ - contained in the cycloalkyl group may be substituted into -O- , -CO-, -NH- or -NR ¹⁶ -, the aromatic hydrocarbon group and the hydrogen atom contained in the aromatic heterocyclic group may also be a halogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -NO ₂ , -CH=CH ₂ or -CH=CHR ¹⁶ substituted).

[2] The dye composition according to [1], which further comprises a compound represented by the formula (3):

(In the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₂ N(R ¹⁸ )R ¹⁹ Or -SO ₂ NHR ¹⁸ ).

[3] The dye composition according to [1] or [2], wherein, in the formula (1), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- or -SO ₃ H, One of R ¹ to R ¹⁵ represents -SO ₃ ^- and at least one represents -SO ₃ H.

[4] The dye composition according to any one of [1] to [3] wherein, in the formula (2), R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , - One of SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , R ²¹ to R ³⁵ represents -SO ₃ ^- and at least one represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ .

[5] The dye composition according to any one of [2] to [4] wherein, in the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ or -SO ₂ NHR ¹⁸ , At least two of R ⁴¹ to R ⁵⁵ represent -SO ₂ NHR ¹⁸ .

[6] The dye composition according to any one of [1] to [5], wherein the content of the compound represented by the formula (1) is 1 part by mass or more and 35 mass based on 100 parts by mass of the dye composition. The content of the compound represented by the formula (2) is 65 parts by mass or more and 99 parts by mass or less.

[A] The dye composition according to any one of [2] to [6], wherein the content of the compound represented by the formula (1) is 1 part by mass or more and 15 parts by mass based on 100 parts by mass of the dye composition. The content of the compound represented by the formula (2) is 65 parts by mass or more and 98 parts by mass or less, and the content of the compound represented by the formula (3) is 1 part by mass or more and 20 parts by mass or less.

[8] A coloring photosensitive resin composition comprising the dye composition (A-1) according to any one of [1] to [7], an alkali-soluble resin (B), and a photopolymerizable compound (C) , photopolymerization initiator (D) and solvent (E).

[9] The colored photosensitive resin composition according to [8], which further comprises a pigment (A-2).

[10] The colored photosensitive resin composition according to [9], wherein the pigment (A-2) is a pigment containing C.I. Pigment Blue 15:6.

[11] The colored photosensitive resin composition according to [10], wherein the mass ratio of the dye composition (A-1) to the C.I. Pigment Blue 15:6 is from 3:97 to 50:50.

[12] A coating film formed by using the dye composition according to any one of [1] to [7].

[13] A color filter formed using the dye composition according to any one of [1] to [7].

[14] The color filter of [13], which is formed by photolithography.

[15] Use of the dye composition according to any one of [1] to [7] for producing a color filter.

[16] A coloring composition comprising the dye composition (A-1) and the pigment (A-2) according to any one of [1] to [7].

[17] The colored composition according to [16], wherein the pigment (A-2) is a pigment containing C.I. Pigment Blue 15:6.

[18] The colored composition according to [17], wherein the mass ratio of the dye composition (A-1) to the C.I. Pigment Blue 15:6 is from 3:97 to 50:50.

The dye composition (A-1) of the present invention contains a compound represented by the formula (1) (hereinafter sometimes referred to as "compound (1)") and a compound represented by the formula (2) (hereinafter, It is called "compound (2)").

In the present specification, although it differs depending on the carbon number, the following substituents are the same in any of the chemical structural formulas unless otherwise specified. Further, a substituent which may be a straight chain or a branch may also be included.

(In the formulae (1) and (2), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K or -SO ₃ H, and one of R ¹ to R ¹⁵ represents -SO ₃ ^- .

R ¹⁶ represents a saturated hydrocarbon group having a carbon number of 1 to 10, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and the saturated hydrocarbon group is contained in - CH ₂ - may also be substituted with -O-, -CO- or -NR ¹⁷ -.

R ¹⁷ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , one of R ²¹ to R ³⁵ represents -SO ₃ ^- , and at least one of R ²¹ to R ³⁵ represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ .

R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heteropoly group having 5 to 10 carbon atoms. a ring group, or may be bonded to each other to form a heterocyclic ring having 2 to 10 carbon atoms, and the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted by a halogen atom, a hydroxyl group or a phenyl group. And -CH ₂ - contained in the cycloalkyl group may be substituted with -O-, -CO-, -NH- or -NR ¹⁶ -, the aromatic hydrocarbon group and the aromatic heterocyclic group The hydrogen atom may also be substituted by a halogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -NO ₂ , -CH=CH ₂ or -CH=CHR ¹⁶ ).

The number of positive (+) charges and the number of negative (-) charges in each of the compounds of the formulae (1) and (2) are the same.

Here, the saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, an alkyl group having an alkyl group and an alkyl group having a cycloalkyl group, which are arbitrarily combined.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1-methylpropyl group or a 2-methyl group. Base, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-ethylhexyl, decyl, decyl, 1,1-dimethylpropyl, 1,2-di Methyl propyl, 2,2-dimethylpropyl and the like.

The cycloalkyl group may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 1-methylpropoxy group, a 2-methylpropoxy group, and a third group. Oxyl, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2 , 2-dimethylpropoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy and the like.

Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an aryl group having an alkyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and a phenanthryl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

As an aryl group having an alkyl group, in addition to tolyl, xylyl, cumyl, The above substituents may be arbitrarily combined in addition to the group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group or the like.

Examples of the aromatic hetero ring include the following heterocyclic rings:

The hetero ring may be an aromatic hetero ring or a heterocyclic ring having no aromaticity.

Examples of the heterocyclic ring having no aromaticity include the following heterocyclic rings and the like:

Further, the bonding key of the ring may be any of the positions and the positions described above.

The -OR ^{16 may} , for example, be the above alkoxy group.

Examples of -CO ₂ R ¹⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentyloxycarbonyl group, and an isopentyloxy group. Carbocarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl , cyclooctyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, tricyclodecyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2- Ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl, and the like.

Examples of -SO ₂ NHR ¹⁸ include an aminesulfonyl group, an N-(methyl)aminesulfonyl group, an N-(ethyl)aminesulfonyl group, an N-(propyl)aminesulfonyl group, and N- (isopropyl)aminesulfonyl, N-(butyl)aminesulfonyl, N-(isobutyl)aminesulfonyl, N-(pentyl)aminesulfonyl, N-(isopentyl Aminesulfonyl, N-(neopentyl)aminesulfonyl, N-(cyclopentyl)aminesulfonyl, N-(hexyl)aminesulfonyl, N-(cyclohexyl)aminesulfonyl , N-(heptyl)amine sulfonyl, N-(cycloheptyl)amine sulfonyl, N-(octyl)amine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N -(1,5-dimethylhexyl)amine sulfonyl, N-(cyclooctyl)amine sulfonyl, N-(fluorenyl)amine sulfonyl, N-(fluorenyl)amine sulfonyl, N-(tricycloindenyl)amine sulfonyl, N-(methoxypropyl)amine sulfonyl, N-(ethoxypropyl)amine sulfonyl, N-(propoxypropyl) Aminesulfonyl, N-(isopropoxypropyl)amine sulfonyl, N-(hexyloxypropyl)amine sulfonyl, N-(2-ethylhexyloxypropyl)amine sulfonate A group, N-(methoxyhexyl)amine sulfonyl group, N-(3-phenyl-1-methylpropyl)amine sulfonyl group, and the like.

Further, examples of the -SO ₂ NHR ¹⁸ include a group represented by the following formula. Here, in the following formula, X ¹ represents a halogen atom. X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom. X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom.

The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may be a perfluoromethyl group or the like in addition to the above alkyl group.

The alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be an alkoxy group, particularly a methoxy group, an ethoxy group or a propoxy group.

Among them, as -SO ₂ NHR ¹⁸ , R ¹⁸ is preferably an alkyl group having 1 to 10 carbon atoms.

As -SO ₂ N(R ¹⁸ )R ¹⁹ , the following groups can be cited:

Examples of the hetero ring formed by bonding R ¹⁸ and R ^{19 to} each other include a group represented by the following formula:

Among them, as R ¹⁸ and R ¹⁹ , an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, and an aralkyl group having 8 to 10 carbon atoms are preferred. a hydroxyl group-containing alkyl group and an aryl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms, and an aryl group, more preferably a branch having a carbon number of 6 to 8. An alkyl group is particularly preferably 2-ethylhexyl.

In the compound (1), R ¹ to R ¹⁵ are each independently a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K or -SO ₃ H, and R ¹ ~. One of R ¹⁵ is -SO ₃ ^- . More preferably, R ¹ to R ¹⁵ are each independently a hydrogen atom, -R ¹⁶ , -SO ₃ ^- or -SO ₃ H, and one of R ¹ to R ¹⁵ is -SO ₃ ^- . Further, R ¹ to R ^{15 are} particularly preferably independently a hydrogen atom, -R ¹⁶ , -SO ₃ ^- or -SO ₃ H, and one of R ¹ to R ¹⁵ is -SO ₃ ^- and R ¹ ~ One of R ¹⁵ is -SO ₃ H.

Further, the compound (1) is more preferably a compound represented by the following formula (1a):

(In the formula (1a), R ^{1 '} independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{2 '} independently represents a hydrogen atom, -SO ₃ ^- , -SO ₃ N _a , -SO ₃ K Or -SO ₃ H. wherein R ^{2 '} represents -SO ₃ ^- ).

As the compound (1), for example, the following compounds can be mentioned:

The compound (2), R ²¹ ~ R ³⁵ each independently is preferably a hydrogen _{^{atom, -R 16, -SO 3 -,}} -SO 3 H, -SO 3 Na, -SO 3 K, -SO 2 N (R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , and at least one of R ²¹ to R ³⁵ is -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ . R ²¹ to R ^{35 are} particularly preferably independently a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , and R ²¹ ~ At least one of R ³⁵ is -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ .

Further, the compound (2) is more preferably a compound represented by the following formula (2a):

(In the formula (2a), R ^{21 'is} independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{22 '} independently represents a hydrogen atom, -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , wherein one R ^{22 '} represents -SO ₃ ^- and at least one R ^22' represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ ).

The compound (2) includes the following compounds (2-1), (2-2) and (2-3).

The compound (2-1) is a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R, in the formula (2). ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, _- SO ₃ H or -SO ₂ N(R ¹⁸ )R ¹⁹ , and one of R ²¹ to R ³⁵ represents -SO ₃ ^- , And one of R ²¹ to R ³⁵ represents a compound of -SO ₂ NR ¹⁸ R ¹⁹ .

The compound (2-1) is preferably a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ , in the formula (2). K, -SO ₃ H or -SO ₂ N(R ¹⁸ )R ¹⁹ , and one of R ²¹ to R ³⁵ represents -SO ₃ ^- , and one of R ²¹ to R ³⁵ represents -SO ₂ NR ¹⁸ R ¹⁹ compound.

The compound (2-2) is a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R, in the formula (2). ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H or -SO ₂ NHR ¹⁸ , and one of R ²¹ to R ³⁵ represents -SO ₃ ^- and R ²¹ ~R One of ³⁵ represents a compound of -SO ₂ NHR ¹⁸ .

The compound (2-2) is preferably a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ , in the formula (2). K, -SO ₃ H or -SO ₂ NHR ¹⁸ , one of R ²¹ to R ³⁵ represents -SO ₃ ^- , and one of R ²¹ to R ³⁵ represents a compound of -SO ₂ NHR ¹⁸ .

The compound (2-3) is a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R, in the formula (2). ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , one of R ²¹ to R ³⁵ represents - SO ₃ ^- and at least two of R ²¹ to R ³⁵ represent a compound of -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ .

The compound (2-3) is preferably a compound in which R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ , in the formula (2). _{K, -SO 3 H, -SO 2} N (R 18) R 19 or -SO ₂ NHR ^18, and R ²¹ ~ R ³⁵ represents one of those _{^{-SO 3 -, R 21 ~ R}} 35 in at least two of A compound representing -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ .

As the compound (2), for example, the following compounds can be mentioned:

These compounds can also be used, for example, by the method disclosed in Japanese Patent Laid-Open No. 2003-201413 or the method according to the method.

When the dye composition of the present invention contains only the compound (1) and the compound (2) as a dye, it is preferably contained in an amount of 1 part by mass or more and 35 parts by mass based on 100 parts by mass of the dye composition. In the following, it is more preferable that the compound (1) is contained in an amount of 1 part by mass or more and 20 parts by mass or less, and particularly preferably 1 part by mass or more and 15 parts by mass or less of the compound (1). Further, the compound (2) is preferably contained in an amount of 65 parts by mass or more and 99 parts by mass or less, more preferably 80 parts by mass or more and 99 parts by mass or less of the compound (2). Furthermore, it is preferable to contain the compound (1) in an amount of 1 part by mass or more and 35 parts by mass or less, and the compound (2) is 65 parts by weight or more and 99 parts by mass or less.

Further, the dye composition of the present invention may further comprise a compound represented by the formula (3) (hereinafter sometimes referred to as "compound (3)"):

(In the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₂ N(R ¹⁸ )R ¹⁹ Or -SO ₂ NHR ¹⁸ ).

The compound (3) is preferably a compound wherein, in the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ or -SO ₂ NHR ¹⁸ , and at least R ⁴¹ to R ⁵⁵ Two compounds representing -SO ₂ NHR ¹⁸ .

Further, the compound (3) is preferably a compound represented by the following formula (3a):

(In the formula (3a), R ^{41 '} independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ ).

As the compound (3), for example, the following compounds can be mentioned:

When the dye composition of the present invention contains the compound (1), the compound (2), and the compound (3) as a dye, it is preferred to contain the compound (1) in an amount of 1 part by mass or more based on 100 parts by mass of the dye composition. 15 parts by mass or less, more preferably 2 parts by mass or more and 13 parts by mass or less of the compound (1). Further, the compound (2) is preferably 65 parts by mass or more and 98 parts by mass or less, more preferably 70 parts by mass or more and 95 parts by mass or less. The compound (3) is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more and 17 parts by mass or less. Furthermore, the compound (1) is preferably 1 part by mass or more and 15 parts by mass or less, the compound (2) is 65 parts by mass or more and 98 parts by mass or less, and the compound (3) is 1 part by mass or more and 20 parts by mass or less. .

The compound (1), the compound (2), and the compound (3) can be produced, for example, by chlorinating a dye or a dye intermediate having -SO ₃ H by a usual method, and then obtaining the obtained -SO ₂ Cl The pigment or pigment intermediate is reacted with an amine represented by R ¹⁸ -NH ₂ or R ¹⁸ -NHR ¹⁹ . Further, it can be produced by chlorinating a dye produced by the method disclosed in the upper right column to the lower left column of page 3 of Japanese Patent Laid-Open No. 3-78702, in the same manner as described above. Reacts with an amine.

The coloring composition of the present invention comprises the above dye composition (A-1) and pigment (A-2).

Examples of the pigment (A-2) include organic pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, and the like; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments. Among them, it is preferred to contain at least one pigment selected from the group consisting of C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, and 15:6, and particularly preferably C.I. Pigment Blue 15:6. These pigments may be used singly or in combination of two or more.

The organic pigment may be subjected to the following treatments as needed: rosin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, graft treatment of a surface of the pigment with a polymer compound, etc., using sulfuric acid The micronization treatment such as the micronization method, the cleaning treatment using an organic solvent or water for removing impurities, the treatment for removing ionic impurities by an ion exchange method or the like.

The organic pigment preferably has a uniform particle size. By performing a dispersion treatment with a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more.

In the case of using a pigment dispersant, the amount thereof is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less per 1 part by mass of the pigment (A-2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained, which is preferable.

The content ratio (mass ratio) of the dye composition (A-1) to the pigment (A-2) is preferably from 1:99 to 99:1, more preferably from 1:99 to 60:40, and further preferably. It is 3:97~50:50, and even better is 5:95~40:60. By setting such a ratio, it is easy to achieve the optimization of the transmission spectrum, and a coating film and a pattern having high contrast and high brightness can be obtained, and heat resistance and chemical resistance are improved.

It is particularly preferred that the mass ratio of the dye composition (A-1) to the C.I. Pigment Blue 15:6 is from 3:97 to 50:50.

The colored photosensitive resin composition of the present invention comprises the above dye composition (A-1), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E).

The content of the dye composition (A-1) is from 0.3 to 30% by mass, preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, based on the solid content of the colored photosensitive resin composition.

Moreover, when the pigment (A-2) is contained, the total amount of the dye composition (A-1) and the pigment (A-2) is 0.3 to 50 mass with respect to the solid content of the colored photosensitive resin composition. %, preferably from 1 to 40% by mass, more preferably from 1 to 30% by mass.

Further, when the pigment (A-2) is CI Pigment Blue 15:6, the total amount of the dye composition (A-1) and CI Pigment Blue 15:6 is relative to the solid content of the colored photosensitive resin composition. It is 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

Here, the solid content component means the total of the components other than the solvent in the colored photosensitive resin composition.

The alkali-soluble resin (B) is not particularly limited, and any resin can be used.

For example, the alkali-soluble resin (B) contains a constituent unit having a carboxyl group. As the structural unit having a carboxyl group, it is preferred to have a structural unit derived from (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

In all the structural units constituting the alkali-soluble resin (B), the content of the structural unit derived from (meth)acrylic acid is preferably 16 mol% or more, 40 mol% or less, more preferably 18 mol%. Above, 38% or less. When the content of the structural unit derived from (meth)acrylic acid is within this range, the solubility in the non-pixel portion becomes good at the time of development. Further, there is a tendency that the residue does not remain in the non-pixel portion after development.

Examples of the other monomer which is a structural unit other than the structural unit derived from (meth)acrylic acid which constitutes the alkali-soluble resin (B) include an aromatic vinyl compound, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid. Aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, vinyl carboxylates, unsaturated ethers, vinyl cyanide compounds, unsaturated decylamines, unsaturated quinones, aliphatic conjugates The olefin is a macromonomer having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the terminal of the polymer molecular chain, a unit represented by the formula (II), a unit represented by the formula (III), and the like.

(In the formulae (II) and (III), R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom or a methyl group. R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

Specific examples of the alkali-soluble resin (B) include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, and methacrylic acid/benzyl methacrylate. /methacrylic acid Ester copolymer, methacrylic acid/styrene/benzyl methacrylate/N-phenyl maleimide copolymer, methacrylic acid/component represented by formula (II) in formula (II), R ⁵³ represents methyl, R ⁵⁴ represents a hydrogen atom) / benzyl methacrylate copolymer, represented by the formula (constituent II) represented by the (wherein, in this formula (II) is, R ⁵³ a methyl group, R ⁵⁴ represents a hydrogen atom) / benzyl methacrylate copolymer, methacrylic acid / a constituent represented by the formula (III) (wherein, in the formula (III), R ⁵⁵ represents a methyl group, R ⁵⁶ represents a hydrogen atom) / styrene copolymer / tricyclodecyl methacrylate copolymer, an alkali-soluble resin represented by the formula (IV) (B)

An alkali-soluble resin (B) having a constituent represented by the formula (II), for example, methacrylic acid / a constituent represented by the formula (II) (wherein, in the formula (II), R ⁵³ represents a methyl group / / benzyl methacrylate copolymer can be obtained by polymerizing methacrylic acid with benzyl methacrylate to obtain a copolymer, and then obtaining the obtained copolymer with the compound represented by formula (V) Carry out the reaction.

(In the formula (V), the meaning of R ⁵⁴ is the same as described above).

Methacrylic acid / a constituent represented by the formula (III) (wherein, in the formula (III), R ⁵⁵ represents a methyl group) / a styrene copolymer / a tricyclodecyl methacrylate copolymer can be made The compound represented by the formula (VI) is obtained by reacting a copolymer of benzyl methacrylate, methacrylic acid and tricyclodecyl monomethacrylate.

The copolymerization is usually carried out in a solvent using a polymerization initiator.

As the polymerization initiator, for example, an azo compound such as 2,2'-azobisisobutyronitrile or 2,2'-azobis(2-methylpropionate) can be used. A peroxide such as benzamidine or a third butyl peroxide.

The solvent may be any one which dissolves each monomer, and for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate may be used. A glycol ether ester of the type, a solvent exemplified as the solvent (E) described below, and the like.

The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator, the boiling point of the solvent and the monomer, and the like.

Further, the side chain of the copolymer obtained as described above may be modified with a compound having a polymerizable group to prepare a photosensitive alkali-soluble resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added.

Examples of the catalyst include tris(dimethylaminomethyl)phenol and the like. Further, an additive for preventing side reactions may be added. Examples of the additive include hydroquinone and the like.

Further, examples of the alkali-soluble resin (B) include the following copolymers [K1] to [K4].

[K1] an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (B1) (hereinafter sometimes abbreviated as "(B1)")) and a monomer (B2) having a cyclic ether structure having a carbon number of 2 to 4. (Hereinafter, it may be simply referred to as "(B2)").

[K2] A copolymer obtained by polymerizing (B1), (B2) and a monomer (B3). Here, the monomer (B3) (hereinafter sometimes abbreviated as "(B3)") is a monomer which can be copolymerized with (B1) and/or (B2) and is not (B1) and/or (B2). .

[K3] A copolymer obtained by reacting a part of a carboxyl group derived from (B1) with a cyclic ether structure derived from (B2) having a carbon number of 2 to 4 in the copolymer of (B1) and (B3).

[K4] a copolymer of (B1) and (B3).

Among them, a copolymer obtained by polymerizing at least (B1) and (B2) is preferred.

Examples of (B1) include an aliphatic unsaturated carboxylic acid and/or an aliphatic unsaturated carboxylic anhydride. Specific examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Acids; and anhydrides of such unsaturated dicarboxylic acids; succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, phthalic acid mono [2-(methyl) propylene oxy oxy group B Unsaturated mono[(meth)acryloxyalkyl]esters of dibasic or higher polycarboxylic acids; etc.; 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-di Carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2 - alkene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] Bicyclo[2.2.1]hept-2-ene containing a carboxyl group or a carboxylic acid anhydride such as hept-2-ene anhydride (bicycloheptylene dicarboxylic anhydride); and α-(hydroxymethyl) acrylate or the like An unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among them, acrylic acid, methacrylic acid or maleic anhydride is preferable in terms of copolymerization reactivity and alkali solubility.

These may be used singly or in combination of two or more. In addition, in the present specification, the compounds, components, agents, and the like exemplified may be used singly or in combination of two or more kinds unless otherwise specified.

(B2), for example, may have a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an ethylene oxide group, an oxypropylene group, and a tetrahydrofuran group), and further Good is a monomer with an unsaturated bond. As (B2), a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenic carbon-carbon unsaturated bond is more preferable, and a cyclic ether structure having a carbon number of 2 to 4 is particularly preferable. And a monomer of (meth)acryloxyloxy group.

Examples of (B2) include a monomer having an oxirane group, a monomer having an oxypropylene group, a monomer having a tetrahydrofuran group, and the like.

The above monomer having an oxirane group means, for example, a polymerizable compound having at least one selected from the group consisting of an aliphatic oxirane group and an alicyclic oxirane group.

The monomer having an oxiranyl group is preferably a compound having at least one selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group, and having an unsaturated bond.

The aliphatic oxirane group means a group having a structure in which a chain olefin is epoxidized.

Specific examples of the compound having an aliphatic oxirane group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethyl shrinkage of (meth)acrylic acid. A compound represented by the following formula (VI), which is disclosed in Japanese Laid-Open Patent Publication No. Hei 7-248625, and the like.

(In the formula (VI), R ⁶¹ to R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group, and m ¹ is an integer of 1 to 5).

Examples of the compound represented by the formula (VI) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinyl group. Benzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidoxymethylstyrene, 2, 4-diglycidoxymethylstyrene, 2,5-diglycidoxymethylstyrene, 2,6-diglycidoxymethylstyrene, 2,3,4-triglycidyloxy Methylstyrene, 2,3,5-triglycidoxymethylstyrene, 2,3,6-triglycidoxymethylstyrene, 3,4,5-triglycidyloxy Styrene, 2,4,6-triglycidoxymethylstyrene, and the like.

The alicyclic oxiranyl group means a group having a structure in which a cyclic olefin is epoxidized.

Examples of the monomer having an alicyclic oxiranyl group include a monomer having an aliphatic monocyclic oxiranyl group, a monomer having an aliphatic polycyclic oxirane group, and the like. The aliphatic monocyclic oxiranyl group means a group having a structure in which a monocyclic cyclic olefin is epoxidized. Moreover, the aliphatic polycyclic oxiranyl group means a group having a structure in which a polycyclic cyclic olefin is epoxidized. The oxiranyl group-containing monomer preferably has at least one selected from the group consisting of an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group, and has an unsaturated bond. The compound is more preferably a compound having at least one selected from the group consisting of an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group, and having a (meth) propylene fluorenyloxy group.

Examples of the monocyclic cyclic olefin include cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Among them, preferred are compounds having a carbon number of 5 to 7.

Specific examples of the monomer having an aliphatic monocyclic oxiranyl group include vinylcyclohexene oxide (1,2-epoxy-4-vinylcyclohexane) (for example, Celloxide) 2000; manufactured by Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.).

Examples of the polycyclic cyclic olefin include dicyclopentene, tricyclodecene, and decane. Alkene Alkene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, bicyclododecene, tricyclododecene, and the like.

Among them, preferred are compounds having a carbon number of 8 to 12.

As the monomer having an aliphatic polycyclic oxiranyl group, for example, it can be selected from a 3,4-epoxy group derived from acrylic acid. Ester, 3,4-epoxy reduction of methacrylic acid And an ester, a compound represented by the formula (VII), and at least one compound of the group consisting of the compound represented by the formula (VIII).

[In the formula (VII) and the formula (VIII), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group.

X ⁷¹ and X ⁷² each independently represent a single ^{bond, -X 73 -, * - X} 73 -OX 74 -, * - X 73 -SX 74 -, * - X 73 -NH-X 74 -. X ⁷³ and X ⁷⁴ represent an alkanediyl group having a carbon number of 1 to 6.

* indicates the bond with O].

Specific examples of R ⁷¹ and R ⁷² include a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or t-butyl; , 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methyl A hydroxy-substituted alkyl group such as ethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl or 4-hydroxybutyl.

Among them, preferred are a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group. More preferred are hydrogen atoms and methyl groups.

Examples of the alkanediyl group include a methylene group, an exoethyl group, a 1,2-propyldiyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, and 1, 6-hexanediyl and the like.

As X ¹ and X ² , preferred are a single bond, a methylene group, an exoethyl group, a *-CH ₂ -O- (* represents a bond to O) group, and *-CH ₂ CH ₂ - The O-group is more preferably a single bond or a *-CH ₂ CH ₂ -O- group.

And at least one compound selected from the group consisting of the compound represented by the formula (VII) and the compound represented by the formula (VIII), preferably selected from the group consisting of the compound represented by the following formula (VII') At least one compound of the group consisting of the compounds represented by the formula (VIII').

In the formulae (VII') and (VIII'), R ^{71 '} and R ^{72' have} the same meanings as R ⁷¹ and R ⁷² described above, respectively.

Examples of the compound represented by the formula (VII) include a compound represented by the formula (VII-1) to the formula (VII-15). Preferred are formula (VII-1), formula (VII-3), formula (VII-5), formula (VII-7), formula (VII-9), formula (VII-11) to formula (VII- 15). More preferred are formula (VII-1), formula (VII-7), formula (VII-9), and formula (VII-15).

Examples of the compound represented by the formula (VIII) include a compound represented by the formula (VIII-1) to the formula (VIII-15). Preferred are formula (VIII-1), formula (VIII-3), formula (VIII-5), formula (VIII-7), formula (VIII-9), formula (VIII-11) to formula (VIII- 15). More preferred are formula (VIII-1), formula (VIII-7), formula (VIII-9), formula (VIII-15).

At least one compound selected from the group consisting of the compound represented by the formula (VII) and the compound represented by the formula (VIII) can be used alone. Also, it can be mixed at any ratio. In the case of mixing, the mixing ratio is in molar ratio, preferably formula (VII): formula (VIII) is 5:95 to 95:5, more preferably 10:90 to 90:10, Further better is 20:80~80:20.

The monomer having an oxypropylene group means, for example, a polymerizable compound having an oxypropylene group. The monomer having an oxypropylene group is preferably a compound having an oxypropylene group and an unsaturated bond, more preferably a compound having an oxypropylene group and having a (meth)acryloxy group.

Specific examples of the monomer having an oxypropylene group include 3-methyl-3-methylpropenyloxymethyloxetane and 3-methyl-3-propenyloxymethyl group. Propylene oxide, 3-ethyl-3-methylpropenyloxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methyl propylene Ethoxyethyl propylene oxide, 3-methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide or 3-ethyl- 3-propenyloxyethyl propylene oxide and the like.

The monomer having a tetrahydrofuran group means, for example, a polymerizable compound having a tetrahydrofuranyl group. The monomer having a tetrahydrofuranyl group is preferably a compound having a tetrahydrofuranyl group and an unsaturated bond, more preferably a compound having a tetrahydrofuranyl group and having a (meth)acryloxy group.

Specific examples of the monomer having a tetrahydrofuran group include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of the copolymerizable monomer (B3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. (meth)acrylic acid alkyl esters such as (butyl) (meth)acrylate; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0 ^2,6 ]癸-8-yl ester (in the technical field, as a customary name, called dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate (meth)acrylic acid (alkyl) (meth)acrylic acid alkyl esters; (meth)acrylic acid phenyl esters, (meth)acrylic acid benzyl esters and other (meth)acrylic acid aryl esters; diethyl maleate, anti a dicarboxylic acid diester such as diethyl phthalate or diethyl itaconate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; [2.2.1] Hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2. 1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-A Oxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5 ,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6- Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5- Third butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1] 2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-methylbutyleneimine, N-ethylbutylene N-alkyl maleimide, such as amine, N-propyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide N-cycloalkyl maleimide, such as N-cyclooctylmethyleneimine, N-adamantyl maleimide, N-lower N-crosslinked carbocyclic group substituted with maleimide, such as maleimide, N-aryl maleimide, N-phenylmethyleneimine, etc.; N N-aralkylalkyleneimine, such as benzyl maleimide, N-butylene imino-3-butanediimide benzoate, N-butyl Dimethylene imino-4-butylimide imine butyrate, N-butyl quinone imido-6-m-butyleneimine hexanoate, N-butyl quinone imine a dicarbenium imine derivative such as 3-methyleneimine propionate or N-(9-acridinyl) maleimide; and styrene, α-methylstyrene, M-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl ester, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, in terms of copolymerization reactivity and alkali solubility, styrene, N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl are preferred. A cis-butenylene imine, a bicyclo [2.2.1] hept-2-ene, and the like.

The copolymer [K1]~[K4] can be referred to, for example, the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Issue: Chemical Tongren (Shares), 1st Edition, 1st Print, March 1, 1972 It is manufactured by the method disclosed in the publication and the cited documents disclosed in the document.

Specifically, the monomers (B1) and (B2) constituting the copolymer, a specific amount of (B3), a polymerization initiator, and a solvent are optionally charged in a reaction vessel, and oxygen is replaced by nitrogen gas. The mixture was stirred, heated, and kept warm in the absence of oxygen, thereby obtaining a polymer. The polymerization conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

As the polymerization initiator and solvent used herein, any of a polymerization initiator and a solvent which are generally used in the field can be used. For example, a polymerization initiator, a solvent, and the like exemplified in the present specification can be used.

Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or a solid (powder) extractor by a method such as reprecipitation.

In particular, by using the following solvent as a solvent in the above polymerization, the solution after the reaction can be used as it is, so that the production step can be simplified.

The ratio of the respective monomers constituting the copolymer [K1] to the total number of moles of the monomers constituting the copolymer [K1] is preferably in the following range.

(B1) 5~95% by mole, more preferably 10~90% by mole

(B2) 5 to 95% by mole, more preferably 10 to 90% by mole.

Further, the ratio of the respective monomers constituting the copolymer [K2] to the total number of moles of the monomers constituting the copolymer [K2] is preferably in the following range.

(B1) 2~40% by mole, more preferably 5~35% by mole

(B2) 2~95% by mole, more preferably 5~80% by mole

(B3) 1 to 65 mol%, more preferably 1 to 60 mol%.

The copolymer [K3] can be produced via a two-stage process.

First, (B1) and (B3) were copolymerized in the same manner as the above method to obtain a copolymer.

In this case, the ratio of each monomer to the total number of moles of the monomers constituting the copolymer is preferably in the following range.

(B1) 5~50 mol%, preferably 10~45 mol%

(B3) 50 to 95% by mole, preferably 55 to 90% by mole.

Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (B1) of the copolymer of (B1) and (B3) is reacted with a cyclic ether derived from (B2).

To this end, the atmosphere in the flask is continuously replaced with nitrogen by air, and (B2), a reaction catalyst, a polymerization inhibitor, and the like are placed in the flask, and then the reaction is continued at, for example, 60 to 130 ° C for 1 to 10 hours. The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the calorific value generated by the polymerization.

At this time, the number of moles of (B2) relative to the number of moles of (B1) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and particularly preferably 15 to 70 mol. ear%.

The reaction catalyst is preferably used, for example, as a reaction catalyst for a carboxyl group with an ethylene oxide group, an oxypropylene group or a tetrahydrofuran group. Specifically, tris(dimethylaminomethyl)phenol or the like is exemplified.

The amount of the reaction catalyst used is, for example, 0.001 to 5% by mass based on the total amount of (B1) to (B3).

Examples of the polymerization inhibitor include hydroquinone and the like.

The amount of the polymerization inhibitor to be used is, for example, 0.001 to 5% by mass based on the total amount of (B1) to (B3).

The ratio of the respective monomers constituting the copolymer [K4] to the total number of moles of the monomers constituting the copolymer [K4] is preferably in the following range.

(B1) 2~40% by mole, more preferably 5~35% by mole

(B2) 60~98 mole%, and more preferably 65~95 mole%.

The polystyrene-equivalent weight average molecular weight of the copolymer [K1] to [K4] is preferably 3,000 to 100,000, more preferably 5,000 to 50,000.

The dispersion (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer [K1] to [K4] are preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0.

The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, particularly preferably 7,000 to 28,000. When the molecular weight is in the above range, the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developer is good, and the resolution tends to increase.

In addition, the weight average molecular weight is a value measured by, for example, a GPC method (gel-permeation chromatography), and specifically, a value measured by the measurement conditions disclosed in the examples, etc. .

The acid value of the alkali-soluble resin (B) is preferably from 50 to 150, more preferably from 60 to 135, particularly preferably from 70 to 135. The acid value here is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin (B), and can usually be determined by titration using an aqueous potassium hydroxide solution.

The content of the alkali-soluble resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, particularly preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. . When the content of the alkali-soluble resin (B) is within this range, a pattern can be formed, and the resolution and the residual film ratio tend to increase.

The photopolymerizable compound (C) is not particularly limited as long as it can be polymerized by an active radical, an acid or the like which is generated by irradiating light to the photopolymerization initiator (D). For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be given.

The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, and Pentaerythritol hexamethacrylate or the like. The photopolymerizable compound (C) may be used singly or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55, based on the solid content of the colored photosensitive resin composition. quality%. When the content of the photopolymerizable compound (C) is within the above range, the curing tends to proceed sufficiently, and the film thickness ratio before and after the development increases, and it is difficult to undercut the pattern and the adhesion tends to be good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D).

The photopolymerization initiator (D) may, for example, be a living radical generator or an acid generator. The living radical generator generates active radicals by irradiating light. Further, the acid generator generates an acid by irradiating light.

Examples of the living radical generating agent include an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, and 9-oxosulfuric acid. Compound, three A compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include diethoxyacetophenone and 2-methyl-2- Lolinyl-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2-hydroxy-2- Methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1 An oligomer of -methylvinyl)phenyl]propan-1-one, etc., preferably exemplified by 2-methyl-2- Orolinyl-1-(4-methylsulfanylphenyl)propan-1-one and the like.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyl group. Phenyl sulfide, 3,3', 4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As the above 9-oxygen sulfur A compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

As the above three The compound is, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the oxime-based compound include an O-fluorenyl fluorene-based compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butane- 1-keto-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-B -6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzylidenyl}-9H-indazol-3-yl] Ethane-1-imine and the like.

Further, as the living radical generating agent, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4,4' may also be used. ,5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, camphorquinone , phenylglyoxylate methyl ester, titanocene compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxyphenyldimethylate. Base p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, An anthracene salt such as phenylhydrazine p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate, or a nitrobenzyl tosylate or a benzoin tosylate.

Further, in the above-mentioned compound as the above-mentioned living radical generating agent, a compound which generates an acid while generating an active radical, for example, three A photopolymerization initiator can also be used as the acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30% by mass, more preferably from 1 to 20% by mass, based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above range, high sensitivity is achieved, exposure time is shortened, and productivity is improved.

The coloring photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (F). The photopolymerization initiation aid (F) is usually used in combination with a photopolymerization initiator (D) to promote polymerization of a polymerizable photopolymerizable compound by a photopolymerization initiator, or a sensitizer. .

Examples of the photopolymerization initiation assistant (F) include an amine compound, an alkoxy ruthenium compound, and 9-oxosulfuric acid. A compound or the like.

Examples of the above amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as rice ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-double (Ethylmethylamino)benzophenone or the like, among which 4,4'-bis(diethylamino)benzophenone is preferred.

Examples of the alkoxy oxime-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2- Ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxygen sulfur A compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

The photopolymerization initiation aid (F) may be used singly or in combination of two or more. Further, the photopolymerization initiation aid (F) can also be used as a commercially available photopolymerization initiation aid (F), and for example, the product name "EAB-F" (Batugu Valley Chemical Industry Co., Ltd.) can be used. Company manufacturing) and so on.

The combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) in the coloring photosensitive resin composition of the present invention may, for example, be diethoxyacetophenone/4,4'- Bis(diethylamino)benzophenone, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-benzene Propane-1-one/4,4'-bis(diethylamino)benzophenone, benzoin dimethyl ketal/4,4'-bis(diethylamino)benzophenone , 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)benzene Oligomer of propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one/4,4'-bis(diethylamino)benzophenone, etc., preferably exemplified by 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one / 4,4'-bis(diethylamino)benzophenone.

In the case of using the photopolymerization initiation assistant (F), it is preferably used in an amount of from 0.01 to 10 mol per 1 mol of the photopolymerization initiator (D), more preferably 0.01~5 moles.

The colored photosensitive resin composition of the present invention contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used.

For example, it can be derived from esters (solvents containing -COO-), ethers other than esters (solvents containing -O-), ketones other than esters (solvent containing -CO-), alcohols, aromatic hydrocarbons It is selected for use in the class, guanamine, N-methylpyrrolidone, dimethyl alum, and the like.

Examples of the esters include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and acetic acid. Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, B Methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxy acetate Butyl ester, cyclohexanol acetate, γ-butyrolactone, and the like.

Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol; tetrahydrofuran , tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, Anisole, phenethyl ether, methyl anisole, and the like.

Examples of the ketones include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

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

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the above guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

The content of the solvent (E) in the coloring photosensitive resin composition is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on 100% by mass of the coloring photosensitive resin composition. In other words, it is preferable to adjust the content of the solvent (E) so that the solid content component is 5 to 30% by mass, preferably 8 to 25% by mass, based on 100% by mass of the colored photosensitive resin composition. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and the color density is sufficient when the color filter is formed. Therefore, the display characteristics tend to be good, which is preferable.

The coloring photosensitive resin composition of the present invention may further contain a surfactant (G). The surfactant (G) is at least one selected from the group consisting of a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.

Examples of the polyfluorene-based surfactant include a surfactant having a decane bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Emu Oil SH8400 (trade name: Toray Silicone; Toray Dow Corning (manufactured by Corning), 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 Japan contract company) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, and Megafac R30 ( DIC (manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass) (manufacturing), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

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

The content of the surfactant (G) is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the mass fraction of the coloring photosensitive resin composition. When the content of the surfactant (G) is in the above range, the flatness of the coating film tends to be good, which is preferable.

The colored photosensitive resin composition of the present invention is preferably a negatively colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention can be preferably used for forming a color filter, a coating film or a colored pattern, and can obtain a good color pattern such as color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like. Color filter. Moreover, it can be used in an optical film, an array substrate, or the like having such a color filter or a colored pattern as a part of the constituent parts, and can be used to provide the color filter, the coating film, or the colored pattern. A display device such as an optical film and/or an array substrate is, for example, a liquid crystal display device, an organic EL (Electroluminescence) device, or a solid-state image sensor.

As a method of forming a color filter, a coating film, or a coloring pattern using the coloring photosensitive resin composition of this invention, the following method, etc. are apply|coated, and the coloring photosensitive resin composition of this invention is apply|coated on a board|substrate or other resin layer. (For example, in the other colored photosensitive resin composition layer formed on the substrate, etc.), a volatile component such as a solvent is removed/dried to form a colored layer, and the colored layer is exposed through a mask, and then developed. Method; and a method of using an ink jet machine that does not require photolithography.

The film thickness of the coating film at this time is not particularly limited, and can be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, more preferably 1 to 6 μm. .

Examples of the coating method of the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a CAP. (Calcium Phosphate, calcium phosphate) coating method, die coating method, and the like. Further, a dip coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater can be used. A slit coater (sometimes referred to as a die coater, a curtain flow coater, or a spinless coater) The cloth machine is coated. Among them, it is preferred to apply using a spin coater.

Examples of the solvent removal/drying include natural drying, air drying, and vacuum drying. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. The drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

The drying under reduced pressure is preferably carried out at a temperature of 20 to 25 ° C under a pressure of 50 to 150 Pa.

Example

Hereinafter, the dye composition, the colored photosensitive resin composition, and the color filter of the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise stated.

Synthesis Example 1: Synthesis of Dye A1

410 parts of chloroform and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 37 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. Further, 4 parts of sulfinium chloride was added to the reaction mixture, followed by a reaction at 35 ° C for 1.5 hours. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 89 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 290 parts of methanol and 20 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 306 parts of ion-exchanged water to be crystallized. The crystals obtained after filtration were washed sequentially with 300 parts of a 50% aqueous methanol solution, 1000 parts of deionized water at 70 ° C, and 300 parts of deionized water at 20 ° C. It was dried under reduced pressure at 60 ° C for one day to obtain 51 parts of a dye A1 as a purple-red solid.

Each compound represented by the formulas (1), (2), and (3) contained in the dye A1 was chemically identified by LC-MS (liquid chromatography-mass spectrometry). The results of the LC-MS analysis are shown below.

Further, the measurement conditions of LC-MS are as follows.

Device: Shimadzu LC-10A

Column: Wakosil II 3C18HG (3 μm, 3 mm Φ × 150 mm)

Mobile Phase A: 0.1% TMAB (Trimethylamine borane, trimethylamine borane) / water: acetonitrile (9:1)

Solution B: 0.1% TMAB / water: acetonitrile (1:9)

Gradient (B solution)

Initial concentration of B: 20%

20%→(30 minutes)→60%→(5 minutes)→100% (for 10 minutes)

Wavelength: 250 nm

Column temperature: 40 degrees

Flow rate: 0.5 mL/min

Injection volume: 5 μL

MASS

Device: HP LC/MSD

Ionization: ESI+

Scanning range: 100-1500

Fragmentor (fragmentation voltage): 120V

Drying Gas: 350 ° C

Compound (1): Found ([M+H] ⁺ ): 655.2

Calculated value (Exact Mass): 654.2

Compound (2-1): Found ([M+H] ⁺ ): 682.2

Calculated value (Exact Mass): 681.2

Compound (2-2): Found ([M+H] ⁺ ): 766.3

Calculated value (Exact Mass): 765.3

Compound (2-3): Found ([M+H] ⁺ ): 957.4

Calculated value (Exact Mass): 956.4

Compound (3): Found (M ⁺ ): 877.5.

Calculated value (Exact Mass): 877.4

Further, for each compound represented by the formulas (1), (2), and (3), the area ratio of each peak is calculated by the area percentage method of LC, and the relative formula is determined according to the following formula. A total of 100 parts of each compound is measured. The results are shown in Table 1.

Compound (1) Hold time: 14.0~16.0 minutes

Compound (2-1) Hold time: 16.0~25.0 minutes

Compound (2-2) Hold time: 25.0~26.5 minutes

Compound (2-3) Hold time: 26.5~31.0 minutes

Compound (3) Hold time: 31.0~41.0 minutes

Synthesis Example 2: Synthesis of Dye A2

410 parts of chloroform and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 37 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. Further, 4 parts of sulfinium chloride was added to the reaction mixture, followed by a reaction at 35 ° C for 1 hour. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 89 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 260 parts of methanol and 25 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 396 parts of ion-exchanged water to be crystallized. The crystals obtained after filtration were washed sequentially with 300 parts of a 50% aqueous methanol solution, 1000 parts of deionized water at 70 ° C, and 300 parts of deionized water at 20 ° C. It was dried under reduced pressure at 60 ° C for one day to obtain 65 parts of dye A2 as a purple-red solid.

Each compound contained in A2 was chemically identified in the same manner as in Synthesis Example 1, and the content was calculated. The results are shown in Table 1.

Synthesis Example 3: Synthesis of Dye A3

220 parts of acetonitrile and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 35 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 69 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 290 parts of methanol and 16 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 306 parts of ion-exchanged water to be crystallized. The crystals obtained after filtration were washed successively with 300 parts of 50% aqueous methanol solution, 800 parts of 5% hydrochloric acid aqueous solution, and 300 parts of deionized water, and then dried under reduced pressure at 60 ° C for one day to obtain 44 parts of purple. Red solid dye A3.

Each compound contained in A3 was chemically identified in the same manner as in Synthesis Example 1, and the content was calculated. The results are shown in Table 1.

Synthesis Example 4: Synthesis of Dye A4

410 parts of chloroform and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 37 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. Then, 4 parts of sulfinium chloride was further added, and the reaction was continued at 35 ° C for 1 hour. Thereafter, the reaction mixture was cooled, and 34 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 89 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 260 parts of methanol and 25 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 415 parts of ion-exchanged water to be crystallized. The crystals obtained after filtration were washed successively with 300 parts of 50% aqueous methanol solution, 800 parts of 5% hydrochloric acid aqueous solution, and 300 parts of deionized water, and then dried under reduced pressure at 60 ° C for one day to obtain 42 parts of purple. Red solid dye composition A4.

Each compound contained in A4 was chemically identified in the same manner as in Synthesis Example 1, and the content was calculated. The results are shown in Table 1.

Synthesis Example 5: Synthesis of Dye A5

410 parts of chloroform and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 41 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. Thereafter, the reaction mixture was cooled, and 33 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 69 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 290 parts of methanol and 16 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 306 parts of ion-exchanged water to be crystallized. The crystals obtained after filtration were washed successively with 150 parts of 50% aqueous methanol solution and 200 parts of deionized water at 20 ° C, and then dried under reduced pressure at 60 ° C for one day to obtain 53 parts of dye A5 as a purple-red solid. .

Each compound contained in A5 was chemically identified in the same manner as in Synthesis Example 1, and the content was calculated. The results are shown in Table 1.

Synthesis Example 6: Synthesis of Dye A6

410 parts of chloroform and 28 parts of dimethylformamide were mixed in a vessel equipped with a cooling tube and a stirring device. To the mixed solution, 37 parts of sulfite chlorine was added dropwise at 10 ° C for 20 minutes. After the completion of the dropwise addition, the reaction was carried out for 30 minutes in a state of heat retention. 57 parts of Acid Red 289 (manufactured by Sino-foreign Chemicals Co., Ltd.) was added to the reaction mixture over 15 minutes, and reacted at 35 ° C for 3 hours. Then, 4.1 parts of sulfinium chloride was further added, and the reaction was continued at 35 ° C for 1.5 hours. Thereafter, the reaction mixture was cooled, and 34 parts of 2-ethylhexylamine was added dropwise at 10 ° C, followed by dropwise addition of 69 parts of triethylamine. After the dropwise addition, the reaction was carried out at room temperature for 15 hours. The reaction mixture was concentrated, and after adding 200 parts of methanol, it was concentrated again until the amount of liquid became about half. Further, 290 parts of methanol and 16 parts of acetic acid were added and reacted for 30 minutes. The reactant was poured into 306 parts of ion-exchanged water to be crystallized. The obtained crystals were sequentially washed with 300 parts of 50% aqueous methanol solution, 500 parts of deionized water at 50 ° C, and 300 parts of deionized water at 20 ° C, and then dried under reduced pressure at 60 ° C for one day. 51 parts of dye A6 as a purplish red solid.

Each compound contained in A6 was chemically identified in the same manner as in Synthesis Example 1, and the content was calculated. The results are shown in Table 1.

Synthesis Example 7: Synthesis of Resin B1

Nitrogen gas was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer at 0.02 L/min to form a nitrogen atmosphere, and then 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, it was dissolved in 84 parts of methacrylic acid, 336 parts of 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I) and formula (II) The compound shown was mixed in a molar ratio of 50:50 by mole and 140 parts of ethyl lactate, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel. On the other hand, using another dropping funnel, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 95 parts of ethyl lactate over 4 hours. The resulting solution was added dropwise to the flask. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 8.0 × 10 ³ , a degree of dispersion of 2.5, and a solid content of 48. %, resin solution B1 having an acid value of 50 mg-KOH/g.

The measurement of the weight average molecular weight in terms of polystyrene of the above resin was carried out under the following conditions using a GPC method.

Device: HLC-8120GPC (made by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

The concentration of the solid content of the detected liquid: 0.001~0.01% by mass

Injection volume: 50 μL

Detector: RI (refractive index detector)

Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500

(made by Tosoh Co., Ltd.)

Example 1

[Preparation of Colored Photosensitive Resin Composition 1]

(A) Colorant: C. I. Pigment Blue 15: 6 20 parts

Acrylic pigment dispersant 5 parts

Propylene glycol monomethyl ether acetate 137 parts

Mixing, using a bead mill to fully disperse the pigment, and then,

(A) Colorant: Dye A1 3 parts

(B) Resin: resin solution B1 65 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 31 parts

(D) Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure OXE-01; Ciba ( Ciba) Made by Japanese company) 9 copies

(E) solvent; 4-hydroxy-4-methyl-2-pentanone 229 parts

The colored photosensitive resin composition 1 was obtained by mixing.

[Formation of patterns]

The colored photosensitive resin composition 1 was applied by spin coating on a glass substrate (Eagle 2000; manufactured by Corning Co., Ltd.), and then prebaked at 100 ° C for 3 minutes.

After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass mask was set to 100 μm, and then exposed to an atmosphere (TME-150RSK; Topcon) Manufactured) The light was irradiated at an exposure of 150 mJ/cm ² (based on 365 nm).

After irradiating the light, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then placed in an oven at 220 ° C. Post-baking was carried out for 20 minutes to obtain a coating film.

After leaving to stand for cooling, the film thickness of the obtained coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.2 μm.

Example 2~6

A colored photosensitive resin composition and a coating film were obtained in the same manner as in Example 1 except that the dye A1 was changed to the dyes shown in Tables 2 and 3.

[Contrast evaluation]

The coating film on the obtained glass substrate was sandwiched between two polarizing plates (POLAX-38S; manufactured by Luceo), and a contrast measuring device (CT-1; manufactured by Tsusaka Electric Co., Ltd.) was used, and brightness was used. Meter (BM-5A; manufactured by Topcon Technohouse), and the cold cathode tube F10 as a light source measures the brightness of the transmitted light in the parallel polarizer and the brightness in the crossed polarizer, and the parallel polarizer The ratio of the brightness in the middle to the brightness in the crossed polarizer (parallel polarizer/straight polarizer) is set to contrast, and the case where the contrast is 6000 or more is determined as ○. The results are shown in Table 2.

Industrial availability

According to the present invention, a dye composition which can provide a color filter of higher contrast can be provided.

Claims (17)

A dye composition comprising a compound represented by the formula (1), a compound represented by the formula (2), and a compound represented by the formula (3): (In the formulae (1) and (2), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K or -SO ₃ H, one of R ¹ to R ¹⁵ represents -SO ₃ ^- , and R ¹⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 10, and the saturated hydrocarbon group The hydrogen atom may be substituted by a halogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and the -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR. ¹⁷ -, R ¹⁷ represents a hydrogen atom or a monovalent saturated hydrocarbon group having a carbon number of 1 to 10, and R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , -SO ₃ ^- , -SO ₃ Na, -SO ₃ K, -SO ₃ H, -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , one of R ²¹ to R ³⁵ Representing -SO ₃ ^- , and at least one of R ²¹ to R ³⁵ represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ , and R ¹⁸ and R ¹⁹ independently represent a carbon number of 1 to 10 An alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 5 to 10 carbon atoms, or may be bonded to each other to form a heterocyclic ring having a carbon number of 2 to 10, the alkyl group and the The hydrogen atom contained in the cycloalkyl group may be substituted by a halogen atom, a hydroxyl group or a phenyl group, and the alkyl group and the -CH ₂ - contained in the cycloalkyl group may be substituted into -O-, -CO-, -NH- or -NR ¹⁶ -, the aromatic hydrocarbon group and the hydrogen atom contained in the aromatic heterocyclic group may also be a halogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -NO ₂ , -CH= CH ₂ or -CH=CHR ^{16 is} substituted. In the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , - SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ ). The dye composition of claim 1, wherein in the formula (1), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- or -SO ₃ H, and one of R ¹ to R ¹⁵ The person represents -SO ₃ ^- and at least one represents -SO ₃ H. The dye composition of claim 1, wherein in the formula (2), R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₂ N(R ¹⁸ ) One of R ¹⁹ or -SO ₂ NHR ¹⁸ , R ²¹ to R ³⁵ represents -SO ₃ ^- , and at least one represents -SO ₂ N(R ¹⁸ )R ¹⁹ or -SO ₂ NHR ¹⁸ . The dye composition of claim 1, wherein in the formula (3), R ⁴¹ to R ⁵⁵ each independently represent a hydrogen atom, -R ¹⁶ or -SO ₂ NHR ¹⁸ , and at least two of R ⁴¹ to R ⁵⁵ represent - SO ₂ NHR ¹⁸ . The dye composition of claim 1, wherein the content of the compound represented by the formula (1) is 1 part by mass or more and 35 parts by mass or less based on 100 parts by mass of the dye composition, and the compound represented by the formula (2) The content is 65 parts by mass or more and 99 parts by mass or less. The dye composition of claim 1, wherein the content of the compound represented by the formula (1) is 1 part by mass or more and 15 parts by mass or less based on 100 parts by mass of the dye composition, and the compound represented by the formula (2) The content of the compound represented by the formula (3) is from 1 part by mass to 20 parts by mass, and the content is from 65 parts by mass to 98 parts by mass. A colored photosensitive resin composition comprising the dye composition (A-1) of claim 1, an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent ( E). The colored photosensitive resin composition of claim 7, which further comprises a pigment (A-2). The colored photosensitive resin composition of claim 8, wherein the pigment (A-2) is a pigment containing C.I. Pigment Blue 15:6. The colored photosensitive resin composition of claim 9, wherein the mass ratio of the dye composition (A-1) to the C.I. Pigment Blue 15:6 is from 3:97 to 50:50. A coating film formed using the dye composition of claim 1. A color filter formed using the dye composition of claim 1. The color filter of claim 12 is formed by photolithography. A use of the dye composition of claim 1 for producing a color filter. A coloring composition comprising the dye composition (A-1) of claim 1 and a pigment (A-2). The colored composition of claim 15, wherein the pigment (A-2) is a pigment containing C.I. Pigment Blue 15:6. The colored composition of claim 16, wherein the mass ratio of the dye composition (A-1) to the C.I. Pigment Blue 15:6 is from 3:97 to 50:50.