TW201341956A - Colored curable composition, color filter and method of producing the same, and image display device - Google Patents

Abstract

The invention provides a colored curable composition, which contains a xanthene dye represented by general formula (1), a copolymer containing a repeat unit having a N-substituted maleimide group, a polymerizable compound and an organic solvent [R1 to R4: a saturated hydrocarbon group having a carbon quantity from 1 to 10, an aromatic hydrocarbon group having a carbon quantity from 6 to 10; R5: -SO3-, -SO3H, -SO3M, -CO2H, -CO2R6, -SO3R6, -SO2NHR8, -SO2NR8R9; R6: a saturated hydrocarbon group having a carbon quantity from 1 to 10; R8, R9: a hydrogen atom, an alkyl group having a carbon quantity from 1 to 10, a cycloalkyl group having a carbon quantity from 3 to 30, an aromatic hydrocarbon group having a carbon quantity from 6 to 10, an aromatic heterocycle group having a carbon quantity from 5 to 10; M: Na, K; m: 0 to 5; n1 to n4: 0, 1; X: a halogen atom; a: 0, 1].

Description

Colored curable composition, color filter, method of manufacturing the same, and image display device

The present invention relates to a color hardening composition containing a dye as a coloring compound, a color filter, a method for producing the same, and an image display device.

As one of methods for producing a color filter used in a liquid crystal display device or a solid-state imaging device, a pigment dispersion method is widely used. As a pigment dispersion method, there is a method in which a color filter is produced by a photolithography method using a color-curable composition in which a pigment is dispersed in various photosensitive compositions. Since this method contains a pigment, it is stable to light or heat, and since it is patterned by the photolithography method, positional accuracy can be sufficiently ensured, and thus it is considered to be suitable for production of a liquid crystal display device, an EL display device, or the like. The color display used is a color filter or the like.

As a coloring compound for producing a color filter, not only a pigment has been extensively studied, but also a pigment compound other than a pigment such as a dye has been extensively studied. Among them, dyes are known to have pyrimidine azo dyes, pyrazoleazo dyes, xanthene dyes, triarylmethane dyes, and the like. Maternal compound (for example, refer to Japanese Patent No. Japanese Patent Laid-Open No. 2009-265641, and Japanese Patent Laid-Open No. 2009-186657.

The dye is useful as a coloring material because of its own color purity or vividness of color tone, so that the color tone or brightness of the display image at the time of image display can be improved. However, in the case of forming a colored pattern (for example, a color filter) using a dye, it is necessary to make the formed coloring pattern have stability against heat or solvent from a practical viewpoint.

In view of the above, an object of the present invention is to provide a color-curable composition which is excellent in heat resistance and solvent resistance after curing (for example, after formation of a colored cured film (coloring pattern such as a color filter)), and long-term A color filter that displays a high-intensity and high-contrast image, a method of manufacturing the same, and a video display device, and an object of the present invention is to achieve the object.

The specific means for achieving the above problems are as follows.

<1> A colored curable composition comprising (A) a dibenzopyran dye represented by the following formula (1), and (B) a repeating unit having an N-substituted maleimine group Copolymer, (C) polymerizable compound and (D) organic solvent,

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; R ⁶ represents a carbon number of 1 to 10 a saturated hydrocarbon group; R ⁸ and R ⁹ each independently represent a hydrogen atom, a linear or branched 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 carbon. The number of 5 to 10 aromatic heterocyclic groups, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms; M represents a sodium atom or a potassium atom; m represents an integer of 0 to 5, at m In the case of an integer of 2 or more, a plurality of R ^{5 's} may be the same or different; n1, n2, n3, and n4 each independently represent 0 or 1, and when n1 to n4 represent 0, R ¹ to R ⁴ respectively represent hydrogen. Atom; X represents a halogen atom; a represents an integer of 0 or 1; when n1 to n4 all represent 1 and R ⁵ does not represent -SO ₃ ^- , a=1, and at least one of n1 to n4 represents 0. When a=0.

<2> The colored curable composition according to <1>, further comprising a binder resin, wherein the binder resin contains a structural unit represented by the following formula (2) and represented by the following formula (3) a structural unit (b-1) in a structural unit, and a structural unit (b-2) having an acidic group, and having an acid value in the range of 150 mg KOH/g to 300 mg KOH/g,

In the formula (2), R ¹¹ represents a hydrogen atom or a methyl group; and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having a carbon atom number of 3 to 20 having an unsaturated double bond as a partial structure, R ¹² and When both of R ¹² and R ¹³ are a hydrogen atom, when at least one of R ¹² and R ¹³ represents a carbonyl group having a carbon number of 3 to 20 having an unsaturated double bond as a partial structure, a carboxyl group may be further contained as a part. structure;

In the formula (3), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

<3> The colored curable composition according to <1> or <2>, further comprising (E) a photopolymerization initiator.

<4> A colored color filter obtained by curing the colored curable composition according to any one of <1> to <3>.

<5> A method of producing a color filter, comprising the step of forming a coloring layer, and applying the coloring curable composition according to any one of <1> to <3> to a support to form a color a layer; an exposure step of exposing the formed coloring layer in a pattern; and a developing step of forming the colored pattern by developing the exposed colored layer.

<6> A color display device obtained by the color filter according to <4> or the color filter obtained by the method of producing a color filter according to <5>.

According to the present invention, it is possible to provide a color hardening composition which is excellent in heat resistance and solvent resistance after curing (for example, after formation of a colored cured film (coloring pattern such as a color filter)).

Further, according to the present invention, it is possible to provide a color filter that displays a high-intensity and high-contrast image for a long period of time, a method of manufacturing the same, and a video display device.

Hereinafter, the color hardening composition of the present invention will be described in detail, and further, a color filter using the colored curable composition, a method for producing the same, and a video display device will be described in detail.

In addition, in this specification, the numerical range represented by the "~" is a range in which the numerical value shown before and after "~" is used as a lower limit and an upper limit.

In the present specification, "alkyl group" is a generic term for "linear, branched, and cyclic" alkyl groups. Further, the substituent (atomic group) in the present specification is used in the sense of including an unsubstituted one and a more substituted one. That is, in the present specification, the "alkyl group" is used in the sense of containing an unsubstituted alkyl group and a substituted alkyl group, and the other substituents are also the same.

<Coloring hardenable composition>

The color hardening composition of the present invention is at least the dibenzopyran dye represented by the general formula (1) shown in (A) below, and (B) the repeat having the N-substituted maleimine group. It is composed of a copolymer of a unit, (C) a polymerizable compound, and (D) an organic solvent. The color hardening composition of the present invention preferably further contains (E) a photopolymerization initiator. Further, the colored curable composition of the present invention may contain (F) a binder resin different from the above copolymer, and may contain other components such as an additive such as another thiol compound or a surfactant.

Conventionally, various dyes have been known as coloring agents for forming a coloring pattern such as a color filter. Dyes are useful in that their own color purity or hue is bright, and when applied to image display applications, the hue or brightness of the displayed image can be improved. On the other hand, the dye generally has poor heat resistance as compared with the pigment, and thus the performance of the dye is not sufficiently exhibited. Further, the liquid crystal display device is usually manufactured by separately producing a color filter substrate and a thin film-transistor (TFT) substrate, sandwiching the liquid crystal, and bonding them. At this time, in the color filter substrate, an alignment film such as polyimide or the like for aligning the liquid crystal on the color filter is formed. Therefore, the coloring cured film is required to have resistance to a solvent having a high polarity such as N-methyl-pyrrolidone (NMP) contained in the polyimide resin.

In the color hardening composition of the present invention, a dibenzopyran dye as a colorant and a resin having a N-substituted maleimine group are contained. In the configuration of the copolymer of the repeating unit, a colored cured film having more excellent heat resistance and more excellent resistance to a solvent having a high polarity such as NMP can be obtained as compared with a colored pattern containing a conventional dye.

Thereby, a colored cured film (a colored pattern such as a color filter) having higher brightness and having an excellent contrast can be obtained as compared with a colored pattern which simply contains a dye, and even a color tone or brightness which the original dye has can be exerted. Image display.

Further, in a color filter of a color filter (COA) type, a layer of a color filter which also functions as an interlayer insulating film is formed on the TFT, so that color filtering is performed on the TFT. The colored cured film of the sheet is also required as the performance of the interlayer insulating film.

According to the colored curable composition of the present invention, a colored cured film which also has properties such as a low dielectric constant or a peeling liquid resistance as an interlayer insulating film can be formed.

Hereinafter, each component constituting the colored curable composition of the present invention will be described in detail.

-(A) dibenzopyran dye -

The color hardening composition of the present invention contains at least one dibenzopyran dye represented by the following formula (1). The dibenzopyran dye can be used as an alkali-soluble dye, for example, exhibits excellent alkali solubility when subjected to alkali treatment (for example, alkali development after exposure) of the colored curable composition.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include 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 cyclopentyl group, a hexyl group, and a ring. Hexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, tricyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl a group such as 2-ethylhexyloxypropyl, methoxyhexyl or ethoxypropyl. Among these, the saturated hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a group such as a phenyl group and a naphthyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms may be a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ^{9 is} substituted. R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. Here, the saturated hydrocarbon group having 1 to 10 carbon atoms is the same as the "saturated hydrocarbon group having 1 to 10 carbon atoms" of R ¹ to R ⁴ , and the preferred embodiment is also the same. Details of R ⁸ , R ⁹ and M will be described later.

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

Examples of the "-SO ₃ R ⁶ " include a methanesulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, and a sulfonyl group.

Examples of the "-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 isopenic group. Oxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxy Carbonyl, cyclooctyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, tricyclodecyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2 Ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl and the like.

R ⁸ and R ⁹ each independently represent a hydrogen atom, a linear or branched 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 a carbon number of 5 to 5; The aromatic heterocyclic group of 10, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. Further, the aromatic hydrocarbon group and the aromatic heterocyclic group represented by R ⁸ and R ⁹ may be -OH, a saturated hydrocarbon group having 1 to 10 carbon atoms, -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH= CHR ⁶ or a halogen atom is substituted. R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. Here, the saturated hydrocarbon group having 1 to 10 carbon atoms is the same as the "saturated hydrocarbon group having 1 to 10 carbon atoms" of R ¹ to R ⁴ , and the preferred embodiment is also the same.

The linear or branched alkyl group having 1 to 10 carbon atoms represented by R ⁸ and R ⁹ may be unsubstituted or may have a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. a group such as isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, 1,5-dimethylhexyl, octyl or the like. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred.

The cycloalkyl group having 3 to 30 carbon atoms represented by R ⁸ and R ⁹ may be unsubstituted or may have a substituent, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, and the like. Group. Among them, a cycloalkyl group having 3 to 15 carbon atoms is preferred.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ⁸ and R ⁹ include a group such as a phenyl group and a naphthyl group.

Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms represented by R ⁸ and R ⁹ include an aromatic heterocyclic group having a hetero atom such as an oxygen atom or a nitrogen atom, and examples thereof include a pyrrole ring group and a pyrazine ring group. , pyridine ring group, thiazine ring group, triazine ring group, pyrancyclo group, furan ring group, morpholine ring group and the like.

A linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms may also be substituted. Examples of the substituent in the case of the substitution include a hydroxyl group, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aromatic heterocyclic group having 5 to 10 carbon atoms, -CH=CH ₂ or -CH=. CHR ⁶ (R ⁶ : a saturated hydrocarbon group having 1 to 10 carbon atoms). The methylene group contained in the cycloalkyl group may be substituted with an oxygen atom, a carbonyl group or -NR ⁶ -(R ⁶ : a saturated hydrocarbon group having 1 to 10 carbon atoms). Here, the saturated hydrocarbon group having 1 to 10 carbon atoms is the same as the "saturated hydrocarbon group having 1 to 10 carbon atoms" of R ¹ to R ⁴ , and the preferred embodiment is also the same.

The aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted. The substituent in the case of substitution is, for example, preferably ethyl, propyl, phenyl, dimethylphenyl, -SO ₃ R ⁶ (R ⁶ : saturated hydrocarbon group having 1 to 10 carbon atoms) or -SO ₂ NHR ⁸ .

Examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, a nonylphenyl group, and a fluorophenyl group. , chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, nonyloxyphenyl, trifluoromethylphenyl Wait.

Further, when R ⁸ and R ⁹ are bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms, the heterocyclic ring having 1 to 10 carbon atoms may have a saturated hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, and a carbon number of 6 to 6 An aromatic hydrocarbon group of 10 or an aromatic heterocyclic group having 5 to 10 carbon atoms is substituted.

In the above, R ⁸ and R ^{9 are} preferably a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, and carbon. a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, a hydroxyl group-containing aryl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms or an alkoxy group-containing aryl group having 2 to 8 carbon atoms Particularly preferred is 2-ethylhexyl.

Examples of the "-SO ₂ NHR ⁸ " include an amine sulfonyl group, a methanesulfonyl group, an ethaneamine sulfonyl group, a propanyl sulfonyl group, an isopropanyl sulfonyl group, a butane sulfonyl group, and a different Butane amine sulfonyl, pentamamine sulfonyl, isoamylamine sulfonyl, neopentylamine sulfonyl, cyclopentylamine sulfonyl, hexane sulfonyl, cyclohexane sulfonate Sulfhydryl, heptanesulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, 2-ethylhexylsulfonyl, 1,5-dimethylhexylsulfonyl, Cyclooctylamine sulfonyl, decylamine sulfonyl, decylamine sulfonyl, tricyclodecylamine sulfonyl, methoxypropane sulfonyl, ethoxypropane sulfonyl, propyl Oxypropanolamine sulfonyl, isopropoxypropanylsulfonyl, hexyloxypropanylsulfonyl, 2-ethylhexyloxypropanylsulfonyl, methoxyhexaneaminesulfonyl, 3-phenyl-1-methylpropanamine sulfonyl group and the like.

Further, examples of "-SO ₂ NHR ⁸ " and "-SO ₂ NR ⁸ R ⁹ " include groups represented by the following structural formulas.

Further, X ¹ to X ³ in the structural formula shown below are as follows.

X ¹ represents a halogen atom. The halogen atom of X ¹ may, for example, be a fluorine atom, a chlorine atom or a bromine 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 the alkyl group and the alkoxy group may be substituted by a halogen atom. The halogen atom of X ² may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a perfluoromethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.

X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the alkyl group and the alkoxy group may be substituted by a halogen atom. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a perfluoromethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.

M represents a sodium atom or a potassium atom.

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ . R ⁶ , R ⁸ , R ⁹ and M are as described above, and the preferred aspects are also the same.

Wherein R ^{5 is} preferably -CO ₂ H, ethoxycarbonyl, sulfoxyl, 2-ethylhexyloxypropanylsulfonyl, 1,5-dimethylhexylamine sulfonate The form of a 3-phenyl-1-methylpropanamine sulfonyl or isopropoxypropane sulfonyl group.

In addition, m represents an integer of 0 to 5. When m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different. N1, n2, n3, and n4 each independently represent 0 or 1. Here, when n1 to n4 represent 0, R ¹ to R ⁴ each represent a hydrogen atom.

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

a represents an integer of 0 or 1. When all of n1 to n4 indicate 1 and R ⁵ does not represent -SO ₃ ^- , a=1, and when at least one of n1 to n4 represents 0, a=0. At a = 0, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may also exist in the form of an anion group from which one hydrogen atom is removed.

In the above (A) dibenzopyran dye, at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or a carbon number. The aspect of the aromatic hydrocarbon group of 6 to 10 is more preferably at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Further, it is preferable that at least one of R ¹ and R ² and at least one of R ³ and R ⁴ are in the form of an aromatic hydrocarbon group having 6 to 10 carbon atoms.

In the compound represented by the above formula (1), the compound represented by the formula (1-1) to the formula (1-5) can be preferably used as the (A) dibenzopyran dye in the present invention. . The compound represented by the formula (1-5) also includes a salt thereof.

In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms may be a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ^{9 is} substituted. R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , and R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or - SO ₂ NR ⁸ R ⁹ . Here, the saturated hydrocarbon group having 1 to 10 carbon atoms is the same as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{6 in} the general formula (1), and the preferred embodiment is also the same.

R ¹¹ to R ¹⁴ in the formula (1-1) have the same meanings as R ¹ to R ⁴ of the compound represented by the formula (1), and preferred embodiments are also the same. R ⁶ , R ⁸ , R ⁹ , X and a in the formula (1-1) have the same meanings as R ⁶ , R ⁸ , R ⁹ , X and a of the compound represented by the formula (1), and are preferred. The same is true.

In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms may pass through a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -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 , and R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. R ²⁸ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

Here, the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{6 of} the formula (1), and the preferred embodiment is also the same, and may be -OR ²⁶ or halogen. Atomic substitution. Here, the aromatic hydrocarbon group having 6 to 10 carbon atoms is the same as the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ to R ^{4 in} the general formula (1), and the preferred embodiment is also the same. -R ²⁶ or -OR ^{26 is} substituted.

R ²¹ to R ²⁴ in the formula (1-2) have the same meanings as R ¹ to R ⁴ of the compound represented by the formula (1), and preferred embodiments are also the same. Further, m, X and a in the formula (1-2) have the same meanings as m, X and a in the formula (1), respectively, and the preferred aspects are also the same.

In the formula (1-3), R ³¹ and R ³² each independently represent a phenyl group. The phenyl group may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ . R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ , and R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ . The formula R (1-3) is ^26, R ^28, X, and a formula (1-2) R ^26, R ^28, X and a have the same meaning, preferred aspects are also the same.

In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The phenyl group can be substituted with R ²⁶ or -SO ₂ NHR ²⁸ . R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ . The formula R (1-4) is ^26, R ^28, X, and a formula (1-2) R ^26, R ^28, X and a have the same meaning, preferred aspects are also the same.

In the formula (1-5), R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ each independently represent a sulfonic acid. A group or a group represented by the following formula (a1).

R ⁵⁷ HNSO ₂ -...(a1)

In the formula (a1), R ⁵⁷ represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, and an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain. An alkyl group having 2 to 12 carbon atoms which is substituted with an alkoxy group having 2 to 12 carbon atoms, an alkylcarboxyalkyl group represented by the following formula (a2), and an alkoxycarbonyl group represented by the following formula (a3) An alkyl group, or a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group]

R ⁶⁰ -CO-OR ⁶¹ -...Formula (a2)

R ⁷⁰ -O-CO-R ⁷¹ -...Formula (a3)

In the formulae (a2) and (a3), R ⁶⁰ and R ⁷⁰ each independently represent an alkyl group having 2 to 12 carbon atoms, and R ⁶¹ and R ⁷¹ each independently represent an alkylene group having 2 to 12 carbon atoms]

In the formula (1-5), examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include a methyl group, an ethyl group, a propyl group and the like.

Examples of the alkyl group having 2 to 20 carbon atoms represented by R ⁵⁷ include ethyl group, propyl group, n-hexyl group, n-decyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, and 1,3-. Dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and the like.

Examples of the "cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain" represented by R ⁵⁷ include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.

Examples of the "alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain" represented by R ⁵⁷ include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-(n-butyl)cyclohexyl group and the like.

The "alkyl group having 2 to 12 carbon atoms substituted by an alkoxy group having 2 to 12 carbon atoms" represented by R ⁵⁷ may, for example, be 3-ethoxy-n-propyl, propoxypropyl or 4-propoxy. Base-n-butyl, 3-methyl-n-hexyloxyethyl, 3-(2-ethylhexyloxy)propyl and the like.

The "phenyl group substituted with an alkyl group having 1 to 20 carbon atoms" represented by R ⁵⁷ is, for example, an o-isopropylphenyl group.

Examples of the "phenyl group substituted with a phenyl group having 1 to 20 carbon atoms" represented by R ⁵⁷ include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group.

Further, examples of the alkyl group having 2 to 12 carbon atoms of R ⁶⁰ and R ⁷⁰ include an ethyl group, a propyl group, a n-hexyl group, a n-decyl group, a n-decyl group, a n-dodecyl group, and a 2-ethylhexyl group. , 3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and the like.

Examples of the alkylene group having 2 to 12 carbon atoms of R ⁶¹ and R ⁷¹ include a dimethylene group and a hexamethylene group.

The compound represented by the formula (1-5) may also be a compound represented by the formula (a). salt. Examples of the salt include an alkali metal salt of an alkali metal such as sodium or potassium, an amine salt such as triethylamine or 1-amino-3-phenylbutane.

When the substituents R ⁵⁴ , R ⁵⁵ and R ⁵⁶ of the compound represented by the formula (1-5) are a sulfonic acid group, the salt forms a salt in the sulfonic acid group.

Specific examples of the compound represented by the formula (1-5) include C.I. Acid Red 289 and the like.

The compound (including a salt) represented by the above formula (1-1) to formula (1-5) may be used alone or in combination of two or more.

Specific examples of the dibenzopyran dye represented by the formula (1) include the following compounds, C.I. Acid Red 289, and the following compounds (1a) to (f).

Further, the dibenzopyran dye represented by the formula (1) may have a tautomer, and for example, the compound (1b) is a tautomer of the compound (1b-1).

In the following compound (1a), compound (1b), and compound (1b-1), R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H, or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. X and a are as described above.

In the following compound (1c) and compound (1d), R ^d , R ^e and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl.

In the following compound (1e) and compound (1f), 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 2-ethylhexyl.

The dibenzopyran dye represented by the formula (1) can be produced, for example, by chlorinating a dye or a dye intermediate containing -SO ₃ H by a usual method to obtain a -SO ₂ Cl-containing product. The pigment or pigment intermediate reacts with the amine represented by R ⁸ -NH ₂ . Further, the dibenzopyran dye represented by the formula (1) can be produced by chlorinating a dye produced by the method described in JP-A-3-78702, in the same manner as described above. After that, it reacts with an amine.

Color hardening of the present invention with respect to the solid component of the colored curable composition The content of the dibenzopyran dye represented by the formula (1) in the composition is preferably from 0.1% by mass to 40% by mass, more preferably from 1% by mass to 30% by mass. When the content of the dibenzopyran dye is 0.1% by mass or more, a desired color density and color tone can be obtained. In addition, when the content of the dibenzopyran dye is 40% by mass or less, it is advantageous in securing the relative amount of the hardening component such as a resin component or a polymerizable compound.

~Pigment~

In the color hardening composition of the present invention, in addition to the above dibenzopyran dye, a dye or a pigment other than the dibenzopyran dye may be used in combination.

The pigment is preferably a pigment having an average primary particle diameter of 10 nm or more and 30 nm or less. When the average primary particle diameter of the pigment is within the above range, it is easy to obtain a color hardening composition excellent in brightness and contrast.

As the pigment, various inorganic pigments or organic pigments known in the art can be used, and from the viewpoint of reliability, it is preferred to use an organic pigment. The organic pigment in the present invention is, for example, an organic pigment described in paragraph [0093] of JP-A-2009-256572. In particular, the organic pigment in the present invention is preferably a pigment described below from the viewpoint of color reproducibility, but is not limited thereto. These organic pigments may be used singly or in combination in order to improve color purity.

C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264

C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185

C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 71

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58

C.I. Pigment Blue 15:6

C.I. Pigment Violet 23

In the case of using a pigment, the content of the pigment in the colored curable composition of the present invention is preferably from 0.5% by mass to 50% by mass, more preferably 1% by mass, based on the total solid content of the colored curable composition. 30% by mass. When the content of the pigment is within the above range, it is effective in securing excellent color characteristics.

Further, in the present invention, the pigment is preferably used by dispersing the pigment using at least one dispersant, and is used in the form of a pigment dispersion composition. The dispersibility of the pigment can be improved by using a dispersant.

As the dispersant, for example, a known pigment dispersant or a surfactant can be appropriately selected and used. The content of the dispersant is preferably from 1% by mass to 100% by mass, and more preferably from 3% by mass to 70% by mass based on the mass of the pigment.

- (B) a copolymer containing a repeating unit having an N-substituted maleimine group -

The color hardening composition of the present invention contains at least one copolymer (hereinafter also referred to as "the copolymer of the present invention"), and the copolymer contains a repeating unit having an N-substituted maleimine group. In the colored curable composition of the present invention, by incorporating the copolymer together with the dye, the heat resistance of the formed colored cured film is improved, and the performance such as hue or brightness of the display image originally possessed by the dye can be improved.

Further, the copolymer of the present invention is preferably an alkali-soluble resin which exhibits solubility in an alkali solution. In the case where the copolymer of the present invention is an alkali-soluble resin, for example, Good alkali solubility is exhibited upon alkali treatment (for example, alkali development after hardening by exposure).

The repeating unit having an N-substituted maleimine group is not particularly limited, and may be optionally selected, in addition to the N-substituted maleimide group.

The repeating unit having an N-substituted maleimine group may, for example, be a structural unit derived from N-phenylmaleimide, N-o-methylphenylmaleimide, N- M-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenyl malayan An N-(substituted) aryl maleimide such as an amine or N-p-methoxyphenylmaleimine, N-cyclohexylmaleimide or the like.

Among these, in terms of heat resistance and solvent resistance, a structural unit derived from N-phenylmaleimide or N-cyclohexylmaleimine is preferred.

The copolymer of the present invention may contain other repeating units which are bondable to a repeating unit having an N-substituted maleimine group as long as it does not impair the effects of the invention. Examples of such other repeating units include a repeating unit having a double bond, a repeating unit having a hydrophobicity group, and the like. In the present invention, since the copolymer of the present invention contains a repeating unit having a double bond, the strength of the formed cured film is further improved. Further, the copolymer of the present invention can be adjusted in physical properties by containing a repeating unit having a hydrophobic group. In the present invention, by adjusting the physical properties of the copolymer of the present invention, the balance between the curability of the exposed region and the developability of the unexposed region can be further improved. Specific examples of such other repeating units include structural units derived from benzyl (meth)acrylate, glycerol mono(meth)acrylate, allyl methacrylate, glycidyl methacrylate- Methacrylic acid (glycidyl methacrylate adduct) A (meth)acrylate monomer such as cyclohexyl (meth)acrylate, isobutyl (meth)acrylate or 2-hydroxyethyl (meth)acrylate.

The copolymer of the present invention preferably contains a repeating unit having an N-substituted maleimine group in a total range of 0.1 mol% to 70 mol%, more preferably in a range of 1 mol% to 50 mol%. Further, a repeating unit having an N-substituted maleimine group is preferred, and a repeating unit having an N-substituted maleimine group is preferably contained in the range of 20 mol% to 40 mol%. When the content ratio of the repeating unit having an N-substituted maleimine group is within the above range, it is advantageous in terms of both heat resistance and developability.

From the viewpoint of pattern formation, the copolymer of the present invention preferably further contains a repeating unit having an alkali-soluble group as a copolymerizable component. The alkali-soluble group herein may, for example, be a carboxyl group, a hydroxyl group or a sulfonic acid group, and among them, a carboxyl group is preferred.

Examples of the repeating unit having an alkali-soluble group include monocarboxylic acids such as (meth)acrylic acid and crotonic acid, or maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. a repeating unit of a carboxyl group-containing unsaturated monomer such as an unsaturated carboxylic acid such as a dicarboxylic acid, which is derived from succinic acid mono(2-(methyl)acryloxyethyl)ester, -2-ethyl methacrylate Alkoxyethyl ester, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylate, glycerol (meth) acrylate, Morpholine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate Or a repeating unit of an ester monomer such as phenoxy hydroxypropyl (meth)acrylate derived from (meth) acrylamide, N-methylol acrylamide, a secondary or tertiary alkyl acrylamide A repeating unit of isonamide, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, and the like.

Among them, the copolymer of the present invention is preferably a copolymer containing a repeating unit having an N-substituted maleimine group and a repeating unit derived from an unsaturated monomer having a carboxyl group.

The copolymer of the present invention may be a binary copolymer or a trivalent or higher polyvalent copolymer.

The copolymer of the present invention may, for example, be methacrylic acid/N-phenylmaleimide/benzyl methacrylate/styrene copolymer, methacrylic acid/N-phenylmaleimide/methyl group. Benzyl acrylate/glycerol monomethacrylate/styrene copolymer, methacrylic acid/succinic acid mono(2-propenyloxyethyl) ester/N-phenylmaleimide/benzyl methacrylate /styrene copolymer, methacrylic acid / N-phenyl maleimide / benzyl methacrylate / allyl methacrylate copolymer, methacrylic acid / N-phenyl maleimide / A Benzyl acrylate / glycidyl methacrylate - methacrylic acid copolymer, methacrylic acid / N-phenyl maleimide / benzyl methacrylate / styrene / allyl methacrylate / methyl Glycidyl acrylate-methacrylic acid copolymer, methacrylic acid/N-phenylmaleimide/benzyl methacrylate/glycerol monomethacrylate/cyclohexyl methacrylate copolymer, methacrylic acid /N-cyclohexylmaleimide/benzyl methacrylate/glycerol monomethacrylate/cyclohexyl methacrylate copolymer, acrylic acid/N-ring Hexylmaline imidate/benzyl methacrylate/glycerol monomethacrylate/styrene copolymer, and the like.

Among these, the copolymer of the present invention is particularly preferably selected from the group consisting of methacrylic acid/N-phenylmaleimide/benzyl methacrylate/glycidyl methacrylate-methacrylic acid copolymer, and methyl group. One or more of acrylic acid/N-phenylmaleimide/benzyl methacrylate/glycerol monomethacrylate/styrene copolymer.

The copolymer of the present invention is preferably a viewpoint of developability, liquid viscosity, and the like. The weight average molecular weight (polystyrene equivalent value measured by Gel Permeation Chromatography (GPC) method) is 5,000 to 50,000 copolymer, more preferably 5,000 to 30,000 copolymer, and particularly preferably 8,000~ 20,000 copolymer.

Further, the weight average molecular weight is measured by gel permeation chromatography (GPC). GPC is a high-performance liquid chromatography (Gel Permeation Chromatography, GPC) HLC-8220GPC (manufactured by Tosoh Corporation) as a measuring device, and uses TSKgeL Super HZM-H, TSKgeL Super HZ4000, TSKgeL Super HZ2000 (Tosoh ( Manufactured in 4.6 mm ID × 15 cm), three tubes were used as a column and measured using THF (tetrahydrofuran) as a solution.

The content of the copolymer of the present invention in the colored curable composition is preferably from 3% by mass to 70% by mass, and more preferably from 5% by mass to 60% by mass, based on the total solid content of the colored curable composition. When the content of the copolymer of the present invention is 3% by mass or more, the liquid stability when the colored curable composition is prepared is improved, so that generation of development residue at the time of pattern formation can be suppressed, and heat resistance and solvent resistance of the pattern become variable. Excellent. In addition, when the content of the copolymer of the present invention is 70% by mass or less, it is advantageous in terms of coating uniformity and film hardness.

- (C) Polymeric Compound -

The color hardening composition of the present invention contains at least one polymerizable compound.

The polymerizable compound of the present invention is, for example, a polymerizable compound having at least one terminal ethylenically unsaturated double bond. The polymerizable compound of the present invention can be selected from the components of the known constituents, and examples thereof include the components described in paragraph number [0010] to paragraph number [0020] of JP-A-2006-23696, or Japanese patents. Special opening 2006-64921 The components described in paragraph number [0027] to paragraph number [0053] of the bulletin. The polymerizable compound of the present invention is preferably selected from compounds having two or more terminal ethylenically unsaturated bonds.

Such a compound group is widely known in the industrial field to which the present invention pertains, and in the present invention, such a substance can be used without particular limitation. These may, for example, be any of the following chemical forms: monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and such polymers.

Further, the polymerizable compound of the present invention is also preferably a urethane-added polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group, as disclosed in Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent No. Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Application No. Hei. A urethane compound having an oxirane skeleton described in JP-A-62-39417, and JP-A-62-39418 is also preferred.

Further, other examples of the polymerizable compound of the present invention are described in each of the publications of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490. A polyester acrylate such as a polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. Further, as a photocurable monomer and oligomer in the Japanese Adhesive Society vol. 20, No. 7, and pages 300 to 308 (1984), the present invention can also be used as the polymerizable compound of the present invention.

The polymerizable compound of the present invention may be exemplified by the following compounds. Examples: pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isomeric cyanuric acid (methyl Propylene methoxyethyl) ester, pentaerythritol tetra(meth) acrylate ethylene oxide (Ethylene Oxide, EO) modified body, dipentaerythritol hexa (meth) acrylate EO modified body, and the like.

Commercially available products of the polymerizable compound of the present invention include the following products as preferred examples: NK ester A-TMMT, NK ester A-TMM-3, NK oligomeric UA-32P, NK oligomeric UA-7200 (the above is new) Nakamura Chemical Industry Co., Ltd., Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Asia Aronix M-402, TO-1382, TO-2349 (above is manufactured by East Asia Synthetic Co., Ltd.), V # 802 (made by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD D- 330, KAYARAD D-320, KAYARAD D-310, KAYARAD DPHA (above, manufactured by Nippon Kayaku Co., Ltd.).

In the viewpoint of the low-temperature curability, the polymerizable compound of the present invention may be a component described in Paragraph No. [0031] to Paragraph No. [0061] of JP-A-2009-265630. Among them, the polymerizable compound of the present invention is preferably (1) to (20) and (M-1) to (M-8) shown below. In particular, a film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is excellent in terms of low-temperature curability.

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

The content of the polymerizable compound of the present invention in the coloring curable composition (the total content in the case of two or more kinds) is preferably from 10% by mass to 80% by mass based on the total solid content of the colored curable composition. Preferably, it is 15% by mass to 75% by mass, and particularly preferably 20% by mass to 60% by mass.

-(D) organic solvent -

The colored curable composition of the present invention contains at least one organic solvent.

The organic solvent of the present invention is not particularly limited as long as it satisfies the solubility of each component and the coating property in the case of forming a colored curable composition, and it is particularly preferable to consider the solubility and coating properties of the solid component. Security to choose.

The organic solvent of the present invention is preferably exemplified by ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate. , ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, A Methyl oxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate, 2- Alkyl oxypropionates, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propionate c Esters such as ester, ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, methyl cyproterone acetate, ethyl cyproterone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, two Ethylene glycol ethyl methyl ether, propylene glycol single Ethers such as methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone An aromatic hydrocarbon such as toluene or xylene.

In the present invention, the organic solvent is preferably mixed in terms of improving the solubility of each of the above components and the solubility of the alkali-soluble binder and the coating surface when the alkali-soluble binder is contained. Two or more. In this case, the organic solvent of the present invention is particularly preferably a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl. Celluloid, ethyl lactate, diethyl Diol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

The content of the organic solvent in the colored curable composition of the present invention is preferably such that the concentration of the total solid content in the colored curable composition is from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass. The amount of %.

-(E) Photopolymerization initiator -

The color hardening composition of the present invention preferably contains at least one photopolymerization initiator.

The photopolymerization initiator of the present invention is not particularly limited as long as it can polymerize the above polymerizable compound, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator of the present invention is a compound which is photosensitive by exposure light, and which initiates and accelerates polymerization of a polymerizable compound. The photopolymerization initiator of the present invention is preferably a compound which induces and accelerates polymerization of a polymerizable compound by inducing active light having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce active light having a wavelength of 300 nm or more can be preferably used as the photopolymerization initiator of the present invention by being combined with a sensitizer.

Specific examples of the photopolymerization initiator of the present invention include an oxime ester compound, an organic halogenated compound, and Compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxide, azo compound, coumarin compound, azide compound, metallocene a compound, a hexaarylbiimidazole compound, an organoboric acid compound, a disulfonic acid compound, an onium salt compound, a mercaptophosphine (oxide), a benzophenone compound, an acetophenone compound, a derivative thereof, and the like.

In the above, the photopolymerization initiator of the present invention is preferably one or more selected from the group consisting of an oxime ester compound and a hexaarylbiimidazole compound.

The oxime ester compound can be used, for example, in JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, International Publication No. 2005/080337, International Publication No. 2006/ 018 973, Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. Hei. No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, No. 2009-131189 The compound described in the specification and the like.

Specific examples of the oxime ester compound include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(O-phenylene).醯基肟)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)benzene 1,1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O- Benzyl hydrazino)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(methylbenzene) Thio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione , 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl- 6-(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2-A Benzomethane)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzylidene) -9H-carbazol-3-yl]ethanone, 1-(O-ethylhydrazinyl)-1-[9-ethyl-6-(2-butylbenzylidene)-9H-carbazole- 3-yl]ethanone, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O- Acyl oxime A)] and the like. However, in the present invention, it can be used as a photopolymerization initiator The oxime ester compound is not limited to these.

Further, in the present invention, the oxime ester compound as a photopolymerization initiator is preferably a compound represented by the following formula (A) from the viewpoints of sensitivity, stability over time, and coloring upon post-heating. .

In the formula (A), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ¹ represents -R, -OR, -COR, -SR, -CONRR' or -CN, R ² and R ³ each independently represent -R, -OR, -COR, -SR or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these groups may be substituted by one or more selected from the group consisting of a halogen atom and a heterocyclic group, and constitute the One or more of the carbon atoms of the alkyl chain in the alkyl group and the aralkyl group may be substituted with an unsaturated bond, an ether bond or an ester bond, and R and R' may be bonded to each other to form a ring.

In the general formula (A), examples of the halogen atom represented by X ¹ , X ² and X ³ include fluorine, chlorine, bromine, iodine and the like.

Examples of the alkyl group represented by X ¹ , X ² and X ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, and a pentyl group. Isoamyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, alkene Propyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy Ethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole -2'-yl) vinyl and the like.

In the present invention, it is preferred that X ¹ , X ² and X ³ each represent a hydrogen atom, or X ¹ represents an alkyl group and both X ² and X ³ represent a hydrogen atom.

In the general formula (A), examples of the alkyl group represented by R and R' include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a t-butyl group. Pentyl, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, ethylene Base, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy Ethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole -2'-yl) vinyl and the like.

Examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

Examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group.

Examples of the heterocyclic group represented by R and R' include a pyridyl group, a pyrimidinyl group, a furyl group, and a thienyl group.

Further, examples of the ring formed by bonding R and R' to each other include a piperidine ring and a morpholine ring.

The case where R ² and R ³ containing R and R' each independently represent a methyl group, a hexyl group, a cyclohexyl group, -S-Ph, -S-Ph-Cl or -S-Ph-Br is a particularly preferable aspect. Further, Ph represents a phenyl group or a phenyl group.

Among the photopolymerization initiators, the following compounds are particularly suitable as the photopolymerization initiator of the present invention: in the formula (A), X ¹ , X ² and X ³ are each a hydrogen atom; R ¹ is an alkyl group, particularly Is methyl; R ² is alkyl, especially methyl; R ³ is alkyl, especially ethyl.

Preferable specific examples of the photopolymerization initiator represented by the formula (A) include the compounds A to F exemplified below. However, the present invention is not limited by any of the following compounds.

The photopolymerization initiator represented by the formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by the formula (A) used in the present invention is at 250 nm to 500 The absorption wavelength is in the wavelength range of nm. More preferably, it has an absorption wavelength in the wavelength range of 300 nm to 380 nm. Particularly preferred are those with high absorbance at 308 nm and 355 nm.

Further, in the present invention, the oxime ester compound as a photopolymerization initiator is preferably a compound represented by the following formula (B) from the viewpoints of sensitivity, temporal stability, and coloration upon post-heating. .

In the formula (B), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer from 0 to 5. X ²² represents a monovalent substituent. When n is an integer of 2 to 4, a plurality of X ²² existing may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent non-metal atom group shown below.

The monovalent non-metal atom group represented by R ²² may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent A mercapto group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexylcyclopentyl group, a cyclohexyl group, and a trifluoromethyl group.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, for example, Examples of the phenyl group, the biphenyl group, the 1-naphthyl group, the 2-naphthyl group and the like.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, a benzamidine group, and a group. Naphthylmethyl, 2-naphthylmethyl, 4-methyl sulfanyl benzoyl, 4-phenylmercaptobenzyl benzoyl, 4-dimethylaminobenzimidyl , 4-diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzhydryl, 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzene Formyl, 4-methoxybenzhydryl and the like.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

In terms of high sensitivity, R ^{22 is more} preferably an unsubstituted or substituted fluorenyl group, specifically, an unsubstituted or substituted ethyl fluorenyl group, propyl fluorenyl group, and benzoic acid group. Mercapto or tolylmethyl group.

Examples of the substituent include a group represented by the following structural formula, and among them, any of (d-1), (d-4) and (d-5) is preferred.

Examples of the divalent linking group represented by A ²² include an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cyclohexylene group which may have a substituent, an alkynyl group which may have a substituent, and the like.

Examples of the substituent which can be introduced into the groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, and a phenoxy group. An aryloxy group such as a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; and the like.

Among them, in terms of improving the sensitivity and suppressing the coloring caused by heating over time, A ^{22 is} preferably an unsubstituted alkylene group, an alkyl group (for example, methyl group, ethyl group, tert-butyl group, tenth). Dialkyl, etc.) substituted alkylene, alkylene substituted by alkenyl (eg vinyl, allyl, etc.), or aryl (eg phenyl, p-tolyl, xylyl, cumenyl) , naphthyl, anthracenyl, phenanthryl, styryl, etc.) substituted alkylene.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.

Specific examples of Ar include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quater phenyl group, an o-tolyl group, an m-tolyl group, and a p-toluene group. A group, a xylyl group, an o-cumenyl group, a m-cumenyl group, a p-cumenyl group, a 2,4,6-trimethyl group (mesityl), and the like. Among them, the aryl group represented by Ar is preferably a substituted or unsubstituted phenyl group in terms of improving sensitivity and suppressing coloring caused by heating over time.

In the case where the phenyl group has a substituent, the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group. An aryloxy group such as a phenoxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a propenyloxy group, a benzamidine group or the like. An alkyl group such as an anthracene group, an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a methoxalyl group, a methyl group or a cyclohexylamino group. a dialkylamino group such as an amine group, a dimethylamino group, a diethylamino group, a morpholinyl group, a N-hexahydropiperidino group, a phenylamino group, a methyl group, an ethyl group, and a third group An alkyl group such as a decyl group, a hydroxyl group, a carboxyl group or the like.

In the general formula (B), the structure of "SAr" formed by the above Ar and the adjacent S is preferably the following structure, and is preferable in terms of sensitivity.

The monovalent substituent represented by X ²² may, for example, be an alkyl group which may have a substituent (including a halogenated alkyl group which may have a substituent), an aryl group which may have a substituent, an alkenyl group which may have a substituent, may have a substitution Alkynyl group, alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, may be on N A mercapto group having a substituent, an amine group which may have a substituent, a halogen atom or the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, and a 2- Ethylhexyl, phenacyl and the like.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a triphenylene group, a biphenyl group, and an adjacent group. Tolyl, m-tolyl and p-tolyl, xylyl and the like.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a benzyloxy group.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenoxy group, and a 2-methyl group. Phenoxy group, 2-methoxyphenoxy group, and the like.

The alkylthio group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, and a butyl sulfide. Oxyl, isobutylthiooxy, second butoxythio, tert-butoxy, pentylthio, isopentyloxy, hexylthio, heptylthio, octyloxy, 2 -ethylhexyloxyoxy, oxime thiooxy, dodecylthiooxy, octadecylthiooxy, benzylthiooxy and the like.

The arylthio group which may have a substituent is preferably an arylthio group having 6 to 30 carbon atoms, and examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 2-chlorobenzene group. Thiooxy, 2- Methylphenylthiooxy, 2-methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorophenylthiooxy, 3-trifluoromethylphenylthiooxy, 3-cyano Phenylthiooxy, 3-nitrophenylthiooxy, 4-fluorophenylthiooxy, 4-cyanophenylthiooxy, 4-methoxyphenylthiooxy, 4-dimethylaminophenylthio An oxy group, a 4-methylmercaptophenylthio group, a 4-phenylmercaptophenylthio group, or the like.

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

The halogenated alkyl group which may have a substituent may, for example, be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group or a tribromomethyl group. Wait.

Examples of the guanamine group which may have a substituent on N include N,N-dimethylammonium group, N,N-diethylguanamine group and the like.

The amine group which may have a substituent may, for example, be an N,N-dimethylammonium group or the like.

In the above, X ^{22 is} preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, and may have a substituent in terms of solubility in a solvent and absorption efficiency in a long wavelength range. Alkenyl group, alkynyl group which may have a substituent, alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, A halogenated alkyl group which may have a substituent, an amine group which may have a substituent or a guanamine group which may have a substituent on N, and more preferably an alkyl group which may have a substituent.

Further, n in the general formula (B) represents an integer of 0 to 5, and is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, from the viewpoint of easiness of synthesis.

In the general formula (B), when a plurality of X ²² are present, the plurality of X ²² may be the same or different.

Specific examples of the photopolymerization initiator represented by the formula (B) are shown below.

The compound represented by the formula (B) which can be used in the present invention has an absorption wavelength in a wavelength range of from 250 nm to 500 nm, more preferably an absorption wavelength in a wavelength range of from 300 nm to 380 nm, particularly preferably The absorbance is high at wavelengths of 308 nm and 355 nm.

Specific examples of the organic halogenated compound include: Bull. Chem. Soc. Japan, No. 42, 2924 (1969), U.S. Patent No. 3,905,815, and Japanese Patent Publication No. Sho 46-4605 Japanese Patent Laid-Open No. Sho-48-36281, Japanese Patent Laid-Open No. Hei 55-32070, Japanese Patent Laid-Open No. Sho 60-239736, Japanese Patent Laid-Open No. 61-169835, and Japanese Patent Laid-Open 61-169837 Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. SHO-62-212401, Japanese Patent Laid-Open Publication No. SHO-63-70243, Japanese Patent Laid-Open No. SHO-63-298339, MP Hart The compound described in "Journal of Heterocyclic Chemistry" (No. 3), (1970), and the like, and specifically, an oxazole compound substituted with a trihalomethyl group, a s-triazine compound Wait.

Examples of the hexaarylbiimidazole compound include, for example, various compounds described in each specification, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Listed: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5 , 5'-tetraphenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( O-Chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-o-o-dichlorophenyl)-4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (ortho Methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenyl Imidazole and the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds of photopolymerization initiators are used, a plurality of compounds represented by the formula (A) may be used, and a plurality of compounds represented by the formula (B) may also be used. Further, in the present invention, at least one of each of the compounds represented by the general formula (A) and the general formula (B) may be used. Further, in the present invention, at least one of the compounds represented by the general formula (A) and the general formula (B) and the hydrazine other than the compound represented by the general formula (A) and the general formula (B) may be used. A photopolymerization initiator other than the compound or hydrazine compound. Further, in the present invention, a photopolymerization initiator and a sensitizer may be used in combination.

In the case of using a photopolymerization initiator, the total content of the photopolymerization initiator in the color hardening composition of the present invention is preferably from 0.1% by mass to 20% based on the total solid content of the colored curable composition. The mass % is more preferably 0.5% by mass to 10% by mass, most preferably 1% by mass to 5% by mass. When the total content of the photopolymerization initiator is within this range, the sensitivity at the time of exposure is high, and the color characteristics are also good.

-(F) Adhesive resin -

The color hardening composition of the present invention may further contain at least one type of binder resin different from the above-described copolymer of the present invention. In the color hardening composition of the present invention, the film forming property can be further improved by including a binder resin.

For example, the binder resin can be appropriately selected from known ones according to the purpose and the like, as long as it is a polymer compound capable of forming a film which can form a film when it is applied. In the present invention, it is preferable to contain a binder resin (hereinafter also referred to as "the binder resin of the present invention"), and the binder resin contains a structural unit represented by the following formula (2) and below. The structural unit (b-1) in the structural unit represented by the general formula (3), and the structural unit (b-2) having an acidic group, and having an acid value of 150 mg KOH/g to 300 mg KOH/ The range of g.

As shown in the following structure, the binder resin has a crosslinkable group in the molecule because the structural unit (b-1) is a monomer having an unsaturated double bond.

In the formula (2), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having a carbon atom number of 3 to 20 which has an unsaturated double bond as a partial structure, and both of R ¹² and R ¹³ are a hydrogen atom.

Here, R ^{11 is} preferably a methyl group.

When at least one of R ¹² and R ¹³ represents a carbonyl group having 3 to 20 carbon atoms which has an unsaturated double bond as a partial structure, a carboxyl group may be contained as a partial structure. Preferably, R ¹² and R ¹³ each independently represent an α,β unsaturated carbonyl group having 3 to 4 carbon atoms.

Specific examples of the structural unit represented by the general formula (2) are shown below. However, the invention is not limited to these.

In the formula (3), R ²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

Specific examples of the halogen atom represented by R ²¹ to R ²⁵ include, for example, Cl, Br, and I.

The alkyl group represented by R ²¹ to R ²⁵ may be any of a straight chain, a branched group and a cyclic group, and specific examples thereof include a methyl group, a n-propyl group, an isopropyl group, a t-butyl group and the like, and preferably a carbon number of 1. ~7 alkyl.

Examples of the aryl group represented by R ²¹ to R ²⁵ include a phenyl group, a furyl group, and a naphthyl group.

It is preferred that at least one of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ is a hydrogen atom, and more preferably all are hydrogen atoms.

Specific examples of the monomer which forms the structural unit represented by the formula (3) include the following compounds. However, the invention is not limited to these.

The binder resin of the present invention further contains a structural unit derived from a monomer having an acidic group (structural unit (b-2) having an acidic group).

The acidic group in the structural unit (b-2) having an acidic group may, for example, be a carboxyl group, a sulfoxy group or the like.

Further, examples of such a monomer having an acidic group include acrylic acid, methacrylic acid, sulfonic acid, phosphoric acid, etc., of which acrylic acid and methacrylic acid are preferred.

In the adhesive resin of the present invention, the content ratio of the structural unit (b-1) to the structural unit (b-2) (b-1: b-2 [mole ratio]) is preferably 1:0.3 to 1:3. The range is preferably in the range of 1:0.3 to 1:2.

Further, the binder resin of the present invention further contains other structural units different in structure from the structural unit (b-1) and the structural unit (b-2). Examples of the monomer forming another structural unit include benzyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, isobutyl methacrylate, styrene, and the like. .

When the other structural unit is contained, the content of the other structural unit in the adhesive resin of the present invention is preferably more than 0 mol% and 40 mol% or less, more preferably more than 0 mol% and not more than 30 mol%.

The binder resin of the present invention preferably has a weight average molecular weight (polystyrene equivalent value measured by a GPC method) of 5,000 to 50,000, more preferably 10,000 to 40,000, from the viewpoints of developability, liquid viscosity, and the like. Copolymer. Further, the weight average molecular weight is determined by gel permeation chromatography (GPC), as described above for GPC.

Specific examples of the binder resin of the present invention are listed below. Illustrative Compound 1 to Exemplary Compound 9 are binder resins produced by the methods described below. In the following Table 1, the weight average molecular weight and the acid value of the monomer constituting each binder and measured by the GPC gel permeation method are described together. Furthermore, in the present invention, it is not limited to these.

[Table 1]

The details of the monomers in Table 1 are as follows.

. GMA-MAA: glycidyl methacrylate-methacrylic acid

. Allyl-MA: allyl methacrylate

. MAA: Methacrylic acid

. AA: Acrylic

. BzMA: benzyl methacrylate

. CHMA: cyclohexyl methacrylate

The synthesis of the binder resin of the present invention can be carried out by a usual method. Hereinafter, a synthesis example of the exemplified compound 1 and the exemplified compound 6 is shown. Other exemplary compounds can be synthesized by a method similar to the above.

(Illustration of Compound 1 Synthesis)

Methacrylic acid (55 parts by mass), cyclohexyl methacrylate (61 parts by mass), 1-methoxy-2-propanol (175 parts by mass), and V-601 (trade name; manufactured by Wako Pure Chemical Industries, Ltd.) Polymerization initiator (dimethyl-2,2'-azobis(2-methylpropionate) (Dimethyl) A mixed solution of 2,2'-azobis(2-methylpropionate))) (6.8 parts by mass) was polymerized at 90 ° C for 4 hours under a nitrogen stream. Then, glycidyl methacrylate (37 parts by mass), tetraethylammonium bromide (0.6 parts by mass), and methyl ethyl ketone (40 parts by mass) were added to the polymerized reaction mixture solution at 100 ° C. The reaction was carried out for 4 hours, whereby the exemplified compound 1 was synthesized.

(Exemplified synthesis of compound 6)

Allyl methacrylate (79 parts by mass), methacrylic acid (32 parts by mass), 1-methoxy-2-propanol (140 parts by mass), and V-65 (trade name; Wako Pure Chemical Industries, Ltd.) A mixed solution of the produced polymerization initiator (2,2'-azobis(2,4-dimethyl)pentanenitrile) (0.6 parts by mass) was polymerized under a nitrogen stream at 70 ° C for 8 hours. After the reaction mixture solution was cooled to room temperature, water (200 parts by mass) was added and reprecipitation treatment was carried out. The agglomerated polymer was filtered, washed with water, and dried to synthesize the exemplified compound 6.

When the colored curable composition of the present invention contains the adhesive resin of the present invention, the content of the adhesive resin of the present invention in the colored curable composition is preferably from 0.1 part by mass to 20 parts by mass based on 1 part by mass of the dye. .

-(G) Other ingredients -

The colored curable composition of the present invention may contain, in addition to the above components, a known additive such as a polyfunctional thiol compound, a sensitizer, a chain transfer agent, or a polymerization, as long as the effects of the present invention are not impaired. An inhibitor, an organic solvent, a surfactant, a adhesion improving agent, a crosslinking agent, a development accelerator, etc. are other components.

(multifunctional thiol compound)

The colored curable composition of the present invention may also contain a polyfunctional thiol compound.

The colored curable composition of the present invention contains a polyfunctional thiol compound, and the sensitivity is improved, and ion elution or the like caused by a colored material such as a dye is suppressed. Therefore, the present invention is used in the production of a color filter of a liquid crystal display device. When the color-curable composition is colored, deterioration of image quality such as crosstalk can be prevented, and clear and high-quality display can be performed.

In the present invention, the "polyfunctional thiol compound" means a compound having two or more thiol groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more. Specifically, the molecular weight is preferably from 100 to 1,500, more preferably from 150 to 1,000. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6 thiol groups in the molecule, and particularly preferably 2 to 4 groups in the molecule. Mercaptan group. Moreover, it is preferable that the polyfunctional thiol compound is set to be used in the case of polymerization of the above-mentioned radical polymerizable monomer. Specifically, it is preferable to set the amount of the polyfunctional thiol compound to be added in an amount of from 1% by mass to 20% by mass based on the total solid content of the colored curable composition, or less than the above-mentioned The amount of addition of the radical polymerizable monomer.

Preferable specific examples of the polyfunctional thiol compound which can be used in the present invention include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and tetraethylene glycol. Bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptobutyrate), butanediol bis(3-indenyl) Butyrate), 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione and the like. A particularly preferred polyfunctional thiol compound is a compound containing a secondary SH, and further preferably has a triazine skeleton from the viewpoint of liquid stability. Specifically, a Karenz MT series (manufactured by Showa Denko Electric Co., Ltd.) or the like can be cited.

In the case of using a polyfunctional thiol compound, the content of the polyfunctional thiol compound in the color hardening composition of the present invention is preferably 0.01% by mass to 20% by mass based on the total solid content in the colored curable composition. % is more preferably 0.1% by mass to 10% by mass. When the content of the polyfunctional thiol compound is within this range, the sensitivity and storage stability of the colored curable composition are good, and the adhesion of the pixels in the obtained color filter is good without pattern defects, and is used for liquid crystal. In the case of a display device, a color hardening composition having good electrical characteristics can be provided.

(sensitizer)

The colored curable composition of the present invention may further contain a sensitizer. Typical sensitizers which can be used in the present invention can be exemplified in JVCrivello, Adv. in Polymer Sci, 62, 1 (1984), and specifically 芘 ( Pyrene), perylene, acridine, thioxanthone, 2-chlorothiazepine, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy Anthraquinone, anthracene, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives, and the like. In the case of using a sensitizer, it is preferably added in a proportion of 50% by mass to 200% by mass based on the photopolymerization initiator.

(chain transfer agent)

The color hardening composition of the present invention may also contain a chain transfer agent. Examples of the chain transfer agent which can be used in the present invention include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2 a mercapto compound having a heterocyclic ring such as mercaptobenzoxazole, 2-mercaptobenzimidazole or N-phenylmercaptobenzimidazole.

The chain transfer agent may be used alone or in combination of two or more.

In the case of using a chain transfer agent, the content of the chain transfer agent in the color hardening composition of the present invention is preferably from the viewpoint of reducing the sensitivity unevenness with respect to the total solid content in the colored curable composition. The range of 0.01% by mass to 15% by mass is more preferably 0.1% by mass to 10% by mass, particularly preferably 0.5% by mass to 5% by mass.

(polymerization inhibitor)

The color hardening composition of the present invention may also contain a polymerization inhibitor.

The term "polymerization inhibitor" refers to a substance that performs hydrogen supply (or hydrogen donation) and energy supply (or grant) to a polymerization starting species such as a radical generated in a colored curable composition by light or heat. Energy), electron donation (or electron donation), etc., inactivate the polymerization starting species, and inhibit polymerization from starting unintentionally. In the present invention, a polymerization inhibitor or the like described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used.

Among these, a polymerization inhibitor which can be used in the present invention is preferably a p-methoxyphenol.

In the case of using a polymerization inhibitor, the content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass, based on the total mass of the polymerizable compound. ~5 mass%, particularly preferably 0.001 mass% to 1 mass%.

(surfactant)

The color hardening composition of the present invention may also contain a surfactant.

The surfactant which can be used in the present invention may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant. With The nonionic surfactant described in paragraph 0057 of JP-A-2009-098616 is preferred, and among them, a fluorine-based surfactant is preferred.

Other surfactants which can be used in the present invention include, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Megafa (commercially available). Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac ) F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R -90 (made by DiCai (DIC)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (made by Sumitomo 3M (share)), Asahiguard AG7105, Asahiguard 7000, Asahiguard 950, Asahiguard 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Sha Fulong (Sur Flon) SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Sha Fulong ( Surflon) SC-106 (made by Asahi Glass Co., Ltd.), F-Top EF351, F-Top 352, F-Top 801, F-Top 802 (Mitsubishi) The material is electronically produced (manufactured by the company), Ftergent 250 (manufactured by Neos), and the like.

Further, as the surfactant which can be used in the present invention, the following copolymers are preferred. In the case of the structural unit A and the structural unit B represented by the following formula (W), the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1,000 or more. a copolymer of 10,000 or less.

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkyl group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 The above-mentioned alkyl group of 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, and q is a value. a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less)

L is preferably a branched alkyl group represented by the following formula (W-2). R ⁵ in the formula (W-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and the carbon number is preferably 1 or more in terms of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms.

The sum (p+q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

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

In the case of using a surfactant, the content of the surfactant in the color hardening composition of the present invention is preferably from 0.01% by mass to 2.0% by mass based on the total solid content of the colored curable composition. It is 0.02% by mass to 1.0% by mass. When the content of the surfactant is within this range, the coatability and the uniformity of the cured film become good.

(close contact improver)

The colored curable composition of the present invention may further contain a adhesion improving agent.

The adhesion improving agent which can be used in the present invention is a cured film for improving an inorganic substance (for example, a ruthenium compound such as glass, ruthenium, osmium or bismuth oxide, gold, copper, aluminum, etc.) and a color-curable composition layer to be a support. The adhesion of the compound. Specific examples thereof include a decane coupling agent and the like. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known one can be used.

The decane coupling agent is preferably a decane coupling agent described in paragraph [0048] of JP-A-2009-98616, wherein γ-glycidoxypropyltrialkoxydecane or γ-methylpropene is more preferable.醯oxypropyl trialkoxy decane. These may be used alone or in combination Two or more.

When the adhesion improving agent is used, the content of the adhesion improving agent in the colored curable composition of the present invention is preferably from 0.1% by mass to 20% by mass, more preferably, based on the total solid content of the colored curable composition. It is 0.2% by mass to 5% by mass.

(crosslinking agent)

In the colored curable composition of the present invention, the crosslinking agent may be additionally used to further increase the hardness of the colored layer obtained by curing the colored curable composition.

The crosslinking agent which can be used in the present invention is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin, and (b) a solvent selected from the group consisting of a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of a methyl group and a decyloxymethyl group, (c) selected from a methylol group A phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted with at least one substituent of an alkoxymethyl group and a decyloxymethyl group.

Among these, an epoxy resin is particularly preferable because it can be formed into a stronger one by reacting with an acid (resin, monomer, etc.), an SH compound, or the like which is present in the resist system as a curing agent. membrane. From the viewpoint of low viscosity, heat resistance and stability, an alicyclic epoxy is preferred.

For details of specific examples of the crosslinking agent, etc., reference is made to paragraphs [0134] to [0147] of JP-A-2004-295116.

(development accelerator)

When it is intended to promote the alkali solubility in the non-exposed region when the colored curable composition layer is exposed, and further improve the developability of the colored curable composition, A development accelerator may be contained in the color hardening composition of the present invention.

The development accelerator which can be used in the present invention is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less or a low molecular weight phenol compound having a molecular weight of 1,000 or less.

Specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid, and the like. Aliphatic monocarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, azelaic acid (sebacic acid), trisallic acid (brassylic acid), methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid (citraconic) Acid) an aliphatic dicarboxylic acid; an aliphatic tricarboxylic acid such as tricarballylate, aconitic acid, camphoronic acid; benzoic acid, toluic acid, An aromatic monocarboxylic acid such as cumic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, etc.; phthalic acid, isophthalic acid Formic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid (mellophanic acid), pyromellitic acid Aromatic polycarboxylic acid (pyromellitic acid); phenylacetic acid, hydroatropic acid, hydrogen cinnamic acid, mandelic acid, phenyl succinic acid, atopic acid, cinnamic acid, cinnamic acid Ester, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbellic acid, and the like.

(other additives)

In the color hardening composition of the present invention, various additions can be further adjusted as needed. Examples of the material include a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, and the like. The additives are also described in paragraphs [0155] to [0156] of JP-A-2004-295116.

The light-stable composition of the present invention may contain a light stabilizer described in paragraph [0078] of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph [0081] of the publication, and the like.

~Preparation method of colored hardening composition~

The colored curable composition of the present invention is prepared by mixing the above components and optionally any of the components. Further, when preparing a colored curable composition, each component constituting the colored curable composition may be formulated at once, or each component may be dissolved and dispersed in a solvent, and then sequentially formulated. In addition, the order of input or the operating conditions at the time of preparation are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and mixed at the time of use (at the time of coating). A colored hardening composition. The prepared color hardening composition is preferably used after being filtered using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

Since the colored curable composition of the present invention is excellent in heat resistance and solvent resistance, a colored cured film excellent in brightness and contrast can be obtained. Therefore, it can be preferably used for forming a coloring pattern of a color filter or the like constituting a liquid crystal display device, and can be preferably used as a printing ink, an inkjet ink, a paint, or the like.

<Color filter and method of manufacturing the same>

The color filter of the present invention includes a substrate and a colored pixel, and the colored pixel is included in the color filter A colored film formed on the substrate by the colored curable composition of the present invention. The colored region on the substrate is composed of a coloring layer such as red (R), green (G), blue (B) or the like of each pixel forming the color filter.

The color filter of the present invention can be produced by a method comprising the steps of: a colored layer forming step of applying the colored curable composition to a support to form a colored layer (colored curable composition layer); and an exposure step And performing a pattern-like exposure on the colored layer formed in the colored layer forming step; and developing a step of developing the exposed colored layer to form a pattern.

Further, in the method of producing a color filter of the present invention, it is particularly preferable to provide a post-baking step (post-heating step) of heat-treating the coloring pattern obtained in the developing step. In the case of setting a multi-colored coloring pattern, the post-baking step can also be performed after setting the coloring pattern of the last color.

Further, a step of irradiating the colored pattern with ultraviolet rays (post exposure step) may be provided between the development step and the post-baking step.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

First, a method of manufacturing a color filter for a liquid crystal display device of the type used in the prior art will be described as an effective color filter array (Color Filter on) for improving brightness and yield. A method of manufacturing a color filter for a liquid crystal display device of the Array, COA) method will be described.

[Manufacturing method of color filter]

- Colored layer forming step -

In the method of fabricating the color filter of the present invention, first by rotating on the support Coating method such as coating, slit coating, cast coating, roll coating, bar coating, or inkjet is applied to the colored curing composition of the present invention to form a colored layer, followed by heating (pre-heating) The colored layer is dried by baking or vacuum drying or the like.

Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a liquid crystal display device. In addition, a support substrate for a liquid crystal display device of a thin film transistor (TFT) type can be used as a support for a color filter for a COA liquid crystal display device, which will be described later.

On the support, an undercoat layer, an interlayer insulating film, or the like may be provided as needed to improve adhesion to the upper layer, prevent diffusion of substances, or achieve planarization of the surface.

The prebaking conditions may be a condition of heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

Further, the thickness of the coloring layer (thickness after drying) formed by coloring the curable composition can be appropriately selected depending on the purpose. In the color filter for a liquid crystal display device, the thickness of the colored layer is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 1.0 μm to 4.0 μm.

Further, in the color filter for a COA liquid crystal display device to be described later, the thickness of the colored layer (thickness after drying) is preferably in the range of 0.3 μm to 5.0 μm, more preferably in the range of 0.5 μm to 3.5 μm. .

- Exposure step -

Then, in the method of producing a color filter of the present invention, the colored layer formed on the support is subjected to pattern exposure. The light or radiation that can be applied to the exposure is preferably g-rays, h-rays, i-rays, various kinds of laser light, and particularly preferably i-rays. When the i-ray is used for the irradiation light, it is preferably irradiated with an exposure amount of 5 mJ/cm ² to 500 mJ/cm ² .

In addition, other exposure light sources can be used: ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser sources.

~ Exposure step using a laser source~

In the exposure mode using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, more preferably a wavelength in the range of 300 nm to 360 nm. Specifically, it is preferable to use a solid-state Nd: Yttrium Aluminum Garnet (YAG) laser third harmonic (355 nm) or a quasi-molecular thunder with a particularly large output and relatively inexpensive output. XeCl (308 nm) and XeF (353 nm) were shot. The pattern exposure amount is preferably in the range of 1 mJ/cm ² to 100 mJ/cm ² from the viewpoint of productivity, and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² .

The exposure apparatus is not particularly limited, and commercially available products can be used by Callisto (made by V-Technology), EGIS (made by V-Technology), and DF2200G ( Large Japanese screen (share) manufacturing) and so on. Further, it is also preferable to use a device other than the above.

- development step -

Then, the exposed coloring layer is developed with a developing solution. Thereby, a colored pattern can be formed. As long as the developer dissolves the uncured portion of the colored layer and does not dissolve the hardened portion, a combination of various organic solvents or an aqueous alkaline solution can be used. In the case where the developer is an alkaline aqueous solution, it is preferred that the pH of the alkali concentration can be adjusted to 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, and sodium metasilicate. Ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperididine, 1,8-diazabicyclo - [5.4.0]-7-undecene (1,8-diazabicyclo-[5.4.0]-7-undecene).

The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, more preferably from 20 ° C to 30 ° C.

Development can be performed by a puddle method, a shower method, a spray method, or the like.

Further, after development using an aqueous alkaline solution, it is preferred to wash with water.

In the method for producing a color filter of the present invention, in particular, a post-exposure by ultraviolet irradiation may be performed on a colored pattern (pixel) formed using a colored curable composition.

- post baking step -

It is preferable to further heat-treat the colored pattern after development or the colored pattern of post-exposure by ultraviolet irradiation as described above. The colored pattern can be further hardened by heat-treating the formed colored pattern (so-called post-baking treatment). This heat treatment can be performed, for example, by a hot plate, various heaters, an oven, or the like.

The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

The color pattern thus obtained constitutes a pixel in the color filter. In the case of producing a color filter having a plurality of hues of pixels, the colored layer forming step, the exposing step, the developing step, and the post-baking step may be repeated in accordance with the desired number of colors.

Furthermore, each time the formation, exposure and development of the monochromatic color layer is completed (every 1 The above post-baking step may be carried out once after the formation, exposure and development of all the colored layers of the desired color number are completed.

(Method for Manufacturing Color Filter for Liquid Crystal Display Device of COA Method)

The color filter for a COA liquid crystal display device is formed by first applying a coloring curable composition of the present invention containing a colorant onto a TFT substrate to form a coating film of a colored curable composition. The coating film is subjected to pattern exposure, alkali development, post-baking treatment or the like to form respective pixels, and a transparent electrode (Indium Tin Oxide (ITO)) film is formed by sputtering on the respective pixels. Then, a positive photoresist coating film is formed, pattern exposure and development are performed on the photoresist film, and necessary ITO is etched to form a pixel electrode pattern. Thereafter, the photoresist film remaining on the pixel electrode pattern is removed by the stripping liquid, whereby a COA liquid crystal display device color filter can be manufactured.

The formation of the coating film of the colored curable composition can be carried out by a coating method such as spin coating (spin coating), slit coating, cast coating, roll coating, inkjet, or the like. The colored curable composition is applied onto the substrate directly or via another layer, and dried (prebaked) or the like. Further, drying (prebaking) of the colored curable composition coated on the substrate can be carried out by heating at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 using a hot plate, an oven or the like. second. Further, in recent years, the size of substrates has been increasing, and as a method of forming a coating film, slit coating is effective, and this coating method has become widespread.

In the coating film described above, only a portion which is a colored pattern in the coating film is cured by exposure (pattern exposure) through a predetermined mask pattern. Radiation suitable for exposure In particular, ultraviolet rays such as g-rays and i-rays can be cited.

In the case of a negative type, after the above pattern is exposed, an alkali development treatment is performed, whereby the unexposed non-hardened portion is eluted into the alkaline aqueous solution, and only the photohardened portion remains. The developer suitable for the alkali development treatment is preferably an organic alkali developer which does not cause damage to the underlying circuit or the like. The organic alkali developer may be, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, using pure water. An organic basic compound such as 8-diazabicyclo-[5.4.0]-7-undecene is diluted in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. . In the case of using a developer containing such an organic alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Further, the development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

After the alkali development treatment, the excess developer is washed and removed, dried, and then subjected to heat treatment (post-baking). The post-baking is a heat treatment after development for development to achieve complete hardening, and is usually performed at a temperature of 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C. The post-baking treatment can be carried out by heating a hot plate, a convection oven (hot air circulation dryer), a high-frequency heating machine or the like so that the temperature of the coating film after development becomes the above condition. The device is heated. Further, the post-baking treatment can be carried out by either continuous or batch type.

In this manner, by repeating the above-described steps of sequentially forming the coloring-hardening composition of the three colors of red green blue (RGB) in order to form the coloring pattern of the RGB color, a pattern like a pixel containing a plurality of colors can be formed. A color filter that hardens the film.

(How to use color filter for COA liquid crystal display device)

The color filter formed by the above method is used in a COA liquid crystal display device as described below. First, a transparent electrode (ITO) film is formed by sputtering on the pixel of the color filter, and a positive photoresist film having etching resistance is formed thereon. Then, after pattern exposure and development are carried out, unnecessary ITO is etched by a chemical such as hydrofluoric acid to form a pixel electrode. Further, pattern exposure, development, and etching can be carried out without limitation using a generally known method.

Then, the positive resist remaining on the formed pixel electrode was quickly peeled off by the stripping liquid. The peeling liquid is not particularly limited, and a previously known peeling liquid can be used. For example, each of the publications of Japanese Patent Laid-Open No. 51-72503, Japanese Patent Laid-Open No. Hei 57-84456, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. Various organic solvents are disclosed. A typical peeling liquid is a mixed solvent of monoethanolamine (MEA) and dimethylarylene (DMSO). Further, by using an organic solvent heated to 60 ° C or higher as a peeling liquid, the peeling step can be shortened to a short time, and the problem of development residue can be eliminated. Since the colored curable composition of the present invention is excellent in peeling resistance, even when an organic solvent heated to 60 ° C or higher is used, the coating film without the color filter may be peeled off or swollen/expanded. The resist film is removed.

The color filter of the present invention is generally disclosed in Fig. 1 of Japanese Laid-Open Patent Publication No. Hei 9-311347, and can be used in various display devices such as a TFT liquid crystal display device.

The color filter obtained as described above is suitable for a COA type image display device because it is easy to align and can increase the aperture ratio. Further, since the color filter forms a pixel by using the colored curable composition of the present invention, the peeling liquid has high resistance, and thus the yield is high. Production efficiency is also high. In addition, the heat-resistant discoloration property, the low dielectric constant property, the film thickness uniformity, the resolution, the voltage retention ratio, the light resistance, and the like which are required for the color filter are generally good.

In addition to the form in which only one layer of the pixel formed by the colored curable composition of the present invention is formed between the substrate and the pixel electrode, the color filter may have a configuration in which the color is obtained by the present invention. The layer formed by the curable composition and the pixel protective film formed on the film of the pixel are two layers.

The film thickness of the above pixel is preferably from 0.3 μm to 5.0 μm, more preferably from 0.5 μm to 3.5 μm. The thicker the film thickness of the pixel, the higher the chromaticity is achieved, but the resolution of the contact hole is deteriorated, so balance is required.

The film thickness of the above pixel protective film is preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3.0 μm. Further, the above-mentioned pixel protective film can flatten the unevenness of the pixel of the lower layer, and it is desirable that the surface thereof is smooth.

<display device>

The display device of the present invention includes the color filter of the present invention which is excellent in brightness and contrast.

Specific examples of the display device of the present invention include a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a game device display device, and a mobile phone. A display device such as a display device, a digital camera display device, or a car navigation display device. Among these, the object to which the color filter of the present invention is applied is particularly preferably a color display device.

The color filter of the present invention is used for an organic EL display device or a liquid crystal display device In the case of the like, an image with high brightness and excellent spectral characteristics and contrast can be displayed.

~LCD display device~

A liquid crystal display device using the color filter of the present invention will be described. The definition of the organic EL display device or the liquid crystal display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association, issued in 1990)", "Display device" Shunzhang, Industrial Books (shares), issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "New Generation Liquid Crystal Display Technology (Edited by Uchida Ryuo, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be preferably applied to, for example, various types of liquid crystal display devices described in the "New Generation Liquid Crystal Display Technology".

Among them, the color filter of the present invention is particularly effective for a color TFT liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to a liquid crystal with a wide viewing angle such as a horizontal electric field driving method such as In-Plane Switching (IPS) or a multi-Domain Vertical Alignment (MVA) pixel dividing method. Display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching ( Fringe Field Switching (FFS) and Reflective-Optically Compensated Bend (R-OCB). Further, as described above, the color filter of the present invention can also be used in a COA liquid crystal display device.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and further, by emitting red, green, and blue light A Light Emitting Diode (LED) light source (RGB-LED) is used as a backlight to provide a liquid crystal display device having high brightness and high color reproducibility.

~Method of manufacturing liquid crystal display device~

In the following, an application of a color filter formed by using the colored curable composition of the present invention is an example of an image display device (hereinafter also simply referred to as "COA") which is an optimum COA method.

A typical color filter is disposed on a glass substrate and bonded to a TFT substrate. On the other hand, since the technology of COA directly forms a color filter on a TFT substrate, the following aspects (i) to (iii) must be considered as compared with a normal color filter material.

(i) low dielectric constant

In the COA, a pixel electrode is directly disposed on the TFT, so that the voltage is directly applied to the color filter, and therefore the material of the color filter is required to be a low dielectric constant material.

(ii) Contact hole

In the COA, the ITO wiring of the pixel electrode must be connected to the TFT provided under it. Therefore, it is required to reliably form the contact hole at the time of development.

(iii) Stripping liquid resistance

In COA, electrode formation must be performed for each pixel. In the formation of the electrode, ITO is applied to the pixel by sputtering, and wiring by patterning and etching is performed by a positive resist, and then a residual liquid having a high temperature of usually about 80 ° C is used. Type resist Remove the agent. Therefore, in the COA, the color filter or the like is required to have a low swelling ratio, and is not corroded by the peeling liquid, and does not swell due to the peeling liquid, and may not be broken by following the ITO.

On the other hand, when a color filter is formed on a TFT substrate, the occurrence of defective products in the color filter manufacturing step also includes a TFT substrate, which is a defective product, and thus the risk is extremely high. However, in recent years, with the increase in size of LCDs as represented by liquid crystal TVs, the size of manufactured substrates has also increased in size year by year. Further, since the injection time of the liquid crystal is also long, the liquid crystal injection method is gradually changed to the dropping method. As described above, with the increase in the size of the substrate and the application of the liquid crystal dropping method, when the color filter is bonded to the TFT substrate, the alignment accuracy of the color filter and the TFT is made stricter. It is extremely difficult to correct the positional deviation between the center portion and the peripheral portion of the substrate.

In this respect, since the COA is directly provided with a pixel on the TFT, it is not necessary to worry about the positional deviation, and the counter substrate to which the liquid crystal is sandwiched may be prepared by sputtering a substrate on which ITO is entirely deposited. Therefore, only the position of the sealant must be aligned, and the operation efficiency is drastically improved. As described above, the COA technology does not require alignment accuracy (looseness), and therefore has the advantages of making the black matrix's line width very narrow, expanding the aperture ratio, and suppressing the backlight power consumption low. . As a result, various studies on COA have become possible technologies for large LCD substrates in the future. However, as described above, since the risk of producing a color filter on the TFT and the requirement of satisfying the above requirements (i) to (iii) are not provided as the color filter material, the current situation is not carried out. use.

In view of the above, the colored hardening composition of the present invention can be solved by COA The problems caused by the above-mentioned color filter materials can be used in accordance with the respective purposes.

That is, the most preferable method is a method of producing a color filter using the colored curable composition of the present invention containing a colorant.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, unless otherwise indicated, "part" is a quality standard.

(Example 1)

- Preparation of colored curable composition (1) -

First, 20 parts of CI Pigment Blue 15:6, acrylic pigment dispersant (Disper BYK-2020, manufactured by BYK CHIMIE Co., Ltd.) as a coloring pigment And 127 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill.

Then, each component in the following composition was mixed therein. Thus, the colored curable composition (1) was prepared.

<composition>

(A) the following compound 1...13.5 parts

(Dibenzopyran dye represented by the formula (1))

(B) Resin 1...127 parts as described in Table 2 below

(copolymer containing a repeating unit having a N-substituted maleidinium group)

(C) dipentaerythritol hexaacrylate...50 parts

(Manufactured by Nippon Chemical Co., Ltd.; Polymeric Compound)

(D) Propylene glycol monomethyl ether acetate...289 parts

(Organic solvents)

(E) Iruka (IRGACURE) OXE-01...15 servings

(1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenehydrazine)], manufactured by BASF Japan; photopolymerization initiator)

(F) The above-exemplified compound 1 [(F) specific example of the binder resin] 30 parts

(G) Megafac F554...0.02 parts

(Manufactured by Di Love (DIC); surfactant)

- Formation of colored film -

Then, the colored curable composition prepared above was applied onto glass (EAGLE XG; manufactured by Corning) by spin coating, and then heated at 100 ° C for 80 seconds. The volatile component is volatilized, thereby forming a colored film. After cooling, the colored film was irradiated with i-rays (wavelength: 365 nm) to be hardened. At this time, an ultrahigh pressure mercury lamp was used as a light source of i-rays, and the amount of irradiation light was set to 40 mJ/cm ² . Then, after developing for 40 seconds using a 0.05 mass% KOH solution at 25 ° C, the developer was rinsed with pure water to rinse the developer. Thereafter, the dried air was blown and dried, and the colored film was baked at 230 ° C for 30 minutes. Thus, a colored film having a film thickness of 2 μm was formed.

(Example 2 to Example 8, Comparative Example 1 to Comparative Example 4)

The (B) dibenzopyran dye represented by the formula (1) and (B) a copolymer containing a repeating unit having an N-substituted maleimine group are modified as shown in Table 2 below. In the same manner as in Example 1, a colored curable composition (2) to a colored curable composition (12) were prepared, and a colored film was formed and evaluated.

(Evaluation)

The following evaluation was performed using each of the obtained colored curable compositions. The evaluation results are shown in Table 2 below.

-1. Heat resistance (brightness reduction rate) -

The obtained color film was measured for chromaticity using a microscopic spectrophotometer MCPD-3000 (trade name) before and after the post-baking step (heating at 230 ° C for 30 minutes). The index ΔE ^{*ab of the} color change is calculated from the results of the chromaticity measurement before and after the post-baking. In addition, when the value of ΔE ^*ab is 3 or less, it is considered to have excellent heat resistance.

-2. Chemical resistance (solvent resistance; poor chromaticity) -

The colored film obtained after the post-baking step was immersed in NMP (N-methylpyrrolidone) at 25 ° C, and the chromaticity before and after the immersion was measured to calculate a color change index ΔE ^*ab . In addition, when the value of ΔE ^*ab is 3 or less, the change in color tone is small, and it is considered to have excellent stability.

-3. Stability over time -

Each of the prepared colored curable compositions was stored in a refrigerator at 4° C. to 10° C., and the composition stored for 120 days was applied onto a glass substrate, and the presence or absence of foreign matter was observed by light microscopy. Further, in the case where no foreign matter was generated after 120 days passed, it was considered to have excellent stability.

-4. Residue on Resin Black Matrix (BM) -

The presence or absence of the residue was evaluated by the operation shown below.

[Preparation of black curable composition]

Each component in the following composition was mixed to prepare a black curable composition.

<composition>

. Benzyl methacrylate/methacrylic acid copolymer (resin)...30 parts

(Morby ratio is 70/30, weight average molecular weight is about 30,000)

. Dipentaerythritol hexaacrylate (polymerizable compound)...40 parts

. IRGACURE OXE-01...10 copies

(1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenehydrazine)], manufactured by BASF Japan; photopolymerization initiator)

. Carbon black dispersion (pigment)...400 parts

(Dispersion of carbon black (Regal 400R manufactured by Cabot))

. Propylene glycol monomethyl ether acetate...520 parts

. Megafac F554 (made by Di Love (DIC) company)...0.02 parts

[Coating, developing treatment]

The obtained black curable composition was applied onto the glass by a spin coating method, and then heated at 100 ° C for 80 seconds to volatilize the volatile component, thereby forming a black film. After cooling, the black film was irradiated with i-rays (wavelength: 365 nm) to be hardened. At this time, an ultrahigh pressure mercury lamp was used as a light source of i-rays, and the amount of irradiation light was set to 60 mJ/cm ² . Then, after developing for 40 seconds with a 0.05 mass% KOH solution at 25 ° C, the rinse was treated with pure water, thereby washing the developer. Then, the black film was post-baked at 230 ° C for 30 minutes to form a black matrix film (BM film) having a film thickness of 1.1 μm.

Then, 12 kinds of color-curable compositions prepared as described above were sequentially applied to the BM film formation surface of the glass substrate on which the BM film was formed so as to have a film thickness of 2.0 μm, and were used without exposure. A 0.05% by mass KOH solution at ° C was subjected to development treatment for 50 seconds. The color hardening composition provided on the BM film is removed by the development treatment.

Then, the glass substrate on which the BM film was formed after the development treatment was observed with an optical microscope (200 times), and it was confirmed whether or not the residue derived from the colored curable composition was present on the BM film. When no residue was observed, it was evaluated that the pattern formation property was good and it was easy to form a fine image, and it had excellent overlap coating suitability.

The details of the monomer components of the resin (B) in Table 2 above are as follows.

. GMA-MAA: glycidyl methacrylate-methacrylic acid (glycidyl methacrylate adduct of methacrylic acid)

. Allyl-MA: allyl methacrylate

As shown in the above Table 2, the curable composition of the example was prepared by using a specific alkali-soluble resin having an N-substituted maleimine group together with a dibenzopyran dye. It exhibits excellent heat resistance and solvent resistance. Thereby, a color filter having high luminance and excellent contrast can be produced. Further, the curable composition of the examples is excellent in stability at a cold temperature, and can suppress the generation of residue after development.

On the other hand, the comparative hardenable composition used for the dibenzopyran dye together with the resin having no N-substituted maleimine group is not only heat resistant and resistant to dissolution. The agent is poor in composition, and the stability of the liquid itself is poor, and the development residue cannot be suppressed. On the other hand, for the comparative curable composition (Comparative Example 3) using a specific alkali-soluble resin having an N-substituted maleimine group but using a dye other than the dibenzopyran dye, The generation of foreign matter due to cold temperature and the generation of residue at the time of development were not observed, but it was inferior in terms of the effect of improving heat resistance and solvent resistance.

Claims (6)

A colored hardening composition comprising (A) a dibenzopyran dye represented by the following formula (1), and (B) a copolymer containing a repeating unit having an N-substituted maleimine group (C) a polymerizable compound and (D) an organic solvent, Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ⁵ represents -SO ₃ ^- and -SO ₃ H , -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms; ⁸ and R ⁹ each independently represent a hydrogen atom, a linear or branched 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 a carbon number of 5 to 10 The aromatic heterocyclic group, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms; M represents a sodium atom or a potassium atom; m represents an integer of 0 to 5, and m is 2 or more. In the case of an integer, a plurality of R ^{5 's} may be the same or different; n1, n2, n3, and n4 each independently represent 0 or 1. When n1 to n4 represent 0, R ¹ to R ⁴ represent a hydrogen atom, respectively; a halogen atom; a represents an integer of 0 or 1, when n1 to n4 all represent 1 and R ⁵ does not represent -SO ₃ ^- , a=1, and when at least one of n1 to n4 represents 0, a= 0]. The colored curable composition according to claim 1, further comprising a binder resin, wherein the binder resin contains a structural unit represented by the following formula (2) and a formula represented by the following formula (3) a structural unit (b-1) in a structural unit, and a structural unit (b-2) having an acidic group, and having an acid value in the range of 150 mg KOH/g to 300 mg KOH/g, Wherein R ¹¹ represents a hydrogen atom or a methyl group; and R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having a carbon number of 3 to 20 containing an unsaturated double bond as a partial structure, and both of R ¹² and R ¹³ In the case where a hydrogen atom is not present; when at least one of R ¹² and R ¹³ represents a carbon group having 3 to 20 carbon atoms having an unsaturated double bond as a partial structure, a carboxyl group may be further contained as a partial structure]; [wherein R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group]. If the coloring hardening composition described in the first or second aspect of the patent application is applied, Contains (E) photopolymerization initiator. A color filter comprising a color-developing film obtained by curing the color-curable composition according to any one of the first to third aspects of the invention. A method of producing a color filter, comprising the steps of: forming a coloring layer, and applying the coloring curable composition according to any one of claims 1 to 3 to a support to form a color a layer; an exposure step of exposing the formed coloring layer in a pattern; and a developing step of developing the exposed colored layer to form a colored pattern. An image display device comprising the color filter according to claim 4 or the color filter obtained by the method for producing a color filter according to claim 5 of the patent application.