KR20100109415A - Dye composition - Google Patents

Abstract

PURPOSE: A dye composition is provided to easily optimizing the transmission spectra, and to obtain a pattern and a coated layer with the high brightness. CONSTITUTION: A dye composition includes a compound marked with chemical formula 1, and a compound marked with chemical formula 2. In the chemical formulas, R1~R15 are a hydrogen atom, -R, -OH, -OR, -CO2H, -CO2R, -SO3-, -SO3Na, -SO3K or -SO3H, respectively. R21~R35 are the hydrogen atom, -R, -OH, -OR, -CO2H, -CO2R, -SO3-, -SO3Na, -SO3K or -SO3H.

Description

Dye composition {DYE COMPOSITION}

The present invention relates to a dye composition.

Conventionally, various azo pigments, xanthium type pigment | dyes, etc. are used in order to provide desired spectral characteristics and to form a fine coloring pattern with a thin film (for example, patent document 1, patent document 2, etc.). .

In recent years, higher contrast is desired in color filters.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 7-134207

[Patent Document 2]

Japanese Patent Application Laid-Open No. 7-146402

This invention is made | formed in view of the said subject, and an object of this invention is to provide the dye composition which can manufacture a higher contrast color filter.

That is, this invention provides the following [1]-[18].

[One]. The dye composition containing the compound represented by Formula (1), and the compound represented by Formula (2).

[In formula (1) and formula (2),

R ¹ ~R ¹⁵ comprise, each independently, a hydrogen ^{atom, -R 16, -OH, -OR 16} , -CO 2 H, -CO 2 R 16, -SO 3 -, -SO 3 Na, -SO 3 K or denotes a -SO ₃ H, R ¹ ~R ¹⁵ one group of, -SO ₃ ^- represents,

R <^16> represents a C1-C10 monovalent saturated hydrocarbon group, The hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom, the hydroxyl group, or the C1-C10 alkoxy group, and is contained in the said saturated hydrocarbon group. -CH ₂ -to be substituted may be substituted with -O-, -CO- or -NR ^17- , R ¹⁷ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms,

~R ³⁵ R ²¹ comprise, each independently, 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 , and R ²¹ to R ³⁵ One group represents -SO ₃ ^- and R ²¹ to R ³⁵ At least one represents -SO ₂ N (R ¹⁸ ) R ¹⁹ or -SO ₂ NHR ¹⁸ ,

R ^l8 And R ¹⁹ each independently represent a C1-C10 alkyl group, a C3-C30 cycloalkyl group, a C6-C10 monovalent aromatic hydrocarbon group, or a C5-C10 monovalent aromatic heterocyclic group, or mutually May be bonded 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 with a halogen atom, a hydroxy group, or a phenyl group and included in the alkyl group and the cycloalkyl group. -CH ₂ -to be substituted with -O-, -CO-, -NH- or -NR ¹⁶ -may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is a halogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -NO ₂ , -CH = CH ₂ Or -CH = CHR ^16. ]

[2]. Moreover, the dye composition as described in [1] containing the compound represented by Formula (3).

In the formula (3), R ⁴¹ ~R ⁵⁵ is, independently, a hydrogen ^{atom, -R 16, -OH, -OR 16} , -CO 2 H, -CO 2 R 16, -SO 2 N (R 18 each ) R ¹⁹ or -SO ₂ NHR ^18. ]

[3]. In formula ^(1), R 1 ~R ¹⁵ is, independently, a hydrogen atom, -R ^16, -SO ₃ ^- or denotes a -SO ₃ H,

R ¹ to R ¹⁵ The dye composition as described in [1] or [2] in which one represents -SO ₃ ^- and at least one represents -SO ₃ H.

[4]. In formula (2), R ²¹ ~R ³⁵ is, independently, a hydrogen atom, -R ^16, -SO _3, respectively _{^{-, -SO 3 H, -SO 2}} N (R 18) R 19 or -SO ₂ NHR ¹⁸ Indicates,

R ²¹ ~R ³⁵ is one of -SO ₃ ^- shows a further dye as described in any of [1] to [3] at least one represents a ^{_{-SO 2 N (R 18) R}} 19 or -SO ₂ NHR ¹⁸ Composition.

[5]. In formula (3), each of R ⁴¹ to R ⁵⁵ independently represents 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 [2] ] The dye composition as described in any one of [4].

[6]. Content of the compound represented by Formula (1) is 1 mass part or more and 35 mass parts or less with respect to 100 mass parts of dye compositions,

The dye composition as described in any one of [1]-[5] whose content of the compound represented by Formula (2) is 65 mass parts or more and 99 mass parts or less.

[7]. Content of the compound represented by Formula (1) is 1 mass part or more and 15 mass parts or less with respect to 100 mass parts of dye compositions,

Content of the compound represented by Formula (2) is 65 mass parts or more and 98 mass parts or less,

The dye composition as described in any one of [2]-[6] whose content of the compound represented by Formula (3) is 1 mass part or more and 20 mass parts or less.

[8]. Colored photosensitive resin containing the dye composition (A-1) in any one of [1]-[7], alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). Composition.

[9]. Furthermore, the coloring photosensitive resin composition as described in [8] containing a pigment (A-2).

[10]. Pigment (A-2) is a C.I. The coloring photosensitive resin composition as described in [9] which is a pigment containing pigment blue 15: 6.

[11]. Dye composition (A-1) and C.I. The coloring photosensitive resin composition as described in [10] whose mass ratio of pigment blue 15: 6 is 3: 97-50: 50.

[12]. The coating film formed using the coloring photosensitive resin composition in any one of [1]-[7].

[13]. The color filter formed using the coloring photosensitive resin composition in any one of [1]-[7].

[14]. The color filter as described in [13] formed by the photolithographic method.

[15]. Use for manufacturing the color filter of the dye composition as described in any one of [1]-[7].

[l6]. The coloring composition containing the dye composition (A-1) and pigment (A-2) in any one of [1]-[7].

[17]. Pigment (A-2) is a C.I. The coloring composition as described in [16] which is a pigment containing pigment blue 15: 6.

[18]. Dye composition (A-1) and C.I. The coloring composition as described in [17] whose mass ratio of pigment blue 15: 6 is 3: 97-50: 50.

The dye composition (A-1) of the present invention is a compound represented by formula (1) (hereinafter may be referred to as "compound (1)") and a compound represented by formula (2) (hereinafter "compound (2)"). May be referred to).

In addition, in this specification, although it changes with carbon number, unless otherwise indicated, the substituent demonstrated later is the same in both chemical structural formulas. In addition, the thing which can take both a straight chain or a branch includes either.

[In formula (1) and formula (2),

R ¹ ~R ¹⁵ comprise, each independently, a hydrogen ^{atom, -R 16, -OH, -OR 16} , -CO 2 H, -CO 2 R 16, -SO 3 -, -SO 3 Na, -SO 3 K or denotes a -SO ₃ H, R ¹ ~R ¹⁵ one group of, -SO ₃ ^- represents,

R <^16> represents a C1-C10 saturated hydrocarbon group, and the hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom, the hydroxyl group, or the C1-C10 alkoxy group, and is contained in the said saturated hydrocarbon group- CH ₂ -may be substituted with -O-, -CO-, or -NR ^17- ,

R <^17> represents a hydrogen atom or a C1-C10 saturated hydrocarbon group.

~R ³⁵ R ²¹ comprise, each independently, 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 , and R ²¹ to R ³⁵ One group of represents -SO ₃ ^- and R ²¹ to R ³⁵ At least one group represents —SO ₂ N (R ¹⁸ ) R ¹⁹ or —SO ₂ NHR ¹⁸ .

R ^l8 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 heterocyclic group having 5 to 10 carbon atoms, or are bonded to each other; and may form a heterocyclic ring of to 10, the hydrogen atoms contained in the alkyl groups and the cycloalkyl groups, being optionally substituted by a halogen atom, a hydroxyl group or a phenyl group, -CH ₂ contained in the alkyl group and the cycloalkyl group -May be substituted with -O-, -CO-, -NH- or -NR ^16- , and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is a halogen atom, -R ¹⁶ , -OH , -OR ¹⁶ , -NO ₂ , -CH = CH ₂ Or -CH = CHR ^16. ]

Equations (1) and (2) have the same number of + charges and-charges in each compound.

Here, the saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, or a cycloalkyl group having an alkyl group or a cycloalkyl group having a cycloalkyl group optionally combined with these substituents.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, 1-methylpropyl group, 2-methylpropyl group and 1-methylbutyl group , 2-methylbutyl group, 3-methylbutyl group, 2-ethylhexyl group, nonyl group, decanyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, etc. Can be mentioned.

As a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclo decanyl group, etc. are mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, tert-butoxy group and 1-methylbutoxy group , 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, n-pentyloxy group, n-hexyl ox The time period, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, etc. are mentioned.

As an aromatic hydrocarbon group, the aryl group, an aralkyl group, the aryl group which has an alkyl group, etc. are mentioned. As an aryl group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, etc. are mentioned.

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

As an aryl group which has an alkyl group, said substituent can be arbitrarily combined other than a trilyl group, xylyl group, cumenyl group, mesityl group, 2, 6- diethylphenyl group, 2-methyl-6- ethylphenyl group, etc. can be combined.

As an aromatic heterocycle,

Etc. can be mentioned.

As a heterocycle, an aromatic heterocycle may be sufficient and it may not have aromaticity.

As a heterocyclic ring having no aromaticity,

Etc. can be mentioned.

In addition, any of the positions mentioned above may be sufficient as the bond of the said ring.

As -OR <^16> , an alkoxy group etc. which were mentioned above are mentioned.

Examples of —CO ₂ R ¹⁶ include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group and cyclopentyloxycarbonyl group , Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, tricyclodecyloxycarbonyl group, men Oxypropoxycarbonyl group, ethoxypropyloxycarbonyl group, hexyloxypropoxycarbonyl group, 2-ethylhexyloxypropoxycarbonyl group, methoxyhexyloxycarbonyl group, etc. are mentioned.

Examples of -SO ₂ NHR ¹⁸ include sulfamoyl group, N- (methyl) sulfamoyl group, N- (ethyl) sulfamoyl group, N- (propyl) sulfamoyl group, N- (isopropyl) sulfamoyl group, and N- (Butyl) sulfamoyl group, N- (isobutyl) sulfamoyl group, N- (pentyl) sulfamoyl group, N- (isopentyl) sulfamoyl group, N- (neopentyl) sulfamoyl group, N- (cyclo Pentyl) sulfamoyl group, N- (hexyl) sulfamoyl group, N- (cyclohexyl) sulfamoyl group, N- (heptyl) sulfamoyl group, N- (cycloheptyl) sulfamoyl group, N- (octyl) sulfate Pamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (cyclooctyl) sulfamoyl group, N- (nonyl) sulfamoyl group, N- (Decyl) sulfamoyl group, N- (tricyclodecyl) sulfamoyl group, N- (methoxypropyl) sulfamoyl group, N- (ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group , N- (isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamo Group, N- (3- phenyl-1-methylpropyl), and the sulfamoyl group and the like.

In addition, there may be mentioned as -SO ₂ NHR ^18, to a group represented by the following formula. However, in the following formula, X <^1> represents a halogen atom. X <^3> represents a C1-C3 alkyl group or a C1-C3 alkoxy group, and the hydrogen atom of the said alkyl group and the alkoxy group may be substituted by the halogen atom. X <^2> represents a C1-C3 alkyl group, a C1-C3 alkoxy group, a halogen atom, or a nitro group, and the hydrogen atom of the said alkyl group and the alkoxy group may be substituted by the halogen atom.

As a C1-C3 alkyl group which may be substituted by the halogen atom, a perfluoromethyl group etc. are mentioned besides the said alkyl group.

As a C1-C3 alkoxy group which may be substituted by the halogen atom, said alkyl group, especially a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

As most of all, -SO ₂ NHR ^18, it is preferable that R ¹⁸ is an alkyl group of 1 to 10 carbon atoms.

Examples of -SO ₂ N (R ¹⁸ ) R ¹⁹ include the following groups.

Examples of the heterocyclic ring formed by bonding of R ¹⁸ and R ¹⁹ to each other include groups represented by the following formulas.

Especially, as R <^18> and R <^19> , a C1-C10 alkyl group, a C5-C7 cycloalkyl group, an allyl group, a phenyl group, a C8-C10 aralkyl group, a C2-C8 hydroxy group containing alkyl group, and an aryl Group, a C2-C8 alkoxy group containing alkyl group, and an aryl group are preferable, A C6-C8 branched alkyl group is more preferable, It is especially preferable that it is a 2-ethylhexyl group.

In the compound ^(1), R 1 ~R ¹⁵ are each independently a hydrogen atom, -R ^16, -SO ₃ ^- and, -SO ₃ Na, -SO ₃ K or -SO ₃ H, also R ¹ ~R one of the ^15, -SO ₃ ^- is preferably. R ¹ ~R ¹⁵ comprise, each independently, a hydrogen atom, -R ^16, -SO ₃ ^- and -SO ₃ H or, one of R ¹ ~R ¹⁵ is also, -SO ₃ ^- which is more preferable. In addition, R ¹ ~R ¹⁵ comprise, each independently, a hydrogen atom, -R ^16, -SO ₃ ^- or a -SO ₃ H, and one of R ¹ ~R ^15, -SO ₃ ^-, and, also, R ¹ is one of ~R ¹⁵ is a, -SO ₃ H is particularly preferred.

Moreover, it is more preferable that compound (1) is a compound represented by the following formula (1a).

[Formula (1a),

R ^{1 ′} each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R ^{2 'are,} each independently, a hydrogen atom, -SO ₃ ^- represents a, -SO ₃ Na, -SO ₃ K or -SO ₃ H. However, R ² of one ^'is -SO ₃ ^- shows.

As compound (1), the following compounds are mentioned, for example.

In the compound (2), R ²¹ ~R ³⁵ comprise, each independently, 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 R ²¹ to R ³⁵ At least one of them is preferably -SO ₂ N (R ¹⁸ ) R ¹⁹ or -SO ₂ NHR ¹⁸ . ~R ³⁵ R ²¹ comprise, each independently, a hydrogen _{^{atom, -R 16, -SO 3 -,}} -SO 3 H, -SO 2 N (R 18) R 19 or -SO ₂ NHR ^18, and also R ²¹ ~ R ³⁵ At least one of them is preferably -SO ₂ N (R ¹⁸ ) R ¹⁹ or -SO ₂ NHR ¹⁸ .

Moreover, it is more preferable that compound (2) is a compound represented by the following formula (2a).

[Formula (2a),

Each R ^{21 '} is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R ^{22 'are,} each independently, 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 represents With the proviso that 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. ]

As compound (2), the following compound (2-1), a compound (2-2), and a compound (2-3) are mentioned.

In the formula (2-1), in the formula (2), 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 or -SO ₂ N (R ¹⁸⁾ represents an R ^19,

R ²¹ to R ³⁵ One represents -SO ₃ ^- and R ²¹ to R ³⁵ One of them is a compound representing -SO ₂ N (R ¹⁸ ) R ¹⁹ .

Compound (2-1), the formula (2), R ²¹ ~R ³⁵ is, independently, a hydrogen _{^{atom, -R 16, -SO 3 -,}} -SO 3 Na, -SO 3 K, -SO 3 H or —SO ₂ N (R ¹⁸ ) R ¹⁹ ;

R ²¹ ~R one of the ^35, -SO ₃ ^- represents a, R ²¹ is one of ~R ^35, -SO preferably a compound represented the _{^{2 N (R 18) R 19}} .

In the formula (2), R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -CO ₂ H, -CO ₂ R ¹⁶ , It represents _{a, -SO 3 Na, -SO 3 K} , -SO 3 H or -SO ₂ NHR ^{18, -} -SO ₃

R ²¹ ~R a group, -SO ₃ of ^{35 -} represents the, R ²¹ ~R a compound that is one of ^35, -SO ₂ NHR ^18.

Compound (2-2), the formula (2), R ²¹ ~R ³⁵ is, independently, a hydrogen _{^{atom, -R 16, -SO 3 -,}} -SO 3 Na, -SO 3 K, -SO 3 H or -SO ₂ NHR ¹⁸ and R ²¹ to R ³⁵ One, of the -SO ₃ ^- represents,

R ²¹ ~R ³⁵ one of which is preferably a compound represented by -SO ₂ NHR ^18.

In the formula (2), in the formula (2-3), R ²¹ to R ³⁵ each independently represent a hydrogen atom, -R ¹⁶ , -OH, -OR ^l6 , -CO ₂ H, -CO ₂ R ¹⁶ , _{^{-SO 3 -, -SO 3 Na,}} -SO 3 K, -SO 3 H, -SO represents ₂ N (R ¹⁸⁾ R ¹⁹ or -SO ₂ NHR ^18, R ²¹ ~R one of the ^35, -SO ₃ ^- represents the,

R ²¹ ~R a compound that at least two of ^{_{35, -SO 2 N (R 18)}} R 19 or -SO ₂ NHR ^18.

Compound (2-3), the formula (2), R ²¹ ~R ³⁵ is, independently, a hydrogen _{^{atom, -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 a, -SO ₃ ^- represents a, R ²¹ is ~R preferred that at least two of ^35, a compound that exhibits ^{_{-SO 2 N (R 18) R}} 19 or -SO ₂ NHR ^18.

As compound (2), the following compounds are mentioned, for example.

These compounds may use a commercially available thing and can synthesize | combine them by the method of Japanese Unexamined-Japanese-Patent No. 2003-201413, or the method according to this, for example.

When the dye composition of the present invention contains only the compound (1) and the compound (2) as a dye, the compound (1) is preferably 1 part by mass to 35 parts by mass with respect to 100 parts by mass of the dye composition, More preferably, it is 1 mass part or more and 20 mass parts or less, Especially preferably, 1 mass part or more and 15 mass parts or less are contained. The compound (2) is preferably 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. Moreover, it is preferable that compound (1) contains 1 mass part or more and 35 mass parts or less, and compound (2) contains 65 weight% or more and 99 mass parts or less.

In addition, the dye composition of the present invention may further contain a compound represented by the formula (3) (hereinafter sometimes referred to as "compound (3)").

[Equation (3),

R ⁴¹ to R ⁵⁵ are each independently 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. ]

In the formula (3), 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 as compound representing ₂ NHR ¹⁸ are preferred.

In addition, the compound (3) is preferably a compound represented by the following Formula (3a).

In formula (3a),

R ^{41 'comprise,} each independently, represent a hydrogen atom or an alkyl group having a carbon number ^{_{1~l0, -SO 2 N (R 18}} ) R 19 or -SO ₂ NHR ^18.]

As compound (3), the following compounds are mentioned, for example.

When the dye composition of the present invention contains a compound (1), a compound (2) and a compound (3) as a dye, the compound (1) is preferably 1 mass per 100 parts by mass of the dye composition. 15 parts by mass or more and more preferably 2 parts by mass or more and 13 parts by mass or less. 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. Moreover, it is preferable that compound (1) is 1 mass part or more and 15 mass parts or less, compound (2) is 65 mass parts or more and 98 mass parts or less, and compound (3) is 1 mass part or more and 20 mass parts or less.

Compound (1), compound (2), and compound (3), for example, chlorinate a dye or a dye intermediate having -SO ₃ H by a conventional method, and obtain a dye or a dye intermediate having -SO ₂ Cl obtained. R ¹⁸ can be prepared by reacting an amine represented by -NH _2, or -NHR ¹⁹ R ^18. Moreover, it can manufacture by reacting with the amine, after coloring the pigment | dye manufactured by the method as described in the upper right column to the left lower column of Unexamined-Japanese-Patent No. 3-78702, similarly to the above.

The coloring composition of this invention contains said dye composition (A-1) and pigment (A-2).

As the pigment (A-2), an organic pigment, for example, 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, etc. are mentioned. Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3 and 15: 6 preferably contain at least one pigment selected from C.I. It is particularly preferable to contain Pigment Blue 15: 6. You may use these pigments individually or in mixture of 2 or more types.

Organic pigments may be treated with rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group, etc., graft treatment on the surface of the pigment with a high molecular compound, atomization treatment by sulfuric acid atomization, or the like. The washing treatment with an organic solvent, water, or the like to be removed, the removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that an organic pigment is uniform particle diameter. The pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution by containing a pigment dispersant and performing a dispersion process can be obtained.

As a pigment dispersant, surfactant, such as a cation type, anion type, a nonionic type, an amphoteric, a polyester type, a polyamine type, an acryl type, etc. are mentioned, for example. You may use these pigment dispersants individually or in combination of 2 or more types.

When using a pigment dispersant, the usage-amount is per mass part of pigment (A-2), Preferably it is 1 mass part or less, More preferably, it is 0.05 mass part or more and 0.5 mass part or less. When the usage-amount of a pigment dispersant exists in the said range, since the pigment dispersion liquid of a uniform dispersion state tends to be obtained, it is preferable.

The content ratio (mass ratio) of the dye composition (A-1) and the pigment (A-2) is preferably 1:99 to 99: 1, more preferably 1:99 to 60:40, and 3:97 It is more preferable that it is -50: 50, and it is more preferable that it is 5: 95-40: 60. By setting it as such a ratio, optimization of a transmission spectrum becomes easy, a high contrast, high brightness coating film and pattern can be obtained, and heat resistance and chemical-resistance become favorable.

In particular, dye composition (A-1) and C.I. It is preferable that the mass ratio of pigment blue 15: 6 is 3: 97-50: 50.

The coloring photosensitive resin composition of this invention contains said dye composition (A-1), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E).

Content of dye composition (A-1) is 0.3-30 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 1-20 mass%, More preferably, it is 1-15 mass%.

Moreover, when it contains a pigment (A-2), the total amount of a dye composition (A-1) and a pigment (A-2) is 0.3-50 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 1 It is -40 mass%, More preferably, it is 1-30 mass%.

In addition, the pigment (A-2) is C.I. In the case of pigment blue 15: 6, the total amount of dye composition (A-1) and CI pigment blue 15: 6 is 1-50 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 3-40 mass. %, More preferably, it is 5-30 mass%, More preferably, it is 10-25 mass%.

Here, solid content means the sum total of the component except the solvent in a coloring photosensitive resin composition.

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

For example, alkali-soluble resin (B) contains the structural unit which has a carboxy group. As a structural unit which has a carboxy group, it is preferable to have a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Content of the structural unit derived from (meth) acrylic acid becomes like this. Preferably it is 16 mol% or more and 40 mol% or less, More preferably, 18 mol% or more and 38 mol% among all the structural units which comprise alkali-soluble resin (B). It is as follows. When content of the structural unit derived from (meth) acrylic acid exists in this range, the solvent property of a non-pixel part will become favorable at the time of image development. Moreover, there exists a tendency for a residue to remain in the non-pixel part after image development.

As another monomer which induces structural units other than the structural unit derived from the (meth) acrylic acid which comprises alkali-soluble resin (B), For example, aromatic vinyl compound, unsaturated carboxylic acid ester, unsaturated carboxylic acid aminoalkyl ester Unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and monoacryloyl groups or monomethas at the ends of the polymer molecular chains. The macromonomers which have a kryloyl group, the unit represented by Formula (II), the unit represented by Formula (III), etc. are mentioned.

[In Formula (II) and Formula (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.]

Specifically as alkali-soluble resin (B), methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate Copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent represented by formula (II) [wherein in formula (II), R ⁵³ represents a methyl group And R ⁵⁴ represents a hydrogen atom.] / Benzyl methacrylate copolymer, a constituent represented by formula (II) [wherein, in formula (II), R ⁵³ represents a methyl group and R ⁵⁴ represents a hydrogen atom; ] / Benzyl methacrylate copolymer, methacrylic acid / structural component represented by Formula (III) [In this case, in Formula (III), R ⁵⁵ represents a methyl group and R ⁵⁶ represents a hydrogen atom. ] / Styrene copolymer / tricyclodecanyl methacrylate Copolymer, alkali-soluble resin (B) represented by the formula (IV), and the like.

In formula (II) an alkali-soluble resin (B) having a composition represented by, for example, methacrylic acid / expression composition represented by (II) [However, in this case, formula (II), R ⁵³ represents a methyl group .] / Benzyl methacrylate copolymer can be obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a copolymer, and reacting the obtained copolymer with a compound represented by formula (V).

[In formula (V), R ⁵⁴ represents the same meaning as above.]

Methacrylic acid / Structural component represented by Formula (III) [But here, in formula (III), R ⁵⁵ represents a methyl group.] / Styrene copolymer / tricyclodecyl methacrylate copolymer is benzyl methacrylate. And methacrylic acid and tricyclodecyl monomethacrylate copolymer can be obtained by reacting a compound represented by the formula (VI).

Copolymerization is generally performed in a solvent using a polymerization initiator.

As the polymerization initiator, for example, an azo compound such as 2,2'-azobisisobutylonitrile or 2,2'-azobis (methyl 2-methylpropionate), a peroxide such as benzoyl peroxide or tert-butyl peroxide Etc. are used.

The solvent should just melt | dissolve each monomer, For example, glycol ether esters, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, a propylene glycol monomethyl ether acetate, and a propylene glycol monoethyl ether acetate, from behind The solvent etc. which were illustrated as a solvent (E) to demonstrate are used.

What is necessary is just to determine reaction temperature in consideration of the decomposition temperature of a polymerization initiator, the boiling point of a solvent, a monomer, etc.

In addition, the side chain of the copolymer obtained in this way may be modified with the compound which has a polymeric group, and it can also be set as photosensitive alkali-soluble resin (B). At this time, you may add the catalyst for introducing a polymeric group to resin.

As a catalyst, tris dimethylamino methyl phenol etc. are mentioned, for example. Moreover, you may add the additive for preventing a side reaction. As the additive, for example,? Dioxyquinone may be mentioned.

As alkali-soluble resin (B), the following copolymers [K1]-[K4], etc. are mentioned further.

[K1] Unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (B1) (hereinafter, only referred to as "(B1)") and monomer (B2) having a cyclic ether structure having 2 to 4 carbon atoms [ Hereinafter, only the "(B2)" may be described] the copolymer formed by superposing | polymerizing.

[K2] A copolymer obtained by polymerizing (B1), (B2) and a monomer (B3). Here, the monomer (B3) (hereinafter may be described only as "(B3)") is a monomer copolymerizable with (B1) and / or (B2), and is not (B1) and / or (B2). Monomer.

[K3] A copolymer obtained by reacting a part of the carboxyl groups derived from (B1) with a C2-4 cyclic ether structure derived from (B2) in the copolymer of (B1) and (B3).

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

Especially, it is preferable that it is a copolymer formed by superposing | polymerizing at least (B1) and (B2).

As (B1), aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic anhydride etc. are mentioned, for example. Specifically,

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; And

Anhydrides of these unsaturated dicarboxylic acids;

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

5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [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-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6 Carboxylic or carboxylic anhydride-containing bicyclos, such as -ethylbicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride) 2.2.1] hept-2-enes;

Unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, etc. are mentioned.

Especially, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity and alkali solubility.

You may use these individually or in combination of 2 or more types. In addition, in this specification, as long as there is no notice in particular, the illustrated compound, a component, a preparation, etc. can be used individually or in combination of 2 or more types.

(B2) should just have a C2-C4 cyclic ether structure (for example, at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group, an oxetanyl group, and a tetrahydrofuryl group), for example. Moreover, it is preferable that it is a monomer which has an unsaturated bond. As (B2), the monomer which has a C2-C4 cyclic ether structure and ethylenic carbon-carbon unsaturated bond is more preferable, and the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group Is particularly preferred.

As (B2), the monomer which has an oxiranyl group, the monomer which has an oxetanyl group, the monomer which has a tetrahydrofuryl group, etc. are mentioned, for example.

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

It is preferable that the monomer which has an oxiranyl group is a compound which has at least 1 group chosen from the group which consists of an aliphatic oxiranyl group and an alicyclic oxiranyl group, and has an unsaturated bond.

An aliphatic oxiranyl group means the thing of the group which has a structure which epoxidized chain olefin.

Specific examples of the compound having an aliphatic oxiranyl group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. And the compound represented by the following formula (VI) described in JP-A-7-248625.

[In formula (VI), R <^61> -R <^63> is a hydrogen atom or a C1-C10 alkyl group and a cycloalkyl group each independently, m <^1> is an integer of 1-5.].

As a compound represented by Formula (VI), o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, (alpha) -methyl-o-vinyl benzyl glycidy, for example Dil ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxy Methylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxy Methyl styrene, 2,3,6-triglycidyloxymethyl styrene, 3,4,5-triglycidyloxymethyl styrene, 2,4,6-triglycidyloxymethyl styrene, and the like.

An alicyclic oxiranyl group means the thing of the group which has a structure which epoxidized cyclic olefin.

As a monomer which has an alicyclic oxiranyl group, the monomer which has an aliphatic monocyclic oxiranyl group, the monomer which has an aliphatic polycyclic oxiranyl group, etc. are mentioned, for example. An aliphatic monocyclic oxiranyl group means the group which has a structure which epoxidized monocyclic cyclic olefin. Moreover, an aliphatic polycyclic oxiranyl group means group which has a structure which epoxidized polycyclic cyclic olefin. It is preferable that the monomer which has these oxiranyl group is a compound which has at least 1 sort (s) chosen from the group which consists of an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group, and has an unsaturated bond, and is an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group It is preferable that it is a compound which has at least 1 sort (s) chosen from the group which consists of, and has a (meth) acryloyloxy group.

As said monocyclic cyclic olefin, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc. are mentioned, for example. Especially, the C5-C7 compound is preferable.

Specific examples of the monomer having an aliphatic monocyclic oxiranyl group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane [for example, ceoxide 2000; Daicel Chemical Co., Ltd. product], 3, 4- epoxycyclohexyl methyl acrylate [For example, cyclomer A400; Daicel Chemical Co., Ltd. product], 3, 4- epoxycyclohexyl methyl methacrylate [for example, cyclomer M100; Daicel Chemical Industry Co., Ltd.] etc. are mentioned.

As said polycyclic cyclic olefin, For example, dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclononene, bicyclo undecene, tricyclo undecene, bi Cyclododecene, tricyclo dodecene, etc. are mentioned.

Especially, the C8-12 compound is preferable.

Examples of the monomer having an aliphatic polycyclic oxiranyl group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, a compound represented by formula (VII) and a formula (VIII). At least 1 sort (s) of compound chosen from the group which consists of a compound shown, etc. are mentioned.

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

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

* Represents a bond with O.

As R ⁷¹ and R ⁷² , specifically, a hydrogen atom; Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy And hydroxy group substituted alkyl groups such as hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

Especially, Preferably they are a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group. More preferably, they are a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, and a 1,6-hexanediyl group. Etc. can be mentioned.

As X ¹ and X ² , Preferably, a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents a bond with O), * -CH ₂ CH ₂ -O- groups, and more preferably a single bond, * -CH ₂ And a CH ₂ -O- group.

The at least one compound selected from the group consisting of a compound represented by the formula (VII) and a compound represented by the formula (VIII) is a group consisting of a compound represented by the following formula (VII ') and a compound represented by the formula (VIII'). It is preferable that it is at least 1 type of compound chosen from.

In formula (VII ') and formula (VIII'), R ^{71 '} and R ^72' have the same meaning as R ⁷¹ and R ⁷² , respectively.

As a compound represented by Formula (VII), the compound etc. which are represented by Formula (VII-1)-Formula (VII-15) are mentioned, for example. Preferably, formulas (VII-1), (VII-3), (VII-5), (VII-7), (VII-9), (VII-11) to (VII-15) )to be. More preferably, they are Formula (VII-1), Formula (VII-7), Formula (VII-9), and Formula (VII-15).

As a compound represented by Formula (VIII), the compound etc. which are represented by Formula (VIII-1)-Formula (VIII-15) are mentioned, for example. Preferably formulas (VIII-1), (VIII-3), (VIII-5), (VIII-7), (VIII-9), (VIII-11) to (VIII-15) )to be. More preferably, they are Formula (VIII-1), Formula (VIII-7), Formula (VIII-9), and Formula (VIII-15).

At least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (VII) and a compound represented by Formula (VIII) can be used independently, respectively. Moreover, it can mix in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20: in the formula (VII): formula (VIII). 80-80: 20.

The monomer which has an oxetanyl group means the polymeric compound which has an oxetanyl group, for example. It is preferable that the monomer which has an oxetanyl group is a compound which has an oxetanyl group and an unsaturated bond, It is preferable that it is a compound which has an oxetanyl group and has a (meth) acryloyloxy group.

Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, and 3-ethyl-3-methacrylo. Yloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3 -Ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

The monomer which has a tetrahydrofuryl group means the polymeric compound which has a tetrahydrofuryl group, for example. It is preferable that the monomer which has a tetrahydrofuryl group is a compound which has a tetrahydrofuryl group and an unsaturated bond, It is preferable that it is a compound which has a tetrahydrofuryl group and has a (meth) acryloyloxy group.

Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate [for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.], tetrahydrofurfuryl methacrylate, and the like. have.

As a monomer (B3) which can be copolymerized, for example,

(Meth) acrylic-acid alkylesters, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate [in the art, conventionally known as dicyclopentanyl ( (Meth) acrylic acid cyclic alkyl esters such as meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like;

(Meth) acrylic acid aryl esters, such as phenyl (meth) acrylate and benzyl (meth) acrylate;

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

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonyl Bicyclo [ 2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) ratio Bicyclo unsaturated compounds, such as cyclo [2.2.1] hept-2-ene;

N-alkyl maleimides such as N-methyl maleimide, N-ethyl maleimide and N-propyl maleimide;

N-cycloalkyl maleimide, such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, and N-cyclooctyl maleimide;

N-bridged carbocyclic group substituted maleimide, such as N-adamantyl maleimide and N-norbornyl maleimide;

N-aryl maleimide, such as N-phenyl maleimide;

N-aralkyl maleimide, such as N-benzyl maleimide;

N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Dicarbonyl imide derivatives such as cypionate 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.

Especially, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene, etc. are preferable at the point of copolymerization reactivity and alkali solubility.

Copolymers [K1] to [K4] are, for example, the method described in the document "Experimental method of polymer synthesis" (first edition March 1, 1972, First Chemical Co., Ltd., Otsudakayuki Co., Ltd.). It can manufacture with reference to the citation described in the said document.

Specifically, the monomers (B1) and (B2) constituting the copolymer, optionally a predetermined amount of (B3), a polymerization initiator and a solvent, are put in a reaction vessel, oxygen is replaced by nitrogen, stirred and heated in the absence of oxygen. By keeping warm, a polymer is obtained. The polymerization conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production facilities, the amount of heat generated by the polymerization and the like.

As the polymerization initiator and the solvent used herein, any of those commonly used in the field can be used. For example, the polymerization initiator, the solvent, etc. which were illustrated by this specification can be used.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

In particular, by using the solvent described later as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

It is preferable that the ratio of each monomer which comprises copolymer [K1] exists in the following ranges with respect to the total mole number of the monomer which comprises copolymer [K1].

(B1) 5-95 mol%, More preferably, it is 10-90 mol%

(B2) 5-95 mol%, More preferably, it is 10-90 mol%.

Moreover, it is preferable that the ratio of each monomer which comprises copolymer [K2] exists in the following ranges with respect to the total mole number of the monomer which comprises copolymer [K2].

(B1) 2-40 mol%, More preferably, 5-35 mol%

(B2) 2 to 95 mol%, more preferably 5 to 80 mol%

(B3) 1-65 mol%, More preferably, it is 1-60 mol%.

Copolymer [K3] can be manufactured through a two-step process.

First, (B1) and (B3) are copolymerized similarly to the method mentioned above, and a copolymer is obtained.

In this case, it is preferable that the ratio of each monomer exists in the following ranges with respect to the total mole number of the monomer which comprises the said copolymer.

(B1) 5-50 mol%, Preferably 10-45 mol%

(B3) 50-95 mol%, Preferably it is 55-90 mol%.

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

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

In this case, 5 to 80 mol% is suitable with respect to the mole number of (B1), More preferably, it is 10-75 mol%, Especially preferably, it is 15-70 mol%.

The reaction catalyst is preferably used as a reaction catalyst of, for example, a carboxyl group and an oxiranyl group, oxetanyl group or tetrahydrofuryl group. Specifically, trisdimethylaminomethyl phenol etc. are illustrated.

As for the usage-amount of a reaction catalyst, 0.001 to 5% is preferable with respect to the total amount of (B1)-(B3), for example.

Examples of the polymerization inhibitor include hydroquinone.

As for the usage-amount of a polymerization inhibitor, 0.001 to 5% is preferable on a mass basis with respect to the total amount of (B1)-(B3), for example.

It is preferable that the ratio of each monomer which comprises copolymer [K4] exists in the following ranges with respect to the total mole number of the monomer which comprises copolymer [K4].

(B1) 2-40 mol%, More preferably, 5-35 mol%

(B2) 60-98 mol%, More preferably, it is 65-95 mol%.

The weight average molecular weight of polystyrene conversion of copolymer [K1]-[K4] becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000.

The dispersion degree (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of copolymer [K1]-[K4] become like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. .

As for polystyrene conversion weight average molecular weight of alkali-soluble resin (B), 5,000-35,000 are preferable, More preferably, it is 6,000-30,000, Especially preferably, it is 7,000-28,000. When the molecular weight is in the above-described range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution tends to be improved.

In addition, a weight average molecular weight is a value measured by the GPC method, for example, The thing measured by the measurement conditions described in the Example, etc. are mentioned specifically ,.

As for the acid value of alkali-soluble resin (B), 50-150 are preferable, More preferably, it is 60-135, Especially preferably, it is 70-135. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of alkali-soluble resin (B), and can usually be obtained by titrating with an aqueous potassium hydroxide solution.

As for content of alkali-soluble resin (B), 7-65 mass% is preferable with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 13-60 mass%, Especially preferably, it is 17-55 mass%. When content of alkali-soluble resin (B) exists in this range, a pattern can be formed and there exists a tendency for the resolution and residual film rate to improve.

A photopolymerizable compound (C) will not be specifically limited if it is a compound which can superpose | polymerize with the active radical, the acid, etc. which generate | occur | produced from the photoinitiator (D) by irradiating light. For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

As a photopolymerizable compound (C), it is preferable that it is a trifunctional or more than polyfunctional photopolymerizable compound. As a trifunctional or more than trifunctional photopolymerizable compound, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate and the like. Said photopolymerizable compound (C) may be used individually or in combination of 2 or more types.

It is preferable that content of a photopolymerizable compound (C) is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. . When content of said photopolymerizable compound (C) exists in the said range, hardening will fully arise, the film thickness ratio before and behind image development will improve, it will become difficult to enter undercut into a pattern, and adhesiveness tends to become favorable.

The coloring photosensitive resin composition of this invention contains a photoinitiator (D).

As said photoinitiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by being irradiated with light. The acid generator generates acid by being irradiated with light.

As said active radical generator, an acetophenone type compound, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, an oxime type compound etc. are mentioned, for example.

As said acetophenone type compound, diethoxy acetophenone, 2-methyl- 2-morpholino-1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1-, for example (4-morpholinophenyl) -2-benzylbutan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1 -[4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Propan-1-one oligomer etc. are mentioned, Preferably 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one etc. are mentioned.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy city oxanthone etc. are mentioned.

As said triazine type compound, 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- (4-methoxystyryl) -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino -2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-triazine and the like.

As said oxime type compound, an O-acyl oxime type compound is mentioned, for example, As the specific example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -butan-1-one-2- Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyl Oxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like.

As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenansrenquinone, camphorquinone, methyl phenylglyoxylate, titanocene compound Etc. may be used.

As said acid generator, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonite, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium p-, for example Toluenesulfonite, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonite, triphenylsulfonium hexafluoroantimonate, diphenyliodium p-toluene Onium salts, such as sulfonite and diphenyl iodide hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

In addition, among the compounds described above as the active radical generators, there are also compounds which generate an acid simultaneously with the active radicals. For example, a triazine-based photopolymerization initiator is also used as the acid generator.

The content of the photopolymerization initiator (D) is preferably 0.1 to 30 mass%, more preferably 1 to 20 mass%, based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When content of a photoinitiator exists in the said range, it will become highly sensitive and an exposure time will be shortened and productivity will improve.

The photopolymerization start adjuvant (F) may further be contained in the coloring photosensitive resin composition of this invention. A photoinitiator (F) is a compound or sensitizer which is normally used in combination with a photoinitiator (D), and is used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by a photoinitiator.

As photopolymerization start adjuvant (F), an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.

As said amine type compound, triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4- dimethylamino benzoate, 4-dimethylamino benzoate ethyl, 4-dimethylamino benzoate isoamyl, 2-dimethyl benzoate, for example Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino ) Benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable.

As said alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy Anthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy city oxanthone etc. are mentioned.

You may use photopolymerization start adjuvant (F) individually or in combination of 2 or more types. Moreover, a commercial thing can also be used as a photoinitiation start adjuvant (F), As a commercial photoinitiation start adjuvant (F), brand name "EAB-F" [made by Hodogaya Chemical Co., Ltd.] etc. is mentioned, for example. Can be.

As a combination of the photoinitiator (D) and the photoinitiator adjuvant (F) in the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one / 4,4'-bis (diethyl amino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one / 4,4'-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propane-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino ) Benzophenone, oligomer / 4,4'-bis (diethyl amino) benzophenone of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, and the like. There may be mentioned 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4-bis (diethylamino) benzophenone.

When using these photoinitiators (F), the usage-amount is per 0.01 mol of photoinitiators (D), Preferably it is 0.01-10 mol, More preferably, it is 0.01-5 mol.

The coloring photosensitive resin composition of this invention contains a solvent (E).

It does not specifically limit as a solvent (E), The solvent normally used in the said field | area can be used.

For example, esters (solvents containing -COO-), ethers other than esters (solvents containing -O-), ketones other than esters (solvents containing -CO-), alcohols, aromatics Hydrocarbons, amides, N-methylpyrrolidone, dimethyl sulfoxide, etc. can be selected and used.

Examples of the esters include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid To ethyl, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, acetoacetic acid There may be mentioned 2-oxo-butanoic acid methyl, 2-oxo-butanoic acid ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, cyclohexanol acetate, butyl γ- lactone ol.

As said ether, For example, 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetra Hydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, and the like can be mentioned acetate, cellosolve acetate, ethyl cellosolve, methyl cells, ethyl carbitol acetate, butyl carbitol acetate, anisole, phenetole, methyl anisole.

As said ketones, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-, for example Pentanone, cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said amides, N, N- dimethylformamide, N, N- dimethylacetamide, N-methylpyrrolidone, etc. are mentioned, for example.

You may use these solvents individually or in combination of 2 or more types.

The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the mass fraction with respect to 100 mass% of the colored photosensitive resin composition. In other words, it is suitable to adjust content of a solvent (E) so that solid content may be 5-30 mass% with respect to 100 mass% of colored photosensitive resin compositions, Preferably it is 8-25 mass%. When content of a solvent (E) exists in the said range, since flatness at the time of application | coating becomes favorable and color density does not run short when a color filter is formed, it is preferable because there exists a tendency for favorable display characteristics.

Surfactant (G) may be contained in the coloring photosensitive resin composition of this invention further. As surfactant (G), at least 1 sort (s) chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and a silicone type surfactant which has a fluorine atom is mentioned.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Toray silicon DC3PA, Toray silicon SH7PA, Toray silicon DC11PA, Toray silicon SH21PA, Toray silicon SH28PA, Toray silicon SH29PA, Toray silicon SH30PA, Polyether modified silicone oil SH8400 [brand name: Toray silicon; Toray Dow Corning Co., Ltd.], KP321, KP322, KP323, KP324, KP326, KP340, KP341 [Shin-Etsu Chemical Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [ Momentum, performance materials, Japan joint company] etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (brand name) F142D, megapack F171, megapack F172, megapack F173, megapack F177, megapack F183 , Megapack R30 [product made by DIC Corporation], F-top (brand name) EF301, f-top EF303, f-top EF351, f-top EF352 [made by Mitsubishi Material Electronic Chemicals Co., Ltd.], saffron (brand name) S381, Inc. Fron S382, saffron SC101, saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 [manufactured by Daikin Fine Chemical Research Institute Co., Ltd.], BM-1000, BM-1100 (all manufactured by BM Chemie Co., Ltd.), and the like. Can be mentioned.

As silicone type surfactant which has said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

You may use these surfactant individually or in combination of 2 or more types.

Content of surfactant (G) is 0.00001-0.1 mass% with respect to colored photosensitive resin composition, More preferably, it is 0.00005-0.01 mass%. When content of surfactant (G) exists in the said range, since the flatness of a coating film tends to become favorable, it is preferable.

It is preferable that the coloring photosensitive resin composition of this invention is a negative coloring photosensitive resin composition.

The coloring photosensitive resin composition of this invention can be used suitably in order to form a color filter, a coating film, or a coloring pattern, and obtaining the coloring pattern and color filter which are excellent in color density, lightness, contrast, a sensitivity, a resolution, heat resistance, etc. It becomes possible. Moreover, the display apparatus provided with these color filters, a coating film or a coloring pattern, an optical film, and / or an array substrate, etc. which comprise these color filters or a coloring pattern as a part of its component parts, etc., For example, it can use with well-known form for all the apparatuses related to various colored images, such as a well-known liquid crystal display device, an organic electroluminescent apparatus, and 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, for example, the coloring photosensitive resin composition of this invention is made into a board | substrate or another resin layer (for example, first on a board | substrate). The other colored photosensitive resin composition layer, etc.) formed, and removes / drys volatile components such as solvents to form a colored layer, exposes the colored layer through a photomask, and develops the photolithographic method. The method of using an inkjet machine, etc. are mentioned.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material, a use, etc. to use, For example, about 0.1-30 micrometers, Preferably it is about 1-20 micrometers, More preferably, It is about 1-6 micrometers.

As a coating method of a coloring photosensitive resin composition, the extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, the die coating method, etc. are mentioned, for example. Moreover, you may apply | coat using a coater, such as a dip coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater (it may also be called a die coater, a curtain flow coater, and a spin scotcher). Especially, it is preferable to apply | coat using a spin coater.

Examples of the removal / drying of the solvent include natural drying, ventilation drying, reduced pressure drying, and the like. 10-120 degreeC is preferable and, as for specific drying temperature, 25-100 degreeC is more preferable. 10 second-60 minutes are preferable, and, as for drying time, 30 second-30 minutes are more preferable. Drying under reduced pressure is preferably carried out in a temperature range of about 20 to 25 ° C. under a pressure of about 50 to 150 Pa.

Example

Hereinafter, the dye composition, the coloring photosensitive resin composition, and the color filter of this invention are demonstrated in detail by an Example. "%" And "part" in an example are the mass% and a mass part, unless it mentions specially.

Synthesis Example 1 Synthesis of Dye A1

In a vessel equipped with a cooling tube and a stirring device, 410 parts of chloroform and 28 parts of dimethylformamide were mixed. 37 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the mixture was reacted for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and the mixture was reacted at 35 ° C for 3 hours. 4 parts of thionyl chloride was further added to the reaction mixture, and the mixture was reacted at 35 ° C for 1.5 hours. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine and then 89 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Again, 290 parts of methanol and 20 parts of acetic acid were added to react for 30 minutes. The reaction was crystallized by pouring in 306 parts of ion-exchanged water. The crystals obtained after the filtration were washed sequentially with 300 parts of 50% aqueous methanol solution, 1000 parts of 70 ° C deionized water, and 300 parts of 20 ° C deionized water. It dried under reduced pressure at 60 degreeC for 1 day, and obtained 51 parts of dye A1 as a reddish violet solid.

Chemical identification of each compound represented by formulas (1), (2) and (3) contained in the dye A1 was performed by LC-MS. The result of LC-MS analysis is shown below.

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

Device: Shimadzu LC-10A,

column ; Wakosil II 3C18HG (3 μm, 3 mmφ × 150 mm)

Mobile phase A liquid; 0.1% TMAB / water: acetonitrile (9: 1)

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

       Gradient (B liquid)

       B initial concentration; 20%

       20% → (30 minutes) → 60% → (5 minutes) → 100% (hold 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 +

       Scan range; 100-1500

       Fragmentor; 120 V

       DryingGas; 350 ℃

Compound (1): measured value ([M + H] ⁺ ); 655.2,

            Exact Mass; 654.2

Compound (2-1): found value ([M + H] ⁺ ); 682.2,

              Exact Mass; 681.2

Compound (2-2): measured value ([M + H] ⁺ ); 766.3,

              Exact Mass; 765.3

Compound (2-3): measured value ([M + H] ⁺ ); 957.4,

              Calculated Value (Exact Mass): 956.4

Compound (3): measured value (M ⁺ ); 877.5,

            Calculated Value (Exact Mass): 877.4

Moreover, about each compound represented by Formula (1), (2), and (3), the area ratio of each peak is computed by the area percentage method by LC, and content of each compound is 100 parts of total amounts of these compounds. It calculated | required by the following formula. The results are shown in Table 1.

Compound (1) holding time; 14.0 to 16.0 minutes

Compound (2-1) holding time; 16.0 to 25.0 minutes

Compound (2-2) holding time; 25.0-26.5 minutes

Compound (2-3) holding time; 26.5-31.0 minutes

Compound (3) holding time; 31.0 to 41.0 minutes

Synthesis Example 2 Synthesis of Dye A2

In a vessel equipped with a cooling tube and a stirring device, 410 parts of chloroform and 28 parts of dimethylformamide were mixed. 37 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the mixture was reacted for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and reacted at 35 ° C for 3 hours. 4 parts of thionyl chloride was further added to the reaction mixture, and it was made to react at 35 degreeC for 1 hour. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine and then 89 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Furthermore, 260 parts of methanol and 25 parts of acetic acid were added, and it was made to react for 30 minutes. The reaction was poured into 396 parts of ion-exchanged water to crystallize. The crystals obtained after the filtration were washed sequentially with 300 parts of 50% aqueous methanol solution, 1000 parts of 70 ° C deionized water, and 300 parts of 20 ° C deionized water. It dried under reduced pressure at 60 degreeC for 1 day, and obtained 65 parts of dye A2 as a reddish violet solid.

In the same manner as in Synthesis example 1, the chemical identification of each compound contained in A2 was performed, and the content was calculated. The results are shown in Table 1.

Synthesis Example 3 Synthesis of Dye A3

In a vessel equipped with a cooling tube and a stirring device, 220 parts of acetonitrile and 28 parts of dimethylformamide were mixed. 35 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the reaction was carried out for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and reacted at 35 ° C for 3 hours. The reaction mixture was cooled, and 34 parts of 2-ethylhexylamine and then 69 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Further, 290 parts of methanol and 16 parts of acetic acid were added to react for 30 minutes. The reaction was crystallized by pouring in 306 parts of ion-exchanged water. The crystals obtained after the filtration were washed 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 1 day to obtain 44 parts of dye A3 as a reddish violet solid.

In the same manner as in Synthesis example 1, the chemical identification of each compound contained in A3 was performed, and the content was calculated. The results are shown in Table 1.

Synthesis Example 4 Synthesis of Dye A4

In a vessel equipped with a cooling tube and a stirring device, 410 parts of chloroform and 28 parts of dimethylformamide were mixed. 37 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the reaction was carried out for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and reacted at 35 ° C for 3 hours. Thereafter, 4 parts of thionyl 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 and then 89 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Furthermore, 260 parts of methanol and 25 parts of acetic acid were added, and it was made to react for 30 minutes. The reaction was crystallized by pouring in 415 parts of ion-exchanged water. The crystals obtained after filtration were washed 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 1 day to obtain 42 parts of dye composition A4 as a reddish violet solid.

In the same manner as in Synthesis example 1, the chemical identification of each compound contained in A4 was performed to calculate the content. The results are shown in Table 1.

Synthesis Example 5 Synthesis of Dye A5

In a vessel equipped with a cooling tube and a stirring device, 410 parts of chloroform and 28 parts of dimethylformamide were mixed. 41 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the mixture was reacted for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and reacted at 35 ° C for 3 hours. Thereafter, the reaction mixture was cooled, and 33 parts of 2-ethylhexylamine and then 69 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Further, 290 parts of methanol and 16 parts of acetic acid were added to react for 30 minutes. The reaction was crystallized by pouring in 306 parts of ion-exchanged water. The crystals obtained after filtration were washed sequentially with 150 parts of 50% aqueous methanol solution and 200 parts of 20 ° C. deionized water, and then dried under reduced pressure at 60 ° C. for 1 day to obtain 53 parts of dye A5 as a reddish violet solid.

In the same manner as in Synthesis example 1, the chemical identification of each compound included in A5 was performed to calculate the content. The results are shown in Table 1.

Synthesis Example 6 Synthesis of Dye A6

In a vessel equipped with a cooling tube and a stirring device, 410 parts of chloroform and 28 parts of dimethylformamide were mixed. 37 parts of thionyl chlorides were dripped at the mixed solution over 10 minutes at 10 degreeC. After completion of the dropwise addition, the mixture was reacted for 30 minutes while keeping warm. To the reaction mixture, 57 parts of Acid Red 289 (manufactured by Jukai Chemical Co., Ltd.) were added over 15 minutes, and reacted at 35 ° C for 3 hours. Thereafter, 4.1 parts of thionyl 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 and then 69 parts of triethylamine were added dropwise at 10 占 폚. After dripping, it was made to react at room temperature for 15 hours. The reaction mixture was concentrated, 200 parts of methanol was added, and then concentrated again until the liquid volume became approximately half. Further, 290 parts of methanol and 16 parts of acetic acid were added to react for 30 minutes. The reaction was crystallized by pouring in 306 parts of ion-exchanged water. The crystals obtained after the filtration were washed sequentially with 300 parts of 50% aqueous methanol solution, 500 parts of 50 ° C. deionized water, and 300 parts of 20 ° C. deionized water, and then dried under reduced pressure at 60 ° C. for 1 day to obtain 51 parts of dye A6 as a reddish violet solid. .

In the same manner as in Synthesis example 1, the chemical identification of each compound contained in A6 was performed to calculate the content. The results are shown in Table 1.

dyes Compound (unit: part) (One) (2-1) (2-2) (2-3) (2) total (3) A1 4 4 65 15 84 12 A2 7 6 66 15 87 6 A3 13 28 39 10 77 10 A4 10 8 64 14 86 4 A5 4 6 63 14 83 13 A6 2 4 63 15 82 16

Synthesis Example 7 Synthesis of Resin B1

Into a 1 L flask equipped with a reflux condenser, a dropping rod, and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 220 parts of ethyl lactate was added and heated to 70 ° C while stirring. Subsequently, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by Formula (I) and the compound represented by Formula (II) are mixed by 50:50 in molar ratio. .] 336 parts and 140 parts of ethyl lactate were dissolved to prepare a solution. The solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping rod. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of ethyl lactate was dripped in the flask over 4 hours using the other dripping rod. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 8.0 × 10 ³ , the degree of dispersion was 2.5, solid content 48%, and acid value 50. Resin solution B1 of mg-KOH / g was obtained.

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Test liquid solids concentration; 0.001-0.01 mass%

Injection volume; 50 μL

Detector; RI

Calibration standard; TSK STANDARD POLYSTYRENE

                     F-40, F-4, F-1, A-2500, A-500 [made by Tosoh Corporation]

Example 1

[Preparation of Colored Photosensitive Resin Composition 1]

(A) coloring agent; C.I. Pigment Blue 15: 6

5 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 137 parts

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

(A) coloring agent; Dye A1 part 3

(B) resin; Resin solution B1 65 parts

(C) photopolymerizable compound; Dipentaerythritol hexaacrylate

    KAYARAD DPHA; Nihon Kayaku Co., Ltd.]

(D) photoinitiator; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Iggacure OXE-01; Chiba Japan company] 9

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

Was mixed and the coloring photosensitive resin composition 1 was obtained.

[Formation of Pattern]

The colored photosensitive resin composition 1 was apply | coated by the spin coat method on the 2-inch square glass substrate (Eagle 2000; Corning Corporation make), and it prebaked at 100 degreeC for 3 minutes.

After cooling, the interval between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask having a pattern was set to 100 m, and an exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere.

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. After washing with water, post-baking was performed in an oven at 220 ° C. for 20 minutes. And the coating film was obtained.

After cooling, the film thickness of the coating film obtained was measured by a film thickness measuring apparatus [DEKTAK3; It was 2.2 micrometers when measured using Nippon Vacuum Technology Co., Ltd. product.

Examples 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 A2 to A6 shown in Table 1.

[Contrast Evaluation]

The coating film on the obtained glass substrate was made into two polarizing plates [POLAX-38S; Made by Rukeo Co., Ltd., and contrast measuring apparatus [CT-1; Tsubosaka Electric Co., Ltd. product, luminance meter [BM-5A; Topcon Technohouse Co., Ltd.], using a cold cathode F10 lamp as a light source, the luminance in parallel nicol and the luminance in orthogonal nicol of the transmitted light of the sample was measured, The ratio (parallel / orthogonal nicole) to the luminance of was taken as the contrast, and the case where the contrast was 6000 or more was defined as ○. The results are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 dyes A1 A2 A3 A4 A5 A6 Contrast ○ ○ ○ ○ ○ ○

According to this invention, it becomes possible to provide the dye composition which can provide a higher contrast color filter.

Claims (18)

The dye composition characterized by including the compound represented by Formula (1), and the compound represented by Formula (2).

In the formulas (1) and (2), R ¹ ~R ¹⁵ is, independently, 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 represents H,
R ¹ ~R ¹⁵ one group of, -SO ₃ ^- represents,
R <^16> represents a C1-C10 monovalent saturated hydrocarbon group, The hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom, the hydroxyl group, or the C1-C10 alkoxy group, and is contained in the said saturated hydrocarbon group. -CH ₂ -to be substituted may be substituted with -O-, -CO- or -NR ^17- , R ¹⁷ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms,
~R ³⁵ R ²¹ comprise, each independently, 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 , and R ²¹ to R ³⁵ One group represents -SO ₃ ^- and R ²¹ to R ³⁵ At least one represents -SO ₂ N (R ¹⁸ ) R ¹⁹ or -SO ₂ NHR ¹⁸ ,
R ^l8 And R ¹⁹ each independently represent a C1-C10 alkyl group, a C3-C30 cycloalkyl group, a C6-C10 monovalent aromatic hydrocarbon group, or a C5-C10 monovalent aromatic heterocyclic group, or mutually May be bonded 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 with a halogen atom, a hydroxy group, or a phenyl group and included in the alkyl group and the cycloalkyl group. -CH ₂ -to be substituted with -O-, -CO-, -NH- or -NR ¹⁶ -may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is a halogen atom, -R ¹⁶ , -OH, -OR ¹⁶ , -NO ₂ , -CH = CH ₂ Or -CH = CHR ^16. ] The method of claim 1,
The dye composition characterized by further including the compound represented by Formula (3).

In the formula (3), R ⁴¹ ~R ⁵⁵ is, independently, a hydrogen ^{atom, -R 16, -OH, -OR 16} , -CO 2 H, -CO 2 R 16, -SO 2 N (R 18 each ) R ¹⁹ or -SO ₂ NHR ^18. ] The method of claim 1,
In the formula (1), R ¹ to R ¹⁵ each independently represent a hydrogen atom, -R ¹⁶ , -SO ₃ ^- or -SO ₃ H,
R ¹ to R ¹⁵ One of ^- represents -SO _3- , and at least one represents -SO ₃ H. The method of claim 1,
In the formula (2), R ²¹ ~R ³⁵ is, independently, a hydrogen _{^{atom, -R 16, -SO 3 -,}} -SO 3 H, -SO 2 N (R 18) R 19 or -SO ₂ NHR ¹⁸ ,
R ²¹ ~R ³⁵ is one of -SO ₃ ^- shows a further dye composition, characterized in that at least one represents a ^{_{-SO 2 N (R 18) R}} 19 or -SO ₂ NHR ^18. The method of claim 2,
In 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 . Dye composition characterized by the above-mentioned. The method of claim 1,
Content of the compound represented by said Formula (1) is 1 mass part or more and 35 mass parts or less with respect to 100 mass parts of dye compositions,
Content of the compound represented by said formula (2) is 65 mass parts or more and 99 mass parts or less, The dye composition characterized by the above-mentioned. The method of claim 2,
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,
Content of the compound represented by said formula (2) is 65 mass parts or more and 98 mass parts or less,
Content of the compound represented by said Formula (3) is 1 mass part or more and 20 mass parts or less, The dye composition characterized by the above-mentioned. The dye-sensitive photosensitive resin composition containing the dye composition (A-1) of Claim 1, alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). The method of claim 8,
The pigment | dye (A-2) is further included, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 9,
The said pigment (A-2) is a pigment containing CI pigment blue 15: 6, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 10,
The mass ratio of said dye composition (A-1) and CI pigment blue 15: 6 is 3: 97-50: 50, The coloring photosensitive resin composition characterized by the above-mentioned. It is formed using the coloring photosensitive resin composition of Claim 8, The coating film characterized by the above-mentioned. It is formed using the coloring photosensitive resin composition of Claim 8, The color filter characterized by the above-mentioned. The method of claim 13,
The color filter is formed by a photolithography method. The method of claim 1,
A dye composition, characterized in that it is used for producing a color filter. The dye composition (A-1) and pigment (A-2) of Claim 1 are included, The coloring composition characterized by the above-mentioned. 17. The method of claim 16,
The said pigment (A-2) is a pigment containing CI pigment blue 15: 6, The coloring composition characterized by the above-mentioned. The method of claim 17,
The mass composition of the said dye composition (A-1) and CI pigment blue 15: 6 is 3: 97-50: 50, The coloring composition characterized by the above-mentioned.