TWI488003B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The conventional photosensitive resin composition contains a pyrazole squaraine compound as a dye and a blue pigment Pigment Blue (P.B) 15:6 as a pigment (for example, Patent Document 1).

However, the coating film obtained by using the photosensitive resin composition may have insufficient brightness and flatness.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-79012

An object of the present invention is to provide a colored photosensitive resin composition which can further improve the brightness and flatness of a coating film.

[1] A colored photosensitive resin composition comprising: a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), And a surfactant (F), and the colorant (A) comprises both the dye (A-1) and the pigment (A-2) containing the compound represented by the formula (1), and the surfactant (F) has a surfactant of a fluorine atom and/or a ruthenium atom, wherein the content of the surfactant (F) is 0.0005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition;

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms is contained. The hydrogen atom may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ Or -SO ₂ N(R ⁸ )R ⁹ is substituted; R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or - SO ₂ N(R ⁸ )R ⁹ ;m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; X represents a halogen atom; a represents 0 or 1 An integer of R ⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 10; and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be a halogen atom or an alkoxy group having a carbon number of 1 to 10; Substituted; -CH ₂ - contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by -O-, -CO- or -NR ⁷ -; R ⁷ represents a monovalent saturation having a carbon number of 1 to 10. a hydrocarbon group; the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms; and R ⁸ and R ⁹ each independently represent a hydrogen atom and have a carbon number of 1~10 alkyl, carbon number Or a cycloalkyl group of -Q 3 ~ 30; or R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having a carbon number of 1 to 10; a hydrogen atom contained in the alkyl and the cycloalkyl group may be the a halogen atom, -OH, -Q, -CH=CH ₂ or -CH=CHR ⁶ is substituted; the alkyl group and the -CH ₂ - contained in the cycloalkyl group may be -O-, -CO-, - Substituted by NH- or -NR ⁶ -; a hydrogen atom contained in a heterocyclic ring having 1 to 10 carbon atoms may be substituted by -R ⁶ , -OH or -Q; Q represents a carbon number of 6 to 10 An aromatic hydrocarbon group or a monovalent aromatic heterocyclic group of 5 to 10 membered rings, wherein the aromatic hydrocarbon group and the hydrogen atom contained in the aromatic heterocyclic group may pass through a halogen atom, -OH, -R ⁶ , -OR ⁶ And -NO ₂ , -CH=CH ₂ or -CH=CHR ⁶ is substituted; M represents a sodium atom or a potassium atom; wherein the compound represented by the formula (1) has the same charge number as the - charge number).

[2] The composition according to [1], wherein a ratio of the content of the dye (A-1) to the content of the pigment (A-2) is 1:99 to 99:1.

[3] The composition according to [1] or [2] wherein the pigment (A-2) is a pigment containing C.I. (Colour Index, Pigment Index) Pigment Blue 15:6.

[4] The composition according to any one of [1] to [3] wherein the solvent (E) is a solvent containing one hydroxyl group-containing solvent.

[5] A coloring pattern formed using the composition according to any one of [1] to [4].

[6] A color filter comprising a colored pattern as in [5].

[7]. The color filter of [6], which is formed by photolithography.

[8] A liquid crystal display device comprising the color filter of [6] or [7].

[9] The use of a composition according to any one of [1] to [4] for producing a color filter.

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

In the present specification, the following substituents differ depending on the carbon number. However, unless otherwise specified, the same ones are exemplified in any of the chemical structural formulae. Further, a substituent which may take both a straight chain or a branched chain includes a substituent which takes a linear chain and a substituent which takes a branch.

The colorant (A) contains both the dye (A-1) and the pigment (A-2) containing the compound represented by the formula (1).

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms is contained. The hydrogen atom may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ Or -SO ₂ N(R ⁸ )R ⁹ is substituted; R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or - SO ₂ N(R ⁸ )R ⁹ ;m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; X represents a halogen atom; a represents 0 or 1 An integer of R ⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 10; and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be a halogen atom or an alkoxy group having a carbon number of 1 to 10; Substituted; -CH ₂ - contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by -O-, -CO- or -NR ⁷ -; R ⁷ represents a monovalent saturation having a carbon number of 1 to 10. a hydrocarbon group; the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms; and R ⁸ and R ⁹ each independently represent a hydrogen atom and have a carbon number of 1~10 alkyl, carbon number Or a cycloalkyl group of -Q 3 ~ 30; or R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having a carbon number of 1 to 10; a hydrogen atom contained in the alkyl and the cycloalkyl group may be the a halogen atom, -OH, -Q, -CH=CH ₂ or -CH=CHR ⁶ is substituted; the alkyl group and the -CH ₂ - contained in the cycloalkyl group may be -O-, -CO-, - Substituted by NH- or -NR ⁶ -; a hydrogen atom contained in a heterocyclic ring having 1 to 10 carbon atoms may be substituted by -R ⁶ , -OH or -Q; Q represents a carbon number of 6 to 10 An aromatic hydrocarbon group or a monovalent aromatic heterocyclic group of 5 to 10 membered rings, wherein the aromatic hydrocarbon group and the hydrogen atom contained in the aromatic heterocyclic group may pass through a halogen atom, -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ or -CH=CHR ⁶ is substituted; M represents a sodium atom or a potassium atom; wherein the compound represented by the formula (1) has the same charge number as the - charge number)

Here, examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an alkyl group-substituted aryl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl 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.

The aryl group substituted with an alkyl group may be any combination of the above aryl group and the alkyl group exemplified below.

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

The saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group in which the substituents are arbitrarily combined, or a cycloalkyl-substituted alkyl group.

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, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group or a 1-methyl group. Propyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-ethylhexyl, decyl, decyl, 1-dimethyl-positive Propyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like.

Examples of the cycloalkyl group include a cycloalkyl group such as 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 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group, and a heptyloxy group. , octyloxy, 1-methylpropoxy, 2-methylpropoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-ethylhexyl Oxyl, decyloxy, decyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy and the like.

The heterocyclic group may be aromatic or may not be aromatic.

Examples of the aromatic heterocyclic group include:

As the heterocyclic ring having no aromaticity, mention may be made of:

Wait. Further, the bond of the heterocyclic group may be any position other than the position described above.

Examples of -OR ⁶ include alkoxy groups such as a methoxy group, an ethoxypropoxy group, a butoxy group, a hexyloxy group, and a 2-ethylhexyloxy group.

Examples of -CO ₂ R ⁶ 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 the -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

As SO ₂ N(R ⁸ )R ⁹ (i.e., -SO ₂ NHR ⁸ ) wherein R ⁹ is a hydrogen atom, an aminesulfonyl group, an N-(methyl)aminesulfonyl group, and an N-(ethyl group) may be mentioned. Aminesulfonyl, N-(propyl)aminesulfonyl, N-(isopropyl)aminesulfonyl, N-(butyl)aminesulfonyl, N-(isobutyl)aminesulfonate , N-(pentyl)amine sulfonyl, N-(isopentyl)amine sulfonyl, N-(neopentyl)amine sulfonyl, N-(cyclopentyl)amine sulfonyl, N -(hexyl)aminesulfonyl, N-(cyclohexyl)aminesulfonyl, N-(heptyl)aminesulfonyl, N-(cycloheptyl)aminesulfonyl, N-(octyl)amine Sulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethylhexyl)aminesulfonyl, N-(cyclooctyl)aminesulfonyl, N-( Amidoxime, N-(fluorenyl)amine sulfonyl, N-(tricyclodecyl)amine sulfonyl, N-(methoxypropyl)amine sulfonyl, N-(B Oxypropyl)aminesulfonyl, N-(propoxypropyl)aminesulfonyl, N-(isopropoxypropyl)aminesulfonyl, N-(hexyloxypropyl)aminesulfonate Mercapto, N-(2-ethylhexyloxypropyl)amine sulfonyl, N-(methoxyhexyl)amine sulfonyl, N-(3-phenyl-1-methylpropyl)amine Sulfonyl and the like.

Further, as SO ₂ N(R ³ )R ⁹ wherein R ⁹ is a hydrogen atom, a group represented by the following formula may be mentioned. 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 alkyl group, particularly a methoxy group, an ethoxy group or a propoxy group.

Examples of the case where R ⁸ and R ⁹ are each a hydrogen atom other than -SO ₂ N(R ⁸ )R ⁹ include the following groups.

Examples of the hetero ring formed by bonding R ⁸ and R ^{9 to} each other include a group represented by the following formula.

Among them, as R ⁸ and R ⁹ , a linear or branched alkyl group having a carbon number of 1 to 10, a cycloalkyl group having a carbon number of 5 to 7, an allyl group, a phenyl group, and a carbon number are preferred. 8 to 10 aralkyl groups, 2 to 8 hydroxyl group-containing alkyl groups and aryl groups, 2 to 8 carbon atoms containing alkoxy groups and aryl groups, more preferably 6 carbon atoms ~8 branched alkyl group.

As the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms, preferred is ethyl group, propyl group, phenyl group, dimethylphenyl group, -SO ₃ R ⁶ or R ^{9 which} is a hydrogen atom - SO ₂ N (R ⁸ )R ⁹ . Here, as R ⁹ is a hydrogen atom of -SO ₂ N (R ⁸⁾ R in the R ^{9. 8,} especially carbon atoms and an alkyl group having a carbon number of 1 to 10 linear or branched chains of from 3 to 30 The cycloalkyl group is preferably a linear or branched alkyl group having a carbon number of 1 to 10, more preferably a branched alkyl group having a carbon number of 6 to 8, particularly preferably 2 Ethylhexyl.

Examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, hexylphenyl group, and nonylphenyl group. Fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoromethyl A phenyl group or the like, and a group further substituted with -SO ₂ N(R ⁸ )R ^{9 on} the phenyl group.

It is preferred that at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or a substituted carbon number of 6 to 10 Hydrocarbyl group.

Preferably R ¹ and R is at least one of the ^2, R ³ and R ^4, and in at least one of carbon atoms or an alkyl group of 1 to 4 carbon atoms may be substituted with an aromatic of 6 to 10 of Hydrocarbyl group.

More preferably, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ are a substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ^{5 is} preferably a carboxyl group, an ethoxycarbonyl group, a sulfo group, an N-(2-ethylhexyloxypropyl)aminesulfonyl group or an N-(1,5-dimethylhexyl)aminesulfonyl group. N-(3-Phenyl-1-methylpropyl)amine sulfonyl, N-(isopropoxypropyl)amine sulfonyl.

The compound represented by the formula (1) is, for example, preferably at least one compound selected from the group consisting of compounds represented by the formulae (1-1) to (1-4).

(In the formulae (1-1) to (1-4), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10; The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, - Substituted with CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or -SO ₂ NR ⁸ R ⁹ ; R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ N(R ⁸ ) R ⁹ ; R ¹⁶ represents -SO ₃ ^- , -SO ₃ H or -SO ₂ N(R ⁸ )R ⁹ ; R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a carbon number of 6 to 10; a valent aromatic hydrocarbon group; the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may pass through a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ N _a , CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ substituted; R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or SO ₂ NHR ²⁸ ; R ²⁶ represents a saturated hydrocarbon group having a carbon number of 1 to 10; the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may have a carbon number of 1 to 10 Substituted by an alkoxy group or a halogen atom; R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or a carbon number It is a monovalent aromatic hydrocarbon group of 6 to 10, and a hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted by -R ²⁶ or -OR ²⁶ ; and R ³¹ and R ³² each independently represent a carbon number. The 6- to 10-monovalent aromatic hydrocarbon group preferably represents a phenyl group; the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ substituted; R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ ; R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ ; R ⁴¹ and R ⁴² are independently The aromatic hydrocarbon group having a carbon number of 6 to 10 is preferably a phenyl group; the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -R ²⁶ or -SO ₂ NHR ²⁸ ; and R ⁴³ represents -SO ₃ ^- or _{^{-SO 2 NHR 28; R 6,}} R 8, R 9, m, X , and a represents the same as defined above)

Among them, the formula (1-4) is preferred.

The compound represented by the formula (1) is, for example, a compound represented by the formula (1a) to the formula (1f). Among them, the number of + charges in the compound represented by the formula (1) is the same as the number of charges.

(wherein R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a ; R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ N _a or -SO ₂ NHR ^a ; R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a ; R ^a represents an alkyl group of 1 to 10, Preferably, it represents 2-ethylhexyl; X and a have the same meanings as above)

The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

Among them, preferred are the formula (1e) and the formula (1f).

The compound represented by the formula (1) can be chlorinated, for example, by a conventional method, with a dye or a dye intermediate having -SO ₃ H, so that the resulting dye or pigment intermediate having -SO ₂ Cl and R ⁸ -NH The amine represented by ₂ is produced by reacting. Further, in the same manner as described above, the dye produced by the method described in the upper right column to the lower left column of page 3 of Japanese Patent Laid-Open No. Hei 3-78702 can be chlorinated to form an amine and Manufactured by reaction.

Examples of the pigment (A-2) contained in the colorant (A) include organic pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, and the like; 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 Red 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 such as rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment on a pigment surface using a polymer compound, or the like, and a sulfuric acid micronization method. The micronization treatment, the cleaning treatment using an organic solvent for removing impurities, water, or the like, the removal treatment of the ionic impurities by an ion exchange method, or the like.

The organic pigment is preferably uniform in particle size. By performing a dispersion treatment by containing 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 this range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained, which is preferable.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content in the colored photosensitive resin composition. . Here, the solid matter refers to the total of the components other than the solvent in the colored photosensitive resin composition.

When the content of the coloring agent (A) is in the above range, the color density of the color filter is sufficient, and the desired amount of the binder polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed. Therefore, it is better.

The content of the dye (A-1) in the colorant (A) is from 3 to 80% by mass, preferably from 3 to 70% by mass, more preferably from 3 to 50% by mass.

The content of the pigment (A-2) in the colorant (A) is 20 to 97% by mass, preferably 30 to 97% by mass, more preferably 50 to 97% by mass.

The content ratio (mass ratio) of the dye (A-1) to the pigment (A-2) is suitably from 1:99 to 99:1, preferably from 1:99 to 60:40, more preferably at 5:95. 40:60. By setting the above ratio, it is easy to optimize the transmission spectrum, and it is preferable to obtain high contrast and high luminance. Further, heat resistance and chemical resistance are improved.

In particular, the mass ratio of C.I. Pigment Blue 15:6 to Dye (A-1) is preferably from 97:3 to 50:50, more preferably from 97:3 to 70:30.

The colored photosensitive resin composition of the present invention contains an alkali-soluble resin (B). The alkali-soluble resin (B) is not particularly limited, and any resin can be used. For example, the alkali-soluble resin (B) contains a structural unit derived from (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The content of the structural unit derived from (meth)acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 mol%, based on the total structural unit constituting the alkali-soluble resin (B). More than % and less than 38% by mole. When the content of the structural unit derived from (meth)acrylic acid is within the above range, the solubility in the non-pixel portion is improved at the time of development. Further, it is preferable that the residue tends to remain in the non-pixel portion after development.

Examples of the other monomer derived from the structural unit other than the structural unit derived from (meth)acrylic acid constituting the alkali-soluble resin (B) include an aromatic vinyl compound, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid. Acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, vinyl carboxylates, unsaturated ethers, vinyl cyanide compounds, unsaturated decylamines, unsaturated quinones, aliphatic conjugates The diene, a macromonomer having a monopropenylfluorenyl group or a monomethacrylinyl 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; and R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

As the alkali-soluble resin (B), specifically, a methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/methacrylic acid is preferred. Benzyl ester / methacrylic acid [ ] ester copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, methacrylic acid / constituents represented by formula (II) In the formula (II), R ⁵³ represents a methyl group, R ⁵⁴ represents a hydrogen atom) / benzyl methacrylate copolymer, and a constituent represented by the formula (II) (wherein, in the formula (II), R ⁵³ represents 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 or the like.

Particularly preferred in terms of hardenability and developability is an alkali-soluble resin (B) represented by the formula (IV).

An alkali-soluble resin (B) containing 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, R ⁵⁴ represents a hydrogen atom) / benzyl methacrylate copolymer, which is obtained by polymerizing methacrylic acid with benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and formula (V) The compound represented by (wherein, R ⁵⁷ represents a hydrogen atom in the formula (V)) is obtained by a reaction.

(In the formula (V), R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

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 The copolymer can be obtained by reacting a monomethacrylate copolymer of benzyl methacrylate, methacrylic acid or a tricyclodecane skeleton with glycidyl methacrylate.

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) or benzoyl peroxide can be used. Or peroxides such as peroxybutyl 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 group can be used. A glycol ether ester such as an ether acetate; a solvent exemplified as the solvent (E) described below.

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 denatured by using 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-dimethylaminomethylphenol and the like. Further, an additive for preventing side reactions may be added. Examples of the additive include hydroquinone and the like.

As the alkali-soluble resin (B), for example, the following copolymers [K1] to [K4] and the like are exemplified.

[K1] The unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (B1) (hereinafter, simply referred to as "(B1)")) and a group having a cyclic ether having a carbon number of 2 to 4 A copolymer obtained by polymerizing the body (B2) (hereinafter, simply referred to as "(B2)").

[K2] A copolymer obtained by polymerizing (B1), (B2) and a monomer (B3). Here, the monomer (B3) (hereinafter sometimes referred to simply as "(B3)") is a monomer copolymerizable with (B1) and/or (B2), and is not (B1) and/or (B2). ) the monomer.

[K3] In the copolymer of (B1) and (B3), copolymerization of a part derived from a carboxyl group derived from (B1) with a group derived from a cyclic ether having a carbon number of 2 to 4 derived from (B2) Things.

[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; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and 3-vinyl phthalic acid. Dicarboxylic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid Unsaturated dicarboxylic acids such as formic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-lower Aceene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[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- a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl neighbor Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic acid anhydride such as tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride); succinic acid mono[2-( Unsaturated mono[(meth)propene of two or more polycarboxylic acids such as methyl) propylene methoxyethyl ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] phthalate a decyloxyalkyl ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

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

These may be used alone or in combination of two or more. In addition, in the present specification, the compounds, components, agents, and the like which are exemplified may be used singly or in combination of two or more kinds as long as they are not described in advance.

(B2) is, for example, at least one selected from the group consisting of a group having a cyclic ether having 2 to 4 carbon atoms (for example, an oxiranyl group, an oxetanyl group, and a tetrahydrofuranyl group) Further, a monomer having an unsaturated bond is further preferred.

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

The monomer having an oxirane group is a polymerizable compound having at least one group 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 group selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group, and having an unsaturated bond. More preferred are monomers having an oxirane group and a (meth) propylene fluorenyloxy group.

The aliphatic oxirane group means a structure obtained by epoxidizing an aliphatic olefin.

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 described in Japanese Laid-Open Patent Publication No. Hei 7-248625, is a glyceride or a glycidyl vinyl ether.

(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 m ¹ is an integer of 1 to 5)

Examples of the compound represented by the above formula (VI) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-ethylene. Glycidyl 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-triglycidyl Oxymethylstyrene, 2,3,5-triglycidoxymethylstyrene, 2,3,6-triglycidoxymethylstyrene, 3,4,5-triglycidoxy Methylstyrene, 2,4,6-triglycidoxymethylstyrene, and the like.

The alicyclic oxiranyl group means a structure obtained by epoxidizing an alicyclic olefin.

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 monomer having an aliphatic monocyclic oxirane group means a polymerizable compound having a structure in which a monocyclic aliphatic olefin is epoxidized. In addition, the monomer having an aliphatic polycyclic oxirane group means a polymerizable compound having a structure in which a polycyclic aliphatic olefin is epoxidized.

As the monomer having an oxiranyl group, a compound having a structure in which an alicyclic olefin is epoxidized and having an unsaturated bond is preferred, and it is preferred to epoxidize the alicyclic olefin. A compound having a structure of (meth) acrylonitrile.

Examples of the monocyclic aliphatic 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 oxirane group include vinylcyclohexene oxide (1,2-epoxy-4-vinylcyclohexane) (for example, Celloxide 2000; Daicel Chemical) (manufactured by Industries, Inc.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Inc.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer) M100; manufactured by Daicel Chemical Industries Co., Ltd.) and the like.

Examples of the polycyclic aliphatic olefin include dicyclopentene, tricyclodecene, and lower 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, an acrylic acid-3,4-epoxy drop can be cited. Ester, methacrylic acid-3,4-epoxy drop An ester, a compound represented by the formula (VII), a compound represented by the formula (VIII), and the like.

In the formulae (VII) and (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, an alkanediyl group having a carbon number of 1 to 6 or *-(CH ₂ ) _s -X'-(CH ₂ ) _t -, and X' represents -S-, -O- Or -NH-, s represents an integer from 1 to 6, and t represents an integer from 0 to 6; wherein s+t≦6; * indicates a 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; hydroxymethyl group; -hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl An alkyl group substituted with a hydroxy group such as 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl or 4-hydroxybutyl.

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

Specific examples of the alkanediyl group having a carbon number of 1 to 6 include a single bond; a methylene group, an exoethyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, and a 1,4-butanediyl group. 1,5-pentanediyl, 1,6-hexanediyl.

Among them, preferred are a single bond, a methylene group, an ethylidene group, -O-CH ₂ -, and -O-(CH ₂ ) ₂ -. More preferably, it is a single bond, -O-(CH ₂ ) ₂ -.

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

In the formula (VII') and the formula (VIII'), R ^71' and R ^72' each have the same meanings as the above R ⁷¹ and R ⁷² .

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).

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 thereof is in molar ratio, preferably (VII): Formula (VIII) is 5:95 to 95:5, more preferably 10:90 to 90:10. And then better is 20:80~80:20.

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

Specific examples of the monomer having an oxetane group include 3-methyl-3-methylpropenyloxymethyloxetane and 3-methyl-3-propenyloxymethyl group. Oxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl 3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxy B A oxetane or a 3-ethyl-3-propenyloxyethyloxetane or the like.

The above-mentioned 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 having an unsaturated bond, more preferably a monomer having a tetrahydrofuranyl group and 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 methyl butyl acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo(methyl) acrylate [ 5.2.1.0 ^2,6 ]decane-8-yl ester (in the technical field, as a customary name, called dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate (meth)acrylic acid (meth)acrylic acid cyclic alkyl esters; (meth)acrylic acid phenyl ester, benzyl (meth) acrylate and other (meth)acrylic acid aryl esters; diethyl maleate, counter-butyl a dicarboxylic acid diester such as diethyl edeoate or diethyl itaconate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 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-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- 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-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 - tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonyl Bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound such as hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-methylbutyleneimine, N- N-alkyl maleimide, such as ethyl maleimide, N-propyl maleimide, N-cyclopentyl maleimide, N-ring N-cycloalkyl maleimide, such as hexyl succinimide, N-cyclooctyl succinimide, N-adamantyl maleimide, N-lower N-arylbutylene phthalate substituted by N-crosslinked carbocyclic group, such as N-aryl maleimide An amine; N-arylalkyl succinimide, such as N-benzyl succinimide; N-butyl succinimide-3-maleimide benzoate, N-butyl quinone imino-4-butyl succinimide butyrate, N-butyl succinimide-6-m-butylene imidate hexanoate, N-butadiene Dicarbonyl quinone imine derivatives such as amino-3-butylenediamine propionate and N-(9-acridinyl) maleimide; styrene, α-methylbenzene Ethylene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide , vinyl acetate, 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 cis are preferred. Butylenediamine, bicyclo[2.2.1]hept-2-ene, and the like.

The copolymers [K1] to [K4] can be found, for example, in the "Experimental Method for Polymer Synthesis" (produced by Otsu Takayuki Press Chemical Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972). The method and the cited documents described in the literature are manufactured.

Specifically, the monomers (B1) and (B2) constituting the copolymer, any specific amount of (B3), a polymerization initiator, and a solvent are added to the reaction vessel, and oxygen is replaced with nitrogen in the absence of oxygen. Under the conditions, stirring, heating, and heat preservation were carried out, whereby a polymer was obtained. The polymerization conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the heat generation amount of the polymerization, and the like.

Here, any of the polymerization initiators and solvents to be used may be used in any of the fields generally used in the art. For example, the following polymerization initiators, solvents, and the like can be used.

Further, the obtained copolymer may be used as it is, or a solution obtained by concentration or dilution may be used, and a solid (powder) may be taken out by a method such as reprecipitation.

In particular, in the case of the polymerization, the following solvent is used as a solvent, whereby the solution after the reaction can be used as it is, and the production steps can be simplified.

The copolymer [K1] is preferably a total molar ratio of the monomers to the monomers constituting the copolymer [K1], and is in the following range in terms of molar fraction.

(B1) 5 to 95% by mole, more preferably 10 to 90% by mole, and even more preferably 10 to 50% by mole;

(B2) 5 to 95% by mole, more preferably 10 to 90% by mole, and even more preferably 50 to 90% by mole.

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

(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 in two stages.

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

In this case, it is preferred that the ratio of each monomer is within the following range with respect to the total number of moles of the monomers constituting the resin.

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

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

Then, a part of the carboxylic acid and/or carboxylic anhydride of (B1) derived from the copolymer of (B1) and (B3) and an oxiranyl group, oxetanyl group or tetrahydrofuran derived from (B2) The base reacts.

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

In this case, the number of moles of (B2) is preferably from 5 to 80 mol%, preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, relative to the number of moles of (B1). %.

The reaction catalyst is preferably used, for example, as a reaction catalyst for a carboxyl group with an oxiranyl group, an oxetanyl group or a tetrahydrofuranyl group. Specifically, tris(dimethylaminomethyl)phenol or the like can be exemplified.

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

The polymerization inhibitor can be exemplified by hydroquinone.

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

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

(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 5,000 to 35,000, 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 be improved, which is preferable.

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

The content of the alkali-soluble resin (B) is from 7 to 65% by mass, preferably from 13 to 60% by mass, more 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 in the above range, a pattern can be formed, and the resolution and the residual film ratio tend to be improved, which is preferable.

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). 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 from the photopolymerization initiator (D) by irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be given.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having a trifunctional or higher polyfunctional group. Examples of the photopolymerizable compound having a trifunctional or higher polyfunctional group include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, and dipentaerythritol hexaacrylate. Dipentaerythritol 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, and even more preferably from 17 to 55% by mass based on the solid content of the colored photosensitive resin composition. %. When the content of the photopolymerizable compound (C) is in the above range, the film is sufficiently hardened, the film thickness ratio before and after development is increased, and it is difficult to cause undercut in the pattern, and the adhesion tends to be good. Therefore, it is better.

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

Examples of the photopolymerization initiator (D) include a living radical generator, an acid generator, and the like. 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-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one. 2-Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Benzene dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- An oligomer or the like of hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propan-1-one, preferably 2-methyl-2-morpholinyl-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-ethyloxy-1- [9-Ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl -6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzimidyl}-9H-indazol-3-yl]B Alkyl-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',5 can be used. , 5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenyl Methyl glyoxylate, titanium titanate 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, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, two An anthracene salt such as phenylhydrazine p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate; nitrobenzyl tosylate; benzoin tosylate;

Further, in the compound described above as the living radical generating agent, a compound which generates an acid simultaneously with the generation of 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 of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is in the above range, high sensitivity can be achieved, exposure time can be shortened, and productivity can be improved, which is preferable.

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

Examples of the photopolymerization initiation assistant (G) 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-methyl Aniline, 4,4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4'- Among them, bis(ethylmethylamino)benzophenone or the like is preferred, and 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 (G) may be used singly or in combination of two or more. In addition, as a photopolymerization initiation aid (G), a commercially available photopolymerization initiation aid (G) may be used, and for example, the product name "EAB-F" (Batugu Valley Chemical Industry) may be mentioned. Manufacturing company, etc.).

The combination of the photopolymerization initiator (D) and the photopolymerization initiation aid (G) in the coloring photosensitive resin composition of the present invention may, for example, be diethoxyacetophenone/4,4'- Bis(diethylamino)benzophenone, 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one / 4,4'-bis ( Diethylamino)benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one/4,4'-bis(diethylamino)benzophenone, benzoate Dimethyl ketal / 4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane 1-ketone/4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone/4,4'-bis(diethylamino)benzophenone, Oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one/4,4'-bis(diethylamino)benzol Ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one/4,4'-bis(diethylamino)benzophenone And, preferably, 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one/4,4'-bis(diethylamino) Benzophenone.

In the case of using the photopolymerization initiation assistant (G), 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 solvent (E) contained in the colored photosensitive resin composition of the present invention 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 (solvent containing -O-), ketones other than esters (solvent containing -CO-), alcohols, aromatic hydrocarbons It is selected from the group consisting of steroids, guanamines, N-methylpyrrolidone, and dimethyl hydrazine.

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 oxyacetate, 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, and 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, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol single Methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether 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 1,3,5-trimethylbenzene.

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.

Among them, it is preferred to contain one type of hydroxyl group-containing solvent. Examples of the hydroxyl group-containing solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, and 4-hydroxy-4-methyl-2-pentanone.

The content of the solvent (E) in the colored photosensitive resin composition is 70 to 95% by mass, more preferably 75 to 92% by mass, based on the coloring photosensitive resin composition. In other words, the content of the solvent (E) is adjusted so that the solid content is 5 to 30% by mass, preferably 8 to 25% by mass, based on the coloring photosensitive resin composition. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density is not insufficient, so that the display characteristics are good, which is preferable.

The surfactant (F) contained in the colored photosensitive resin composition of the present invention is preferably a surfactant having a fluorine atom or a ruthenium atom. Specific examples thereof include 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 ruthenium oxygen bond. Specific examples include: 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; Dow Corning Toray Limited Manufactured by the company), 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) Made by the Japan subsidiary).

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, Megafac F489, Megafac F554, Megafac R30 (manufactured by DIC Corporation); Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemical Co., Ltd.); BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.).

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a ruthenium oxygen bond or a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC Corporation), and the like.

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

The content of the surfactant (F) is preferably 0.0005 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass, per 100 parts by mass of the colored photosensitive resin composition. When the content of the surfactant (F) is in this range, flatness 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 or a colored pattern, and can obtain a color pattern and a color filter excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like. . Moreover, the colored photosensitive resin composition of the present invention 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 components, and the color filter can be provided in a known manner. A display device such as a coloring pattern, an optical film or an array substrate, or a known liquid crystal display device, an organic EL (electroluminescence) device, a solid-state imaging device, or the like, and various devices related to a color image.

As a method of forming a color filter or a pattern thereof using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, formed in advance) On the other colored photosensitive resin composition layer 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 photomask, and then developed; no photolithography is required. A method of using an inkjet device or the like.

The film thickness of the coating film in this case is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and may be, for example, about 0.1 to 30 μm, preferably about 1 to 20 μm, and more preferably It is about 1~6 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) coating method. , die coating method, etc. Further, a dip coater, a bar coater, a spin coater, a slit & spin coater, or a slit coater (sometimes referred to as a die coater) may be used. Coating with a coater such as a curtain flow coater or a spinless coater. 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 heating temperature is suitably about 10 to 120 ° C, preferably about 25 to 100 ° C. The heating time is suitably from about 10 seconds to about 60 minutes, preferably from about 30 seconds to about 30 minutes. The vacuum drying is exemplified as being carried out at a pressure of about 50 to 150 Pa at a temperature of about 20 to 25 °C.

The colored photosensitive resin composition of the present invention can be preferably used for forming a colored image constituting a color filter used in a liquid crystal display element or a solid-state image sensor.

Example

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

Synthesis Example 1: Synthesis of Dye A1

In a flask equipped with a cooling tube and a stirring device, 15 parts of a pigment represented by the formula A0-1 (manufactured by a chemical conversion method), 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were placed and maintained under stirring. At 20 ° C or less, 10.9 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out for 5 hours at the same temperature, and the mixture was cooled to 20 ° C. While maintaining the cooled reaction solution at 20 ° C or lower with stirring, a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Then, the solvent of the obtained reaction mixture was distilled off by a rotary evaporator, and a small amount of methanol was added thereto, and stirred vigorously. The mixture was added to a mixed solution of 375 parts of ion-exchanged water, and the mixture was stirred to precipitate crystals. The precipitated crystals were separated by filtration, washed carefully with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of the dye A1 (mixed dye of dye A1-1 to dye A1-8).

(In the formula (A1), R _c independently represents -SO ₂ NH-R _a , -SO ₃ H, -SO ₃ ^- or -H; R _a represents 2-ethylhexyl)

Synthesis Example 2: Synthesis of Resin B1

Introduced 210 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and the inside of the flask was replaced with nitrogen by air, and then the temperature was raised to 100 ° C, and the mixture was added dropwise. The following solution, that is, a monomethacrylate containing 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd.) , FA-513M) 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 215 g mixture was added with a solution of 2,2'-azobisisobutyronitrile 3.6 g, and further continued at 100 ° C Stir.

Then, the atmosphere in the flask was replaced with air from nitrogen, and 35.5 g of glycidyl methacrylate [0.25 mol (50 mol% relative to the carboxyl group of the methacrylic acid used in the reaction) was introduced into the flask] , tris-dimethylaminomethylphenol 0.9 g and hydroquinone 0.145 g were continuously reacted at 110 ° C to obtain a resin solution B1 having a solid acid value of 79 mg KOH/g.

The weight average molecular weight in terms of polystyrene measured by GPC (gel-permeation chromatography) was 3.0 × 10 ⁴ .

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

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

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

Solid concentration of the tested liquid: 0.001~0.01% by mass

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1 [Preparation of Colored Photosensitive Resin Composition 1]

(A-2) pigment: C.I. Pigment Blue 15:6 3.0 parts

Acrylic pigment dispersant 1.0 part

Propylene glycol monomethyl ether acetate 23 parts

Mixing, using a bead mill to fully disperse the pigment, and then, (A-1) dye: dye A1 0.5 parts

(B) Resin: resin solution B1 16 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4.6 parts

(D) Photopolymerization initiator: OXE-01 (manufactured by Ciba Japan Co., Ltd.) 1.4 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts

(F) Surfactant: Polyether modified polyoxygenated oil (SH8400 manufactured by Dow Corning Toray Co., Ltd.) 0.0005 parts

The coloring photosensitive resin composition 1 was obtained by mixing.

[Formation of coating film for evaluation]

The colored photosensitive resin composition was applied onto a 3 inch square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then prebaked at 100 ° C for 3 minutes in a clean oven. After cooling, it was irradiated with an exposure apparatus (TME-150RSK; manufactured by Topcon Co., Ltd.) at 150 mJ/cm ² (365 nm) in an atmosphere, and heated at 220 ° C for 20 minutes. Use a film. The film thickness of the coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.8 μm.

[Evaluation of flatness]

The obtained coating film surface was visually confirmed. The results are shown in Table 3.

[Brightness evaluation]

The color spectrum of the coating film on the obtained glass substrate was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the CEZ (Commission International de I'Eclairage, International Commission on Illumination) XYZ was measured using a C light source. The xy chromaticity coordinates (Bx, By) and brightness in the color system. The results are shown in Table 3.

Example 2~3

In the same manner as in Example 1, the colored photosensitive resin compositions 2 and 3 were obtained in the same manner as in Example 1 except that (F) was changed to the number of parts shown in Table 1 in the colored photosensitive resin composition 1. Further, in the same manner as in Example 1, the production and evaluation of the coating film for evaluation were carried out. The results are shown in Table 3.

Example 4 [Preparation of Colored Photosensitive Resin Composition 4]

(A-2) pigment: C.I. Pigment Blue 15:6 3.0 parts

Acrylic pigment dispersant 1.0 part

Propylene glycol monomethyl ether acetate 23 parts

Mixing, using a bead mill to fully disperse the pigment, and then, (A-1) dye: dye A1 0.5 parts

(B) Resin: resin solution B1 16 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4.6 parts

(D) Photopolymerization initiator: OXE-01 (manufactured by Ciba Japan Co., Ltd.) 1.4 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts

(F) Surfactant: Megafac F554 (manufactured by DIC Corporation) 0.003 parts

These were mixed to obtain a colored photosensitive resin composition 4.

[Evaluation]

Production and evaluation of the coating film for evaluation were carried out in the same manner as in Example 1. The results are shown in Table 3.

Example 5~6

In the colored photosensitive resin composition 4, the colored photosensitive resin composition was obtained in the same manner as in Example 4 except that the components (B) to (F) were changed to the parts shown in Table 2. Further, in the same manner as in Example 4, the production and evaluation of the coating film for evaluation were carried out. The results are shown in Table 3.

In addition, in Table 3, the content of the surfactant indicates the content of 100 parts by mass based on the coloring photosensitive resin composition.

In Examples 1 to 6, a coating film having no unevenness in flatness was obtained, and excellent brightness was confirmed.

Industrial availability

According to the present invention, it is possible to provide a colored photosensitive resin composition which provides a coating film and a color filter which are excellent in high brightness and flatness.

Claims (8)

A colored photosensitive resin composition for producing a color filter comprising: a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and a surfactant (F), and the colorant (A) contains both the dye (A-1) and the pigment (A-2) containing the compound represented by the formula (1), and a surfactant ( F) is a surfactant having a fluorine atom and/or a ruthenium atom, and the content of the surfactant (F) is 0.0005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition; (In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms is contained. The hydrogen atom may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ Or -SO ₂ N(R ⁸ )R ⁹ is substituted; R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or - SO ₂ N(R ⁸ )R ⁹ ;m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; X represents a halogen atom; a represents 0 or 1 An integer of R ⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 10; the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be a halogen atom or an alkoxy group having a carbon number of 1 to 10; Substituted; -CH ₂ - contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by -O-, -CO- or -NR ⁷ -; R ⁷ represents a monovalent saturation having a carbon number of 1 to 10. a hydrocarbon group; the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom or an alkoxy group having 1 to 10 carbon atoms; and R ⁸ and R ⁹ each independently represent a hydrogen atom and have a carbon number of 1~10 alkyl, carbon number Or a cycloalkyl group of -Q 3 ~ 30; or R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having a carbon number of 1 to 10; a hydrogen atom contained in the alkyl and the cycloalkyl group may be the a halogen atom, -OH, -Q, -CH=CH ₂ or -CH=CHR ⁶ is substituted; the alkyl group and the -CH ₂ - contained in the cycloalkyl group may be -O-, -CO-, - Substituted by NH- or -NR ⁶ -; a hydrogen atom contained in a heterocyclic ring having 1 to 10 carbon atoms may be substituted by -R ⁶ , -OH or -Q; Q represents a carbon number of 6 to 10 An aromatic hydrocarbon group or a monovalent aromatic heterocyclic group of 5 to 10 membered rings, wherein the aromatic hydrocarbon group and the hydrogen atom contained in the aromatic heterocyclic group may pass through a halogen atom, -OH, -R ⁶ , -OR ⁶ And -NO ₂ , -CH=CH ₂ or -CH=CHR ⁶ is substituted; M represents a sodium atom or a potassium atom; wherein the compound represented by the formula (1) has the same charge number as the - charge number). The composition of claim 1, wherein the ratio of the content of the dye (A-1) to the content of the pigment (A-2) is 1:99 to 99:1. The composition of claim 1, wherein the pigment (A-2) is a pigment containing C.I. Pigment Blue 15:6. The composition of claim 1, wherein the solvent (E) is a solvent containing one hydroxyl group-containing solvent. A colored pattern formed using the composition of claim 1. A color filter comprising a colored pattern as claimed in claim 5. The color filter of claim 6, which is formed by photolithography. A liquid crystal display device comprising the color filter of claim 6.