KR101186536B1 - Dye-containing negative type curable composition, color filter and method of producing the same - Google Patents

Abstract

The present invention provides a dye-containing negative curable composition capable of forming a rectangular pattern, having few residues of unexposed portions, and having excellent light and heat fastness, a color filter using the same, and a method of manufacturing the same.

(A) Alkali-soluble binder, (B) Organic solvent-soluble dye, (C) Photoinitiator, (D) Radical polymerizable monomer, (E) At least a dye-containing negative curable composition containing an organic solvent, The said (B) organic solvent soluble dye contains at least 1 sort (s) of the dye represented by following General formula (A), and the quinophthalone type pigment | dye represented by following General formula (1), The dye containing negative type Curable composition.

[In general formula (A), M <^1> represents metals, Z <^1> , Z <^2> , Z <^3> , and Z <^4> respectively independently represent the atomic group which forms the 6-membered ring which consists of atoms chosen from a carbon atom and a nitrogen atom. ]

[In General Formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -SR ^5, or -SR ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. Provided that at least one of R ¹ to R ⁴ represents -SR ⁵ ]

Moreover, together with an alkali-soluble binder, a photoinitiator, and a radically polymerizable monomer, the dye containing negative type further contains at least 1 sort (s) of the pigment represented by following General formula (C1) or General formula (1). Composition.

[Rc ₁ : halogen, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group and the like; Zc ₁ : group of nonmetallic atoms required to form a 6-membered ring; M: two H, metal atoms, metal oxides and the like; cm = 0-2, cn = 0,1-5; cr1-cr4 = 0-1 (cr1 + cr2 + cr3 + cr4 ≧ 1); R ¹ to R ⁴ : H, halogen, -SR ⁵ , -SR ⁶ (at least one of R ¹ to R ⁴ is -SR ⁵ ); An alkyl group containing R ⁵ : O as the ether bond; R ⁶ : alkyl group having an OH group].

Description

Dye-containing negative curable composition, color filter and manufacturing method thereof {DYE-CONTAINING NEGATIVE TYPE CURABLE COMPOSITION, COLOR FILTER AND METHOD OF PRODUCING THE SAME}

The present invention provides a dye-containing negative curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid-state imaging device (CCD, CMOS, etc.), and the dye-containing negative curable composition. A color filter and a method of manufacturing the same.

As a method of manufacturing the color filter used for a liquid crystal display element or a solid-state image sensor, the dyeing method, the printing method, the electrodeposition method, and the pigment dispersion method are known.

Among these, the pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition obtained by dispersing a pigment in various photosensitive compositions. Since the pigment is used, it is advantageous in that it is stable in light or heat. Have In addition, since it is patterned by the photolithography method, it has been widely used as a preferable method for producing a color filter for a large screen and a high-precision color display with high positional precision.

When manufacturing a color filter by the pigment dispersion method, a radiation-sensitive composition is apply | coated on a glass substrate with a spin coater, a roll coater, etc., and it dries to form a coating film, and the colored film is formed by pattern exposure and development of the said coating film. The color filter can be obtained by repeatedly performing this operation for each color.

As said pigment dispersion method, the negative photosensitive composition which used together the photopolymerizable monomer and the photoinitiator in alkali-soluble resin is described (for example, refer patent documents 1-4).

In addition, in recent years, the color filter for a solid-state image pickup device is required to further improve the precision. However, in the conventional pigment dispersion system, it is difficult to further improve the resolution, and there are problems such as color deviation caused by coarse particles of the pigment. For this reason, it is not suitable for the use which requires a fine pattern like a solid-state image sensor.

In order to solve such a problem, the technique which uses dye instead of a pigment is conventionally proposed (for example, refer patent document 5). However, the curable composition containing a dye generally has a problem that it is inferior to the curable composition using a pigment with respect to various performances, such as light resistance, heat resistance, solubility, and coating uniformity, for example.

Particularly, in the case of manufacturing a color filter for a solid-state image pickup device, a film thickness of 1.5 µm or less is required. Therefore, a large amount of pigment must be added to the curable composition, resulting in insufficient adhesion to the substrate or sufficient curing. There also arises a problem that pattern formation is remarkably difficult, such as not being able to support it, or dyes falling out in the exposed portion.

Furthermore, there is little knowledge about the technique of forming a micropattern of a system using a dye, and only the examples disclosed up to now have no residues in a region to be removed, that is, a non-exposed region (non-image portion), It is difficult to configure the cross-sectional shape into a good rectangular shape.

Patent Document 1: Japanese Patent Application Laid-Open No. 2-181704

Patent Document 2: Japanese Patent Application Laid-Open No. 2-199403

Patent Document 3: Japanese Patent Application Laid-Open No. 5-273411

Patent Document 4: Japanese Patent Application Laid-Open No. 7-140654

Patent Document 5: Japanese Patent Application Laid-Open No. 6-75375

Patent Document 6: Japanese Patent Application Laid-Open No. 54-63903

As described above, although the dye-containing curable composition is useful in applications such as solid-state imaging devices that require high precision and uniform color, it is possible to solve the residue of the non-image part and to maintain the color density and color of the dye stably and heat resistance and light resistance. The improvement of the fastness of the back became a subject.

Accordingly, it is an object of the present invention to provide a dye-containing negative curable composition suitable for use of dyes, specifically, high sensitivity, no residue on unexposed areas, rectangular fine patterns can be formed, and heat fastness And a dye-containing negative curable composition excellent in light fastness and a color filter using the same. At the same time, an object of the present invention is to provide a color filter having excellent pattern formability and high cost performance, particularly a color filter for a solid-state image pickup device and a method of manufacturing the same.

The specific means for solving the said subject is as follows.

Dye-containing negative curable containing at least <1> (A) alkali-soluble binder, (B) organic solvent soluble dye, (C) photoinitiator, (D) radical polymerizable monomer, and (E) organic solvent As a composition, the said (B) organic solvent soluble dye contains at least 1 sort (s) of the dye represented by following General formula (A), and the quinophthalone pigment | dye represented by following General formula (1), The dye characterized by the above-mentioned. It is a containing negative curable composition.

[In general formula (A), M <^1> represents metals, Z <^1> , Z <^2> , Z <^3> , and Z <^4> respectively independently represent the atomic group which forms the 6-membered ring which consists of atoms chosen from a carbon atom and a nitrogen atom. ]

[In General Formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -SR ^5, or -SR ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. Provided that at least one of R ¹ to R ⁴ represents -SR ⁵ ]

<2> The dye represented by the general formula (A) is a phthalocyanine dye represented by the following general formula (B), wherein the dye-containing negative type curable composition of the above <1>.

[In General Formula (B), M ¹ represents metals, and R ¹⁰¹ to R ¹¹⁶ each independently represent a hydrogen atom or a substituent.]

<3> The dye-containing negative curable composition according to <1> or <2>, wherein the photopolymerization initiator (C) is an oxime compound.

<4> The (A) alkali-soluble binder is a dye-containing negative curable composition of the above <1> to <3>, wherein the alkali-soluble binder is a resin having an unsaturated double bond in a side chain thereof.

<5> The said (E) organic solvent is a dye-containing negative curable composition of said <1>-<4> characterized by containing a cyclic ketone solvent.

<6> It is a color filter characterized by using the dye-containing negative curable composition of said <1>-<5>.

<7> A method for producing a color filter comprising applying the dye-containing negative curable composition of <1> to <5> on a support, then exposing through a mask, and developing to form a pattern to be.

<8> A dye-containing negative curable composition containing (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photoinitiator, and (D) a radical polymerizable monomer, wherein said (B) Dye-containing negative curable, characterized in that the organic solvent-soluble dye contains at least one of the dyes represented by the following general formula (C1) and at least one of the quinophthalone dyes represented by the following general formula (1). Composition.

[In Formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, or an aryl. Oxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group , An aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a six-membered ring together with a carbon atom, and four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents the integer of 0 or 1-5, and four cn may be same or different. However, one of the cn a plurality of Rc ₁ represents an integer of 1-5, the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1 and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

[In General formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom, a halogen atom, -SR <^5> or -SR <^6> , and at least 1 of R <^1> -R <^4> is -SR <^5> . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. ]

The <9> above-mentioned (C) photoinitiator is a dye-containing negative curable composition as described in <8> which is an oxime type compound.

The <10> above-mentioned (A) alkali-soluble binder is a dye-containing negative curable composition as described in <8> or <9> which is resin which has an unsaturated double bond in a side chain.

It is a dye-containing negative curable composition in any one of <8>-<10> which contains a <11> organic solvent further and the said organic solvent contains a cyclic ketone solvent.

<12> It is a color filter characterized by containing 1 or more types of dyes represented by the following general formula (C1), and 1 or more types of quinophthalone type dyes represented by the following general formula (1).

The color filter as described in this <12> becomes like this, Preferably it uses using the dye containing negative type curable composition in any one of said <8>-<11>.

[In Formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, or an aryl. Oxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group , An aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a six-membered ring together with a carbon atom, and four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents the integer of 0 or 1-5, and four cn may be same or different. However, one of the cn a plurality of Rc ₁ represents an integer of 1-5, the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1 and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

[In General formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom, a halogen atom, -SR <^5> or -SR <^6> , and at least 1 of R <^1> -R <^4> is -SR <^5> . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group.]

<13> Having a process of apply | coating the dye-containing negative curable composition in any one of said <8>-<11> on a support body, exposing through a mask, developing, and forming a pattern shape, It is characterized by the above-mentioned. It is a manufacturing method of a color filter.

EMBODIMENT OF THE INVENTION Hereinafter, the dye-containing negative curable composition of this invention, the color filter comprised using the said dye-containing negative curable composition, and its manufacturing method are demonstrated in detail.

<< dye-containing negative curable composition >>

The dye-containing negative curable composition of the present invention comprises (A) an alkali soluble binder, (B) an organic solvent soluble dye, (C) a photopolymerization initiator, (D) a radical polymerizable monomer, and (E) an organic solvent. At least 1 type of dye represented by general formula (A) which the said (B) organic solvent soluble dye contains later as a dye containing negative curable composition containing at least, and the quinophthalone represented by general formula (1) mentioned later It is characterized by containing a system pigment | dye (Hereinafter, these may be called "the pigment | dye in this invention.").

Another dye-containing negative type curable composition of the present invention is (A) an alkali-soluble binder and (B) an organic solvent-soluble dye, and at least one of the dyes represented by the general formula (C1) shown below and general formula ( It is made by containing at least 1 sort (s) of the quinophthalone pigment | dye represented by 1) (henceforth "the pigment | dye which concerns on this invention"), (C) photoinitiator, and (D) radically polymerizable monomer. It can comprise using (E) organic solvent, and can also comprise using other components, such as a crosslinking agent, as needed.

The dye-containing negative curable composition of this invention can improve the heat fastness and light fastness of the pattern formed using this by containing the pigment | dye in this invention. In addition, the dye-containing negative curable composition of the present invention can be made highly sensitive, a rectangular pattern can be formed, and the residue can be removed from the unexposed part.

The dye-containing negative curable composition of the present invention may be exposed by any of a proximity method, a mirror projection method, and a stepper method, but in particular, exposure is performed by a stepper method (reduced projection exposure method using a zoom projection exposure machine). It is preferable to carry out. Such a stepper system forms a pattern by performing exposure while varying an exposure amount stepwise, and when performing such stepper exposure, the rectangularity of the pattern which is one of the effects of this invention can be especially made favorable.

Moreover, as an exposure apparatus used for the said stepper exposure, i line | wire stepper (brand name: FPA-3000i5 +, Canon Corporation make) etc. can be used, for example.

-(A) alkali-soluble binder-

First, the alkali-soluble binder in this invention is demonstrated. The alkali-soluble binder in the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

The alkali-soluble binder in the present invention is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution. As such linear organic polymer, a polymer having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid described in each of Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 The copolymer, the partially esterified maleic acid copolymer, etc. are mentioned, The acidic cellulose derivative which has a carboxylic acid in a side chain is useful. In addition, an acid anhydride is added to the polymer having a hydroxyl group, polyhydroxystyrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

Moreover, as an alkali-soluble binder in this invention, the polymer which copolymerized the monomer which has a hydrophilic group can also be used. Examples of the monomer having a hydrophilic group include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-metholacrylamide, secondary and tertiary. Alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) Acrylate, ethyl (meth) acrylate, a branched or linear propyl (meth) acrylate, a branched or linear butyl (meth) acrylate, a phenoxyhydroxypropyl (meth) acrylate, etc. are mentioned.

In addition, as the monomer having a hydrophilic group, a monomer containing a tetrahydrofurfuryl group, phosphoric acid, a phosphate ester, a quaternary ammonium salt, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid and its salt, a morphonylethyl group, and the like are also useful.

Moreover, it is preferable that the alkali-soluble binder in this invention has an unsaturated double bond in a side chain in order to improve crosslinking efficiency. As an unsaturated double bond couple | bonded with the side chain of the alkali-soluble binder in this invention, an allyl group, a (meth) acryl group, a vinyl group, etc. are mentioned, for example, An allyl group and a (meth) acryl group are preferable. These unsaturated double bonds may be introduced by copolymerizing units having the above unsaturated double bonds, or may be introduced later by a polymer reaction. As an alkali-soluble binder which has the said unsaturated double bond in a side chain, KS resist-106 (made by Osaka Yuki Kagaku Kogyo Co., Ltd.), cyclomer P series (made by Daicel Kagaku Kogyo Co., Ltd.), etc. are preferable, for example. Is used.

Moreover, as an alkali-soluble binder in this invention, acrylic resin is preferable among the said various binders, As an acrylic resin, benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) Copolymers consisting of monomers selected from acrylamide and the like, KS-resist-106 (manufactured by Osaka-Yaki Kagaku Kogyo Co., Ltd.), and Cyclomer P series are preferred.

Examples of the alkali-soluble binder, a developing property, the weight-average molecular weight of the polymer of (a polystyrene conversion value measured by GPC method) 1000 ~ 2 × 10 ⁵ in terms of solution viscosity are preferred, and 2000-1 are polymers of × 10 ⁵ More preferably, the polymer of 5000-5 * 10 <^4> is especially preferable.

As for content of the said alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid in a composition from a viewpoint of developability etc., 20-80 mass% is more preferable, 30-70 mass% is especially preferable.

(B) Organic Solvent Soluble Dye

The dye-containing negative curable composition of this invention contains at least 1 sort (s) of the pigment | dye represented by following General formula (A), and at least 1 sort (s) of the quinophthalone pigment | dye represented by following General formula (1).

Dye represented by general formula (A)

The dye-containing negative curable composition of this invention contains at least 1 sort (s) of the dye represented by the following general formula (A). This dye exhibits a good cyan color with high transmittance characteristics, has no sedimentation over time when it is in the state of a liquid preparation or a coated coating film, and is excellent in stability, and particularly has excellent resistance to heat and light.

In said general formula (A), M <^1> represents metals, Z <^1> , Z <^2> , Z <^3> and Z <^4> respectively independently represent the atomic group which forms the 6-membered ring which consists of atoms chosen from a carbon atom and a nitrogen atom.

In General Formula (A), M ¹ represents metals, and examples of the metals include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and AlCl. , InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, GeCl _2, etc. are included in the metal chloride, TiO, metal oxides, and metal hydroxides such as Si (OH) _2, such as VO.

In said general formula (A), Z <^1> , Z <^2> , Z <^3> and Z <^4> respectively independently represent the atom group required in order to form the 6-membered ring which consists of atoms chosen from a carbon atom and a nitrogen atom. The 6-membered ring may be a saturated ring or an unsaturated ring, may be unsubstituted or may have a substituent, and another 5- or 6-membered ring may be condensed. The six-membered ring includes a benzene ring, a cyclohexane ring and the like. The substituent mentioned later as a substituent which the said 6-membered ring has is mentioned. In addition, when the said 6-membered ring has two or more substituents, these substituents may be same or different.

As a substituent which the said 6-membered ring has, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably C1-C48, more preferably 1-18, linear, branched, or cyclic) Alkyl groups, for example methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1 -Norbornyl, 1-adamantyl) and alkenyl groups (preferably alkenyl groups having 2 to 48 carbon atoms, more preferably 2 to 18. For example, vinyl, allyl, 3-buten-1-yl) , An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 12. For example, phenyl, naphthyl), a heterocyclic group (preferably 1 to 32 carbon atoms, more preferably 1 to Heterocyclic group of 12. For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1- Midazolyl, 1-pyrazolyl, benzotriazol-1-yl) and silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably 3 to 12. For example, trimethylsilyl, triethylsilyl, Tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably C1-C48, more preferably 1-12 alkoxy group). For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups (e.g. cyclopentyloxy, cyclohexyloxy) , An aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 12. For example, phenoxy, 1-naphthoxy), heterocyclic oxy group (preferably 1 to 32 carbon atoms) More preferably, it is a heterocyclic oxy group of 1-12. For example, 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy), a seal | sticker Oxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy) and acyloxy group (preferably Preferably it is a C2-C48, More preferably, it is an acyloxy group of 2-12. For example, they are acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy) and an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 12 alkoxycarbonyloxy groups). For example, an ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group (for example, cyclohexyloxycarbonyloxy), and an aryloxycarbonyloxy group (preferably C7-C0) 32, More preferably, it is an aryloxycarbonyloxy group of 7-18. For example, phenoxycarbonyloxy and a carbamoyloxy group (preferably C1-C48, More preferably, 1-12 carbon) Barmoyloxy group, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (Preferably sulfamoyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms) For example, N, N-diethylsulfamoyloxy and N-propylsulfamoyloxy and alkyl sulfonyloxy groups (preferably C1-C38, More preferably, they are 1-12 alkyl sulfonyloxy groups.) For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy) and an arylsulfonyloxy group (preferably C6-C32, More preferably, it is an arylsulfonyloxy group of 6-12. Phenylsulfonyloxy) and acyl groups (preferably acyl groups having 1 to 48 carbon atoms, more preferably 1 to 12. For example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl) ), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbon) Aryl), aryloxycarbonyl groups (preferably carbon 7-32, More preferably, it is an aryloxycarbonyl group of 7-12. For example, it is a phenoxycarbonyl), a carbamoyl group (preferably C1-C48, More preferably, it is a 1-12 carbamoyl group). For example, carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarba Barmoyl, N-methyl-N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl) and an amino group (preferably with 32 or less carbon atoms, more preferably 12 or less amino groups). For example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an anilino group (preferably 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms) For example, an anilino group, an N-methylanilino group, and a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms). Diamino) and a carbonamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetamide, benzamide, tetradecanamide, pivaloylamide and cyclo) Hexaneamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, ureido, N, N-dimethyl ureido, N-phenyl ureido), imide group (Preferably 20 or less carbon atoms, more preferably 12 For example, N-succinimide, N-phthalimide) and the alkoxycarbonylamino group (preferably C2-C48, More preferably, they are the alkoxycarbonylamino group of 2-12. For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), and aryloxycarbonylamino group (preferably having 7 to 6 carbon atoms) 32, More preferably, it is the aryloxycarbonylamino group of 7-12. For example, phenoxycarbonylamino) and a sulfonamide group (preferably C1-C48, More preferably, 1-12 sulfonamide group) For example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide, sulfamoylamino groups (preferably having 1 to 48 carbon atoms, more preferably 1 to 12 sulfamoyls). For example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino, azo groups (preferably C1-C48, more preferably 1-24 azo groups). For example, it is a phenyl azo, 3-pyrazolyl azo), and an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methylthio, ethylthio, octylthio, Cyclohexylthio) and an arylthio group (preferably C6-C48, More preferably, they are an arylthio group of 6-12). For example, it is phenylthio) and heterocyclic thi group (preferably heterocyclic thi group of 1-32 carbon atoms, More preferably, 1-12.) For example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio) and an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, dodecanesulfinyl) and an arylsulfinyl group (preferably 6 carbon atoms). It is -32, More preferably, it is an aryl sulfinyl group of 6-12. For example, it is a phenyl sulfinyl) and an alkylsulfonyl group (preferably C1-C48, More preferably, it is an alkylsulfonyl group of 1-12). For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably Preferably it is an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 12. Cotton phenylsulfonyl, 1-naphthylsulfonyl) and sulfamoyl groups (preferably sulfamoyl groups having 32 or less carbon atoms, more preferably 16 or less), for example sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably C1-C32, more preferably 1- A phosphonyl group of 12. For example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 phosphinoylamino groups). For example, diethoxy phosphinoylamino, dioctyloxy phosphinoylamino), etc. are mentioned.

Among the pigment | dye represented by the said General formula (A), the phthalocyanine pigment | dye represented especially by the following General formula (B) is preferable.

In the general formula (B), M ¹ is the same as M ¹ in the general formula (A), as is also the preferred form.

In said general formula (B), R <^101> -R <^116> represents a hydrogen atom or a substituent each independently, and the substituent represented by R <^101> -R <^116> has a substituent which the 6-membered ring in general formula (A) mentioned above has Same as Moreover, when the substituent represented by R <^101> -R <^116> is a group which can be substituted, the substituent represented by R <^101> -R <^116> may further have a substituent which the 6-membered ring in general formula (A) mentioned above has, In the case of having a substituent, the plurality of teeth may be the same or different.

Examples of the substituents represented by the above R ¹⁰¹ to R ¹¹⁶ (T-1 to T139) are shown below. However, in this invention, it is not limited to these.

Next, the preferable range of the pigment | dye represented by the said General formula (A) is demonstrated. General formula (A), Preferably, it is represented by the said general formula (B).

The general formula (B) is a substituent (α di substituent) in the α position, and includes (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹² ), and (R ¹¹³ and R ^116). At least one set of the combination of) or having a substituent, or as a substituent at the β position (β di substituent), (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ), (R ¹¹⁰ and R ¹¹¹ ), and ( At least one set of a combination of R ¹¹⁴ and R ¹¹⁵ has a substituent, or as a substituent at the α- and β-positions (α-position, β-position substituent), (R ¹⁰¹ and R ¹⁰³ and / or R ¹⁰² and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁷ and / or R ¹⁰⁶ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹¹ and / or R ¹¹⁰ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁵ and / or R ¹¹⁴ and R ¹¹⁶ ) It is preferable to have a substituent in at least 1 set of the combination of these.

Here, as the substituent represented by R ¹⁰¹ to R ¹¹⁶ , halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, hetero Cyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, azo group, alkylthio group, Arylthio group, heterocyclic thi group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl group, phosphinoylamino group.

Examples of M ¹ include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, VO, and the like.

More preferably, the general formula (B) is an α position substituent (mono substituent), and may be represented by (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ^113). Or at least one of R ¹¹⁶ ), or as a β-position substituent (mono substituent), (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and ( At least one of R ¹¹⁴ or R ¹¹⁵ ) has a substituent.

Preferred substituents in this case include halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group , Carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide Group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphinoylamino group And M ¹ includes Zn, Pd, Cu, Ni, Co, TiO, VO and the like.

More preferably, the general formula (B) is an α-position substituent, (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them, or as β-position substituents, at least one of (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) It is a compound which has a substituent in three.

Preferred substituents in this case include halogen atoms, alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxyl groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyl groups, alkoxycarbonyl groups, Carbamoyl group, amino group, anilino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, azo group, alkylsulfinyl group, arylsulfinyl group, there may be mentioned an alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, there may be mentioned include ¹ M, Zn, Pd, Cu, Ni, Co, VO, etc.

More preferably, the general formula (B) is an α position substituent, and among (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of the same substituents or as β-substituents (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) Is a compound having the same substituents, preferred substituents are halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, Carbonamide group, ureido group, imide group, sulfonamide group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, or sulfo group, M ¹ is Zn, Pd, Cu, Ni, Co, or VO.

More preferably, the general formula (B) is an α-position substituent, (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them, or as β-position substituents, at least one of (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) Three substituents, all of which are the same compound; and the substituents are halogen atom, alkyl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, carbamoyl group, alkyl It is a sulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group, and is a compound whose M <^1> is Zn, Cu, Co, or VO.

Most preferably, the general formula (B) is an α-position substituent, (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them, or as β-position substituents, at least one of (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) Three substituents, all of which are the same compound, the substituent being a halogen atom, alkyl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, carbamoyl group, alkylsulfo Or a arylsulfonyl group, sulfamoyl group, or sulfo group, and M ¹ is Zn, Cu, Co, or VO.

Hereinafter, the specific example of the pigment | dye represented by general formula (A) (The phthalocyanine pigment | dye represented by general formula (B) is included.) [Example compound C-1-C-88, Cb-1-Cb-50, and Cc-1 to Cc-4]. However, in this invention, it is not limited to these.

Next, another dye-containing negative curable composition of the present invention is at least one of a dye represented by the following general formula (C1) as a dye compound, and at least one of a quinophthalone dye represented by the following general formula (1). It contains 1 type (pigment which concerns on this invention). Since it contains at least two pigments according to the present invention, it is possible to form a pattern having a good rectangular cross section which is highly sensitive compared to the composition of the conventional dye system, and eliminates the development residue in the non-exposed areas, and heat fastness of the pattern after formation It can effectively improve the sex and light fastness.

Dye represented by general formula (C1)

The dye-containing negative curable composition of this invention contains at least 1 sort (s) of the pigment | dye represented by following General formula (C1) (henceforth "the phthalocyanine type dye which concerns on this invention."). This pigment | dye (dye) has the favorable cyan color with high transmittance | permeability characteristic, there is no sedimentation with respect to the time of making it into the state of a liquid preparation or a coated coating film, and it is excellent in stability, and especially it has the outstanding resistance to heat or light.

Hereinafter, the phthalocyanine-based dye which concerns on this invention is demonstrated centering on the detail of each group of general formula (C1).

In the general formula (C1), the "aliphatic" may be linear, branched, or cyclic and any of saturated and unsaturated aliphatic sites may contain, for example, an alkyl group, an alkenyl group, a cycloalkyl group and a cycloalkenyl group. Or unsubstituted or substituted with a substituent. In addition, "aryl" may be either monocyclic or condensed ring, or may be unsubstituted or substituted with a substituent. The "hetero ring" means that the heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, any of a saturated ring and an unsaturated ring may be used, and either a monocyclic or a condensed ring may be used. Unsubstituted or substituted by a substituent.

Moreover, in general formula (C1), "substituent" may be a group which can be substituted, for example, aliphatic group, aryl group, heterocyclic group, acyl group, imide group, azo group, acyloxy group, acylamino group, aliphatic oxy group , Aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, Heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, Heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, heterocyclic thio group, hydroxy group, c Anano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryl An oxyphosphinyl group etc. are mentioned.

In the general formula (C1), Rc ₁ is a halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, Aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonyl Amino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, or heterocyclic thio group is shown.

Examples of the halogen atom represented by Rc ₁ include a fluorine atom, a chlorine atom and a bromine atom.

As the aliphatic group represented by Rc ₁ above, may be non-substituted may have a substituent, may be saturated may be an unsaturated, may be a cyclic, an aliphatic group of a small number of the bullet 1 to 15 are preferred. For example, a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, 2-ethylhexyl group, etc. are mentioned.

The aryl group represented by Rc ₁ above, may be a substituent which may have a non-substituted, preferably a small number of carbon atoms in total 6-16 aryl, more preferably an aryl group of a small number of bullets 6-12. For example, a phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group And 2-methoxycarbonyl-4-nitrophenyl group.

The heterocyclic group represented by Rc ₁ may be saturated or unsaturated, a heterocyclic group having 1 to 15 carbon atoms is preferable, and a heterocyclic group having 3 to 10 carbon atoms is more preferable. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyridinyl group, 1-piperidyl group, etc. are mentioned. Moreover, you may have a substituent.

As the carbamoyl group represented by Rc ₁ above, may be a substituent which may have a non-substituted, a carbamoyl group of 1 to 16 bullet few preferred, and a carbamoyl group of the car le bullet decimal from 1 to 12 is more preferable. For example, a carbamoyl group, a dimethylcarbamoyl group, a dimethoxyethyl carbamoyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by the Rc _1, non-substituted may be a good and may have a substituent, a saturated may be unsaturated be a good cyclic may be good, the bullet decimal from 2 to 16 aliphatic oxy carbonyl group are preferable, and carbon atoms in total decimal 2-10 aliphatic An oxycarbonyl group is more preferable. For example, a methoxycarbonyl group, butoxycarbonyl group, etc. are mentioned.

As the aryloxycarbonyl group represented by Rc ₁ above, it may be a substituent which may have a non-substituted, an aryloxycarbonyl group of 7 to 17 bullet few preferred, and an aryloxycarbonyl group of a small number of bullets 7-15 is more preferable. For example, a phenoxycarbonyl group etc. are mentioned.

The acyl group represented by the above-mentioned Rc ₁ may be an aliphatic carbonyl group or an arylcarbonyl group, and in the case of showing an aliphatic carbonyl group, may further have a substituent, or in the case of representing an arylcarbonyl group, may further have a substituent, either saturated or unsaturated, It may be fantastic. As said acyl group, the acyl group of 2-15 carbon atoms is preferable, and the acyl group of 2-10 carbon atoms is more preferable. For example, an acetyl group, pivaloyl group, a benzoyl group, etc. are mentioned. Moreover, you may have a substituent.

The aliphatic oxy group represented by Rc ₁ may be unsubstituted or may have a substituent, may be saturated or unsaturated, or may be cyclic. As the aliphatic oxy group, an aliphatic oxy group having 1 to 12 carbon atoms is preferable, and an aliphatic oxy group having 1 to 10 carbon atoms is more preferable. For example, a methoxy group, an ethoxyethoxy group, a phenoxy ethoxy group, a thiophenoxy ethoxy group, etc. are mentioned.

May be a substituent which may have a non-substituted aryl oxy group represented by Rc ₁ above, preferably an aryloxy group of 6 to 18 carbon atoms in total a small number, more preferably an aryloxy group of a small number of bullets 6-14. For example, a phenoxy group, 4-methyl phenoxy group, etc. are mentioned.

As the acyloxy group represented by Rc ₁ above, may be a substituent which may have a non-substituted, preferably an acyloxy small number of carbon atoms in total 2 to 14, more preferably an acyloxy group of a small number of bullets 2-10. For example, an acetoxy group, a methoxyacetoxy group, a benzoyloxy group, etc. are mentioned.

As the carbamoyloxy group represented by the Rc _1, it may optionally have a non-substituted may be substituted, preferably carbamoyl oxy carbon atoms in total having 1 ~ 16 group, more preferably carbamoyl oxy carbon atoms in total a small number from 1 to 12 groups. For example, a dimethylcarbamoyloxy group, a diisopropyl carbamoyloxy group, etc. are mentioned.

The heterocyclic oxy group represented by Rc ₁ may be unsubstituted or may have a substituent, a heterocyclic oxy group having 1 to 15 carbon atoms is preferable, and a heterocyclic oxy group having 3 to 10 carbon atoms is more preferable. For example, 3-furyloxy group, 3-pyridyloxy group, N-methyl- 2-piperidyloxy group, etc. are mentioned.

The aliphatic oxycarbonyloxy group represented by Rc ₁ may be unsubstituted or may have a substituent, may be saturated or unsaturated, or may be cyclic. As an aliphatic oxycarbonyloxy group, the aliphatic oxycarbonyloxy group of 2-16 total carbons is preferable, and the aliphatic oxycarbonyloxy group of 2-10 total carbons is more preferable. For example, a methoxycarbonyloxy group, (t) butoxycarbonyloxy group, etc. are mentioned.

Examples of N- alkylacylamino group represented by Rc ₁ above, may be non-substituted may have a substituent, an acylamino group of the N- alkyl bullet decimal 3-15 are preferred, and the N- alkyl acylamino group of the bullet than decimal 3-12 desirable. For example, N-methylacetylamino group, N-ethoxyethylbenzoylamino group, N-methylmethoxyacetylamino group, etc. are mentioned.

As the carbamoyl group represented by the Rc _1, may optionally have a non-substituted may be substituted, a carbamoyl group of the bullet decimal from 1 to 16 are preferred, and a carbamoyl group of the bullet small number of 1 to 12 is more preferable. For example, N, N- dimethyl carbamoylamino group, N-methyl-N-methoxyethylcarbamoylamino group, etc. are mentioned.

As the sulfamoylamino group represented by Rc ₁ above, it may be a substituent which may have a non-substituted, a sulfamoyl amino group of the bullet decimal 0 to 16 are preferred, and a sulfamoylamino group of a small number of bullets 0-12 is more preferred. For example, a N, N- dimethyl sulfamoyl amino group, a N, N- diethyl sulfamoyl amino group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by the Rc _1, non-substituted may be a good and may have a substituent, an aliphatic oxycarbonyl amino group of the bullet decimal 2-15 are preferred, and an aliphatic oxycarbonyl amino group of the bullet small number of 2 to 10 than the desirable. For example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, etc. are mentioned.

As the aryloxycarbonylamino group represented by the Rc _1, non-substituted may be a good and may have a substituent, an aryloxycarbonylamino group of a bullet decimal 7 to 17 is preferable, and a bullet aryloxycarbonylamino group of a small number of 7 to 15 desirable. For example, a phenoxycarbonylamino group, 4-methoxycarbonylamino group, etc. are mentioned.

The aliphatic sulfonylamino group represented by Rc ₁ may be unsubstituted or may have a substituent, may be saturated or unsaturated, or may be cyclic. As the aliphatic sulfonylamino group, an aliphatic sulfonylamino group having 1 to 12 carbon atoms is preferable, and an aliphatic sulfonylamino group having 1 to 8 carbon atoms is more preferable. For example, a methanesulfonylamino group, butanesulfonylamino group, etc. are mentioned.

As the arylsulfonylamino group represented by the Rc _1, may optionally have a non-substituted may be substituted, an arylsulfonyl group of bullets minority of 6 to 15 is preferable, and an arylsulfonylamino group of the bullet decimal 6-12 is more preferred. For example, a benzenesulfonylamino group, 4-toluenesulfonylamino group, etc. are mentioned.

The aliphatic thi group represented by Rc ₁ may be unsubstituted or may have a substituent, may be saturated or unsaturated, or may be cyclic. As aliphatic thio group, the aliphatic thio group of 1-16 carbon atoms is preferable, and the aliphatic thio group of 1-10 carbon atoms is more preferable. For example, methylthio group, ethylthio group, ethoxyethylthio group, etc. are mentioned.

As the arylthio group represented by Rc ₁ above, may be non-substituted may have a substituent, preferably an aryl thio few carbon atoms in total 6-22 groups, and arylthio groups of 6 to 14 is preferable small number of bullets. For example, a phenylthio group, 2-t-butylphenylthio group, etc. are mentioned.

It may be a substituent which may have a non-substituted aliphatic sulfonyl group represented by Rc ₁ above, preferably an aliphatic sulfonyl small number of carbon atoms in total from 1 to 15 groups, and more preferably an aliphatic sulfonyl group having 1 carbon atoms in total 1-8. For example, a methane sulfonyl group, butane sulfonyl group, a methoxy ethane sulfonyl group, etc. are mentioned.

As the arylsulfonyl group represented by Rc ₁ above, it may be a substituent which may have a non-substituted, preferably an aryl-sulfonyl group, and carbon atoms in total decimal 6-16, arylsulfonyl few carbon atoms in total 6 to 12 groups is more preferred. For example, a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group, etc. are mentioned.

As the sulfamoyl group represented by Rc ₁ above, it may be a substituent which may have a non-substituted, carbon atoms in total 0 to 16 decimal and a sulfamoyl group are preferred, a small number of bullets 0-12 sulfamoyl group is more preferable. For example, a sulfamoyl group, a dimethyl sulfamoyl group, etc. are mentioned.

As an imide group represented by said Rc <_1> , it may be further condensed, the imide group of the total number of carbon atoms of 3 to 22 is preferable, and the imide group of 3 to 15 carbon atoms is more preferable. For example, a succinic acid imide group, a phthalic acid imide group, etc. are mentioned.

As the heterocyclic thio group represented by the Rc _1, non-substituted may be a good and may have a substituent, 5 to 7-membered ring, and preferably a heterocyclic thio group of the bullet decimal from 1 to 20 groups, and heterocyclic thio carbon atoms in total decimal from 1 to 12 groups desirable. For example, 3-furylthio group, 3-pyridylthio group, etc. are mentioned.

In General Formula (C1), Zc ₁ represents a nonmetallic atom group necessary for forming a six-membered ring together with a carbon atom, and four Zc ₁ may be the same or different. The 6-membered ring formed may be either an aryl ring or a hetero ring, may be condensed, or the condensed ring may further have a substituent. As a 6-membered ring, a benzene ring, a pyridine ring, a cyclohexene ring, a naphthalene ring, etc. are mentioned, for example, The form which is a benzene ring is preferable.

In said general formula (C1), M represents two hydrogen atoms, a bivalent metal atom, a bivalent metal oxide, a bivalent metal hydroxide, or a bivalent metal chloride. As the M, for example, VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ , Si (OH) ₂ , H ₂ , and the like, and VO, Zn, Mn, Cu, Ni, and Co are preferred.

In the general formula (C1), cm represents 0, 1 or 2 (preferably 0), and cn represents 0 or an integer of 1 to 5 (preferably 0 or 1). Cn of the four places in the molecule, but be the same or different, one of the cn represents an integer of 1-5, in the case where a plurality of cn in the molecule is or different plurality of Rc ₁ may be the same with each other.

In addition, cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy | fill cr1 + cr2 + cr3 + cr4≥1. Especially, the form whose cr1 + cr2 + cr3 + cr4 is 3 or 4 is preferable.

Among the dyes represented by the general formula (C1), a dye (phthalocyanine-based dye according to the present invention) represented by the following general formula (C1-1) is preferable from the viewpoint of showing the effect of the present invention more effectively.

Wherein the general formula (C1-1), Rc ₂ represents a substituent, the substituent may include groups listed in the section of the "substituent" which may if possible substituted groups, above. Preferably, aliphatic group, aryl group, heterocyclic group, N-alkylacylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic Sulfonyl group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group , Carboxyl group, carbamoylamino group, sulfamoylamino group, halogen atom, more preferably, aliphatic group, N-alkylacylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, aliphatic sulfonyl group, aliphatic thio group, arylthio group, Sulfo groups, carboxyl groups, and halogen atoms.

In said general formula (C1-1), cp represents the integer of 0-4, Preferably it is 0 or 1. However, cp + cr1, cp + cr2, cp + cr3, and cp + cr4 all represent the integer of 0-4. When Rc is ₂ and that there is a plurality in a molecule, a plurality of Rc ₂ may be the same or different.

Also, Rc ₁ in the formula (C1-1), M, cm, cn , and cr1, cr2, cr3, and cr4 is the same as the case in the general formula (C1), as a preferred form.

Among the dyes represented by the general formula (C1-1), from the viewpoint of more effectively expressing the effects of the present invention, the dyes represented by the following general formula (C1-2) (phthalocyanine dyes according to the present invention) are more preferred. desirable.

In the general formula (C1-2), Rc ₁ , Rc ₂ , M, cm, cn and cr ₁ , cr ₂ , cr 3 and cr 4 are the same as in the general formulas (C 1) and (C 1-1), respectively. The preferred form is also the same. In addition, cq in general formula (C1-2) represents 0 or 1. In addition, the phthalocyanine skeleton has a structure in which four benzene rings are condensed on the outside of the tetraazaporphylline skeleton, and each benzene ring has a site (carbon atom) into which four substituents can enter. 2) is a hydrogen atom bonded to two positions (β position) far from the tetraazaporphylline skeleton of each benzene ring.

In the above general formula (C1-2), from the viewpoint of showing the effect of the present invention more effectively, Rc ₁ is a halogen atom, aliphatic group, cyano group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, hydroxy group , Aliphatic oxy group, carbamoyl oxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic tee A form which is a group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group is preferable, and is an aliphatic group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, aliphatic oxy group, aliphatic group Oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, More preferred are a arylsulfonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group, and a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbonyloxy group or a carba. Most preferred is a form that is a monoamino group, an aliphatic oxycarbonylamino group, an arylsulfonyl group, an imide group, or an aliphatic sulfonyl group.

Similarly, in view of the effects of the present invention more effectively, Rc ₂ is an aliphatic group, an N-alkylacylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an aliphatic thi group, an arylthio group, a sulfo group, The form which is a carboxyl group or a halogen atom is preferable, and the form which is an aliphatic group or a halogen atom is more preferable. Similarly, in the point which can show the effect of this invention more, the form where cq is 0 is preferable. Similarly, in the point which can show the effect of this invention more, said M is preferable the form which is VO, Mn, Co, Ni, Cu, Zn, or Mg, and the form which is VO, Co, Cu, or Zn is more preferable, The form which is Cu is the most preferable, Furthermore, the form which cm is 0 is preferable, The form which is cn is 1 or 2 is preferable, The form whose cn is 1 is more preferable.

In view of more effectively exhibiting the effects of the present invention, in the above general formula (C1-2), Rc ₁ represents a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a hydroxyl group. , Aliphatic oxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group , An arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group, wherein M is VO, Co, Cu, or Zn, cq is 0, cm is 0, and cn is the one preferred form, and further wherein Rc ₁ is an aliphatic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, an aliphatic oxy carbonyloxy group, a car Barmoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, imide group, or sulfo group, wherein M is VO, Co , Cu or Zn, cq is 0, cm is 0, and cn is 1 is more preferred.

In particular, in view of the effects of the present invention, Rc ₁ is a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, a carbamoylamino group, an aliphatic oxycarbonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, or an imide group. And M is Cu, cq is 0, cm is 0, and cn is 1, most preferably.

Hereinafter, the specific example (example compound C'-1-C'-59) of the pigment | dye (dye) represented by said general formula (C1)-(C1-2) is shown. However, in this invention, it is not limited to these.

Synthesis Example

Next, the synthesis example of the pigment | dye represented by the said General formula (A) or (B) is demonstrated in detail with reference to the following scheme A which takes the synthesis | combination of the pigment | dye C-1 which is the said exemplary compound as an example.

(Synthesis of intermediates)

100 ml of dimethyl sulfoxide was added to 25.0 g (0.144 mol) of 3-nitrophthalonitrile and 34.7 g (0.159 mol) of mercaptopropionic acid-2-ethylhexyl ester, and it stirred at room temperature. To this was further added 17.0 g of sodium carbonate, and after the addition was completed, the mixture was stirred at room temperature for 2 hours to complete the reaction. The obtained reaction liquid was poured into 500 ml of water, and extracted with 300 ml of ethyl acetate. The ethyl acetate phase was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain an oily intermediate A quantitatively.

To 50 g (0.144 mol) of the obtained intermediate A and 1.0 g of sodium tungstate, 200 ml of ethanol and 1 ml of acetic acid were added and stirred by heating. Subsequently, 36.5 g (0.288 mol) of 30% hydrogen peroxide aqueous solution was dripped at this solution. After completion of the dropwise addition, the mixture was heated and stirred for 4 hours at 65 to 70 ° C to complete the reaction. After the reaction was completed, the mixture was cooled to room temperature, 10 g of sodium sulfite and 700 ml of water were added, and the crystals were precipitated by stirring at room temperature. The crystals were filtered, washed with water, recrystallized with 200 ml of methanol, and purified to obtain 32.5 g of intermediate B (yield 60%).

Synthesis of Pigment C-1

150 mL of butanol was added to 34.4 g (0.081 mol) of intermediate B and 6.7 g (0.070 mol) of ammonium carbonate obtained as mentioned above, and it heated and stirred at 50 degreeC. Then, 4.7 g (0.035 mol) of cupric chlorides were added to this, and it heated at 100-110 degreeC, and stirred for 7 hours. After the reaction was completed, butanol was distilled off, and then the residue was dissolved in chloroform, separated and purified by silica gel column chromatography (eluent: chloroform / methanol = 10/1) to obtain 25 g of powdery pigment C-1 ( Yield 72.7%).

The maximum absorption wavelength ((lambda)) was measured by the spectrophotometer UV-2400PC (made by Shimadzu Corporation) by the maximum absorption wavelength ((lambda) _max ) and molar extinction coefficient ((epsilon)) in ethyl acetate of the obtained pigment | dye. _max ) 706.8 nm and a molar extinction coefficient (ε) of 55,600.

Moreover, also about other exemplary compound other than said pigment | dye C-1, it can synthesize | combine by the method similar to the above.

Next, the synthesis example of the dye (dye) represented by the said general formula (C1) is demonstrated in detail with reference to the following scheme which makes synthesis of dye C'-1 which is the said exemplary compound an example.

(Synthesis of Intermediate Product B)

First, 25.0 g (0.162 mol) of Compound A was dissolved in a mixed solvent of 100 ml of methanol and 23 ml of triethylamine, and this was added dropwise while maintaining 9 ml of 30% hydrogen peroxide solution at 25 ° C while cooling and stirring at 5 ° C. The reaction solution after the dropwise addition was stirred for 30 minutes at 25 ° C, further cooled to 5 ° C, and after stirring, 15 ml of concentrated hydrochloric acid was added dropwise, 200 ml of water was further added, and the mixture was stirred at 25 ° C for 1 hour. The precipitated crystals were filtered, thoroughly washed with water and dried to give 24.7 g of an intermediate product B as a white crystal (yield 99.5%).

(Synthesis of Intermediate Products C, D, and E)

Subsequently, 100 ml of toluene and 0.25 ml of dimethylacetamide were added to 17.5 g (0.114 mol) of the intermediate product B obtained above, and refluxed, and 25 ml of thionyl chloride was further added dropwise over 10 minutes. This was heated to reflux again for 1 hour, and then concentrated under reduced pressure to obtain a viscous liquid. On the other hand, 10 ml of dimethylacetamide and 100 ml of acetonitrile were added to 38.0 g (0.235 mole) of diethoxyethylamine, and the viscous liquid was added dropwise while maintaining the mixture at 15 ° C for 15 minutes while stirring at 10 ° C. After stirring for another 30 minutes, this was poured into a mixed solution of 100 ml of water and 100 ml of ethyl acetate, the ethyl acetate phase was separated by liquid, and washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain an intermediate product C as a pale yellow viscous liquid.

Subsequently, 50 ml of water, 200 ml of ethanol, and 12 g of zinc powder were added to the intermediate product C, and the mixture was heated to reflux, and then a solution of 10 ml of sulfuric acid was added dropwise to 40 ml of water over 20 minutes. After further stirring for 30 minutes, the mixture was cooled and the insolubles were separated by filtration. 50 ml of saturated saline and 100 ml of ethyl acetate were added to the obtained solution, and the liquid was separated, and then the ethyl acetate phase was washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain an intermediate product D as a pale yellow viscous liquid.

Subsequently, after stirring under nitrogen atmosphere to this intermediate product D, 70 ml of dimethylacetamide and 15 g (0.108 mol) of potassium carbonate were added, followed by stirring at 20 DEG C, followed by 19.7 g (0.113 mol) of 3-nitrophthalonitrile. Was added slowly, keeping it below 25 ° C. After stirring this again for 30 minutes, it stirred with 300 ml of water, and poured, the obtained crystal was filtered and the crystal was washed with water sufficiently. The obtained crystals were recrystallized from 70 ml of methanol, and the precipitated crystals were washed with 30 ml of cold methanol and dried to obtain 35.0 g of an intermediate product E as a white crystal (yield 72.6%).

Synthesis of Dye C'-1

Next, 150 mL of butanol, 6.7 g (0.070 mol) of ammonium carbonate, and 4.7 g (0.035 mol) of copper chloride were added to 34.4 g (0.081 mol) of intermediate E, and heating and stirring were performed for 7 hours. Thereafter, butanol was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain 25 g of a powder of dye C'-1 (yield 72.7%). The maximum absorption in the ethyl acetate, the resulting dye-wavelength (λ _max) and molar extinction coefficients (ε) spectrophotometer UV-2400PC (manufactured by Shimadzu Seisakusho Co., Ltd.) Results The maximum absorption wavelength (λ _max) subjected to measurement by the 706.8㎚ and ε 55,600.

Moreover, also about said other exemplary compound, it can synthesize | combine similarly to the above by changing into a desired compound according to the target dye.

Quinophthalone-type pigment | dye represented by General formula (1)

The compound represented by following General formula (1) is a compound which satisfies the high light resistance and high heat resistance which are not conventionally simultaneously, and can melt | dissolve in water or a solvent freely if necessary.

In the general formula ^{(1), R 1 ~ R} 4 represents a hydrogen atom, a halogen atom, -SR ⁵ or -SR ⁶ independently of each other. S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. Provided that at least one of R ¹ to R ⁴ represents -SR ⁵ ;

In General Formula (1), R ⁵ is preferably an alkyl group having 2 to 16 carbon atoms containing 1 to 6 oxygen atoms in the form of an ether bond, and R ² and R ³ are -SR ⁵ , It is preferable that R ¹ and R ⁴ be a hydrogen atom or a halogen atom. Moreover, one of the structural features of the quinophthalone type pigment | dye represented by General formula (1) in this invention is the point which has at least 1 alkyl group which has an ether bond in the benzene ring of the phthaloyl side of a quinophthalone frame | skeleton. Is in.

In the general formula (1), examples of the halogen atom represented by R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom and a bromine atom.

In the case where R ¹ to R ⁴ are -SR ⁵ , as R ⁵ , an alkyl group having 2 to 16 carbon atoms containing 1 to 6 oxygen atoms in the form of ether bonds is preferable, and in particular, oxygen atoms are in the form of ether bonds. The alkyl group of 2-12 total carbon atoms containing 2-4 is preferable. Here, the alkyl group may be linear or branched chain, and may have a part which formed the ring.

As an example of said R <^5> , 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 3-ethoxypropyl group, 2-ethoxy-1- Methylpropyl group, 3-propoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 4-methoxybutyl group, 4-propoxybutyl group, 6-methoxyhexyl group, 6-ethoxy Hexyl group, 2,3-dimethoxypropyl group, 2,3-diethoxypropyl group, 2,3-dipropoxypropyl group, 2,3-diisopropoxypropyl group, 2,3-dibutoxypropyl Group, 2,3-dicyclohexylpropyl group, 2,3-di (2-ethoxyethoxy) propyl group, 2,3-di (2-ethoxyethoxyethoxy) propyl group, 2- (2 -Ethoxyethoxy) -3- (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxyethoxy) -3- (2-propoxyethoxyethoxy) propyl group, 2,3-di (1,3-dioxolan-2-yl-ethoxy) propyl group, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl group, (2-ethyl -2-methyl-1,3-dioxolan-4-yl) methyl group, (2,2-die Yl-1,3-dioxolan-4-yl) methyl group, (2-propyl-1,3-dioxoran-4-yl) methyl group, (2,2-dipropyl-1,3-dioxolane -4-yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2-pentyl-1,3-dioxolan-4-yl) methyl group, 2- (tetrahydro Furfuryloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) ethyl group, 2- (1,3-dioxoran-2-ylethyloxy) ethyl group, 2- (1,3 -Dioxoran-2-ylmethyloxy) propyl group, 2- (tetrahydropyran-2-methyloxy) ethyl group, 2- (1,3-dioxan-2-ylethyloxy) ethyl group, 2- (1 , 3-dioxan-2-ylethyloxy) propyl group, hydroxyethoxyethyl group, hydroxyethoxyethoxyethyl group, 2- (hydroxyethoxy) propyl group, 2-hydroxy-3-methoxypropyl Group, 2-hydroxy-3-ethoxypropyl group, 2-hydroxy-3-butoxypropyl group, 2-hydroxy-3- (ethoxyethoxy) propyl group, etc. are mentioned.

When R <^1> -R <^4> is -SR <^6> , as R <^6> , a C2-C12 alkyl group containing 1-4 hydroxyl groups is preferable, and 1-3 hydroxyl groups are the point of optical density of a pigment | dye. Particularly preferred is an alkyl group having 2 to 8 carbon atoms in total.

As an example of said R <^6> , 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3- dihydroxypropyl group, 2-hydroxy-1-methylpropyl group, 4-hydroxy Hydroxybutyl group, 2,3,4-trihydroxybutyl group, 2,3,4,5-tetrahydroxypentyl group, 6-hydroxyhexyl group, 11-hydroxy undecanyl group, 12-hydroxy degree Decanyl group etc. are mentioned.

In the quinophthalone dye and the tautomers represented by formula (1), the total number of ether bond oxygen atoms as contained in the R ¹ ~ R ⁴ is 1 to 16 private preferably, the optical density of the solubility and dye 2-12 are especially preferable at the point of.

The total number of oxygen atoms contained in R ¹ to R ⁴ containing oxygen atoms contained in the hydroxy group is preferably 2 to 24, particularly preferably 3 to 16.

In addition, quinophthalone dyes and their tautomers represented by formula (1) in terms of the absorption characteristic of the dye is preferably of the structure -SR ⁵ is introduced on R ² and / or R ^3.

In the quinophthalone type pigment | dye represented by General formula (1) (following compound (1)), tautomers of structures, such as a compound (1 ') and (1 ") shown below, exist, but also about these tautomers It is included in the scope of the present invention.

Hereinafter, the specific example (specific example 1-227) of the quinophthalone type pigment | dye (quinophthalone compound) represented by General formula (1) in this invention is shown in a table. However, these specific examples do not limit the scope of the compound in the present invention.

(Method for producing quinophthalone dye represented by General Formula (1))

The manufacturing method of the quinophthalone type pigment | dye (quinophthalone compound) represented by General formula (1) in this invention is demonstrated below. The outline of the typical manufacturing method (first and second manufacturing methods) is as follows.

First Manufacturing Method

As a 1st manufacturing method, first, in an organic solvent, 1-16 mol amount of alkali compounds are used with respect to 1 mol amount of the following compound (A), 20-200 degreeC with 1-8 mol amount of the following compound (B) React 1-8 hours at.

[In compound (A), R ⁷ represents a halogen atom, and R ⁸ represents a hydrogen atom. a shows the number of introduction of R <^7> , and shows the integer of 1-4. b shows the number of introduction of R <^8> , and shows the integer of 0-3. A + b is 4.

HS-R ⁵ (B)

[In compound (B), R <^5> is the same as that of the said General formula (1).]

At this time, as the organic solvent, N-methylpyrrolidone, DMI, sulfolane, DMF, DMAC, toluene, ethyl acetate, and the like are used. As the alkali compound, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like are used. Used. After the reaction, the reaction solution is discharged into water, extracted with an organic solvent such as ethyl acetate, washed with water, concentrated, and purified by column chromatography, if necessary, to form Quinophthalone represented by the general formula (1). System pigment | dye can be obtained.

Second Manufacturing Method

As a 2nd manufacturing method, 1-16 mol of alkali compounds are used with respect to 1 mol of said compounds (A) in an organic solvent first, and it is 1- at 20-200 degreeC with 1-8 mol of following compound (C) Reaction for 24 hours.

HS-R ⁶ (C)

[In compound (C), R <^6> shows the same thing as in General formula (1). "

Subsequently, the solution is discharged into water, neutralized with dilute hydrochloric acid, acetic acid, or the like, filtered and washed with water to obtain the following compound (D). Under the present circumstances, as the organic solvent and alkali compound used for the said reaction, the same thing as what was used by the said 1st manufacturing method is used.

[In compound (D), R <^7> and R <^8> shows the same thing as said compound (A), and R <^6> shows the same thing as in general formula (1). Ac represents 0-3, b represents 0-3, and c represents 1-4. However, (ac) + c + b is 4.

Next, the target compound (D) is used in an organic solvent by using 1 to 24 molar amounts of an alkali compound and reacting with 1 to 24 molar amounts of the following compound (E) at 20 to 200 ° C. for 1 to 24 hours. The quinophthalone pigment | dye represented by Formula (1) is obtained. As said organic solvent and said alkali compound, the same thing as what was used by the said 1st manufacturing method is used.

ZR ⁹ (E)

[In the compound (E), Z represents a halogen atom, a toluenesulfonyloxy group or a methanesulfonyloxy group, and R ⁹ represents an alkyl group which may contain an oxygen atom in the form of an ether bond or a hydroxy group.]

In addition, even when the compound (D) and the compound (E) are reacted in an organic solvent in a two-phase system using a phase transfer catalyst and an alkaline aqueous solution, the quinophthalone pigment represented by the general formula (1) can be similarly produced. As an organic solvent used for the said reaction, the same thing as what was used by the said 1st manufacturing method is used. As said alkaline aqueous solution, the sodium hydroxide aqueous solution, the potassium hydroxide aqueous solution, etc. are mentioned. As the phase transfer catalyst, tetrabutylammonium bromide, tetramethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate and the like are used.

In addition, when R <^6> of the said compound (D) is an alkyl group which has a (alpha), (beta)-dihydroxy group, in the organic solvent, dehydrating reflux of acid catalysts, such as the following compound (F) and p-toluenesulfonic acid, is carried out by carrying out dehydration reflux. The quinophthalone type pigment | dye represented by 1) can be obtained.

[In compound (F), R <^10> may represent a hydrogen atom or an alkyl group, R <^11> may represent an alkyl group, and R <^10> and R <^11> may combine with each other and form a ring.]

In the dye-containing negative curable composition of the present invention, one or more types of pigments represented by the general formula (A) and the one of the quinophthalone pigments represented by the general formula (1) or It is comprised using multiple types together and can use a well-known xanthene type pigment | dye, a triaryl methane type pigment | dye, etc. further as needed.

Although the total concentration in the dye-containing negative curable composition of the dye in the present invention depends on the molecular weight and the molar extinction coefficient, 0.5 to 80% by mass is preferable, and 10 to 60 to the total solid component of the composition. Mass% is more preferable.

In addition, when mixing and coloring the pigment | dye represented by General formula (A) and the quinophthalone type pigment | dye represented by General formula (1), the addition amount of the pigment | dye to add the smallest quantity among the pigment | dyes to add is a It is preferable that it is at least 10% or more in addition amount, and 10 to 80% is more preferable.

The dye according to the present invention represented by the above general formula is a color filter for recording and reproducing a color image used for a solid-state image pickup device such as a CCD or a CMOS, a display such as an LCD or a PDP, or for producing these color filters. It is preferable to a curable composition. When producing a color filter, it is comprised using the pigment | dye which concerns on this invention, ie, the 2 or more types of pigment | dye containing the pigment | dye represented by general formula (C1) mentioned above, and the quinophthalone type pigment | dye represented by general formula (1). It can be produced by either method as long as it is a form, and for example, as described below, a curable composition containing a dye according to the present invention is prepared, and the prepared composition is applied to form a pattern through exposure, development, or the like. A process can be installed and it can manufacture preferably.

-(C) photoinitiator-

Next, a photoinitiator is demonstrated. A photoinitiator is contained with the radically polymerizable monomer mentioned later in the dye-containing negative curable composition of this invention. The photopolymerization initiator is not particularly limited as long as it can polymerize the radically polymerizable monomer. However, the photopolymerization initiator is preferably selected from the viewpoints of characteristics, starting efficiency, absorption wavelength, availability, cost, and the like.

As the photoinitiator, for example, at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a tropine dimer, a benzophenone compound, acetophenone A compound, its derivative (s), a cyclopentadiene benzene- iron complex, its salt, an oxime type compound, etc. are mentioned.

As an active halogen compound which is the said halomethyloxadiazole compound, the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound of Unexamined-Japanese-Patent No. 57-6096, etc., 2-trichloro Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(p-methoxystyryl) -1,3,4-oxadiazole, etc. are mentioned.

As an active halogen compound which is a halomethyl-s-triazine type compound, the vinyl-halomethyl-s-triazine compound described in JP-A-59-1281 and 2- (described in JP-A-53-133428 Naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound have.

Specific examples of the halomethyl-s-triazine-based compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6 -p-methoxystyryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphtho- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine , 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1- Yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s -Triazine, 2- [4- ( 2-butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6 -Methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloro Romethyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naph To-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl- s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N -Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro) Rhomethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [M-fluoro-pN, N-di (ethoxycarbonylmethyl) amino Nil] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro) Romethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [O-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [M-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro- pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o -Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluor R-pN-chloroethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o -Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Romethyl) -s-triazine and the like.

In addition, as a photoinitiator, the TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ) made by Midori Chemical Co., Ltd. -123), T series (e.g. T-OMS, T-BMP, TR, TB) made by PANCHIM company, Ilga Cure series (e.g., Ilgacua 651, Ilgacua 184, Ilgacua) 500, Ilgacua 1000, Ilgacua 149, Ilgacua 819, Ilgacua 261), Darocua series (e.g., Tarocua 1173), 4,4'-bis (diethylamino) -benzophenone, 2- (O -Benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyl oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorphenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-di Phenylimidazolyl Dimer, 2- (p-methoxyfe ) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4, 5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether and the like are also usefully used.

Among these, as a photoinitiator in this invention, an oxime type compound is preferable. As said oxime type compound, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, and 1- (O-acetyl oxime) -1-, for example Particular preference is given to [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

Moreover, a sensitizer and a light stabilizer can be used together for these photoinitiators.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluolinone, 2-chloro-9-fluolenonone, 2-methyl-9-fluolelenone, 9-anthrone, 2-bromo-9- Anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9 , 10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridon, 10-butyl-2 -Chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone ( Or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, or the benzothiazole compound described in Japanese Patent Publication No. 51-48516; .

The well-known photoinitiator other than the photoinitiator mentioned above can be used for the dye-containing negative curable composition of this invention.

Specifically, bisinal polyketolaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828 Acyloin ethers, aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758 Combination of triarylimidazole dimers / p-aminophenyl ketones disclosed in the specification of 3,549,367, benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in Japanese Patent Publication No. 51-48516 Etc. can be mentioned.

As total content of the said photoinitiator, 0.01 mass%-50 mass% are preferable with respect to solid content (mass) of the radically polymerizable monomer mentioned later, 1 mass%-30 mass% are more preferable, 1 mass%-20 Mass% is particularly preferred. When content of the said photoinitiator exists in the range of 0.01-50 mass%, superposition | polymerization will advance easily and film strength can fully be improved. Moreover, when using the said oxime type compound and another photoinitiator together, 30 mass% or more is preferable and, as for content with respect to the total amount of the photoinitiator of the said oxime type compound, 50 mass% or more is more preferable.

(D) radically polymerizable monomer

Next, the said radically polymerizable monomer is demonstrated. As a radically polymerizable monomer used in this invention, the compound which has at least 1 addition-polymerizable ethylenic double bond and has a boiling point of 100 degreeC or more under normal pressure is preferable. By containing together with the photoinitiator mentioned above, the composition of this invention can be comprised in negative form.

delete

As an example of the said radically polymerizable monomer, Monofunctional acrylates and methacrylates, such as polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocy (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimetholethane; Urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Application Laid-open No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. In addition, Japan Adhesion Society Vol.20, No. 7, 300-308 is mentioned as a photocurable monomer and oligomer. It is preferable that it is a polyfunctional (meth) acryl compound as a radically polymerizable monomer in this invention.

As content of the said radically polymerizable monomer, it is preferable that it is 1-60 mass% with respect to the total solid in a composition, and it is more preferable that it is 10-50 mass%. When content of the said radically polymerizable monomer exists in the range of 1-60 mass%, the sclerosis | hardenability of an exposure part is enough and the solvent release property of an unexposed part can be improved.

(E) organic solvents-

The organic solvent which can be used in the present invention is not particularly limited as long as it satisfies the solubility of each component and the applicability of the dye-containing negative curable composition, but is selected in particular in consideration of the solubility, coating property and safety of the dye and binder. It is preferable, for example, a cyclic ketone solvent is preferable. Moreover, when preparing the dye-containing negative curable composition of this invention, it is preferable to use the mixed solvent containing at least 2 type of organic solvent. Moreover, it is also preferable to use a cyclic ketone solvent independently.

When using the mixed solvent which mixed two or more types of organic solvents, it is preferable that it is a mixed solvent of a cyclic ketone solvent and another 1 type of organic solvent as said mixed solvent. As said cyclic ketone solvent, cyclopentanone, cyclohexanone, cycloheptanone, etc. are mentioned, for example, cyclohexanone is especially preferable.

As solvents other than the said cyclic ketone, esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl acetate, butyric acid ethyl, butyrate butyl Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, methoxyacetic butyl, ethoxyacetate, ethyl ethoxyacetate, and the like; 3-oxypropionic acid alkyl esters, such as methyl 3-oxypropionate and ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropionic acid Ethyl and the like; 2-oxypropionic acid alkyl esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and 2-methoxypropionic acid propyl , Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate and the like; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetacetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like; Aromatic hydrocarbons such as toluene, xylene and the like are preferable.

Among these, as other organic solvents used together with the cyclic ketone solvent, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate are preferable, and ethyl lactate, Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

When the said cyclic ketone solvent and another organic solvent are mixed, it is preferable that content of the said cyclic ketone solvent in the total amount of a mixed solvent is 40 mass% or more, and it is more preferable that it is 60 mass% or more.

It is preferable that the usage-amount of the organic solvent in this invention sets it as the quantity used as the total solid content concentration of 5-80 mass% of the dye-containing negative curable composition of this invention from a coatability viewpoint, and 5-60 mass% furthermore It is preferable and 10-50 mass% is especially preferable.

Bridge

In this invention, it is also possible to obtain the film | membrane hardened | cured even more highly using a crosslinking agent complementarily. Hereinafter, a crosslinking agent is demonstrated.

The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction, and is selected from, for example, (a) epoxy resins, (b) methrol groups, alkoxymethyl groups, and acyloxymethyl groups. A phenol compound, a naphthol compound substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methrol group, an alkoxymethyl group, and an acyloxymethyl group substituted with at least one substituent Or a hydroxyanthracene compound. Especially, polyfunctional epoxy resin is preferable.

As said (a) epoxy resin, as long as it has an epoxy group and has crosslinkability, any may be sufficient, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexane Divalent glycidyl group-containing low molecular weight compounds such as diol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester, N, N-diglycidyl aniline, and the like, trimethylol Trivalent glycidyl group-containing low molecular compounds represented by propane triglycidyl ether, trimetholphenol triglycidyl ether, TrisP-PA triglycidyl ether, and the like, pentaerythritol tetraglycidyl ether, tetramethyrol bisphenol A Tetravalent glycidyl group-containing low molecular weight compounds represented by tetraglycidyl ether, and the like, dipentaerythritol pentaglycidyl ether, dipentaerythriri 1,2-epoxy-4- (2) of polyhydric glycidyl group-containing low molecular weight compounds such as hexaglycidyl ether, polyglycidyl (meth) acrylate, and 2,2-bis (hydroxymethyl) -1-butanol A glycidyl group containing high molecular compound etc. represented by -oxyranyl) cyclohexane addition product etc. are mentioned.

As the number substituted by the metharol group, the alkoxy methyl group, and the acyloxy methyl group contained in the crosslinking agent (b), it is 2 to 6 for the melamine compound, 2 to 4 for the glycoluril compound, guanamine compound, and urea compound. Preferably, it is 5-6 for a melamine compound, and 3-4 for a glycoluril compound, a guanamine compound, and a urea compound.

Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of the above (b) may be generally referred to as a (methol group, alkoxymethyl group or acyloxymethyl group-containing compound) according to (b).

The metyrol group-containing compound according to (b) is obtained by heating the alkoxymethyl group-containing compound according to (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid in alcohol. The acyloxymethyl group-containing compound according to (b) is obtained by mixing and stirring the metyrol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, the specific example of the compound which concerns on (b) which has the said substituent is given.

As said melamine compound, the compound or its mixture, hexamethoxy ethyl melamine, and hexaacyloxy which methoxymethylated 1-5 of the methol groups of hexametholol melamine, hexamethoxymethylmelamine, and hexamethololamine were methoxymethylated, for example. The compound in which 1-5 of the metyrol groups of methyl melamine and hexamethol melamine acyloxymethylated, its mixture, etc. are mentioned.

As said guanamine compound, the compound or its mixture, tetramethoxyethylguanamine which methoxymethylated 1-3 methyrol groups of tetrametholguanamine, tetramethoxymethylguanamine, and tetrametholguanamine, for example. And a compound obtained by acyloxymethylation of one to three metyrol groups of tetraacyloxymethylguanamine and tetramethyrolguanamine.

As said glycoluril compound, For example, the compound or mixture which tetramethylol glycoluril, tetramethoxymethylglycoluril, and 1 -3 of the metharol groups of tetrametholglycoluril methoxymethylated, or its tetramethylol glycol The compound which carried out acyloxymethylation of 1-3 of usryl methirol groups, or its mixture, etc. are mentioned.

As said urea compound, the compound which made the methoxymethylation of 1-3 methyrol groups of tetrametholurea, tetramethoxymethyl urea, tetramethyrolurea, or its mixture, tetramethoxyethylurea, etc. are mentioned, for example. .

The compounds according to these (b) may be used alone or in combination.

The crosslinking agent of (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methrol group, an alkoxymethyl group, and an acyloxymethyl group, is the same as that of the crosslinking agent (b). By crosslinking, intermixing with the overcoated photoresist is suppressed and the film strength is further increased. Hereinafter, these compounds may be generally called (methol group, alkoxy methyl group, or acyloxy methyl group containing) compound as described in (c).

As the number of the methirol group, acyloxymethyl group, or alkoxy methyl group contained in the crosslinking agent (c), at least two are required per molecule, and from the viewpoint of thermal crosslinkability and storage stability, 2-position, 4 of the phenol compound to be a skeleton Preferred are compounds in which all of the positions are substituted. Moreover, the naphthol compound and the hydroxyanthracene compound which become a frame | skeleton are also preferable in which the ortho position and para position of an OH group are substituted. The 3 or 5 position of the phenol compound may be unsubstituted or may have a substituent.

Also in the said naphthol compound, it may be unsubstituted or may have a substituent except the ortho position of OH group.

The metyrol group-containing compound according to the above (c) uses a compound whose 2- or 4-position of the phenolic OH group is a hydrogen atom as a raw material, which is sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide Obtained by reacting with formalin in presence of basic catalysts, such as these.

The alkoxymethyl group-containing compound according to (c) is obtained by heating the metyrol group-containing compound according to (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid and methanesulfonic acid in alcohol.

The acyloxymethyl group-containing compound according to (c) is obtained by reacting the metyrol group-containing compound according to (c) with acyl chloride in the presence of a basic catalyst.

As a skeletal compound in a crosslinking agent (c), a phenol compound, a naphthol, a hydroxyanthracene compound, etc. which are unsubstituted in the ortho position or para position of a phenolic OH group are mentioned, for example, each isomer of phenol and cresol Bisphenols, such as 2, 3- xylenol, 2, 5- xylenol, 3, 4- xylenol, 3, 5- xylenol, and bisphenol A, 4,4'-bishydroxy biphenyl , TrisP-PA (manufactured by Honshu Kagaku Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

As a specific example of the said crosslinking agent (c), As a phenol compound, For example, the compound which methoxymethylated 1-2 methyrol groups of a trimethol phenol, a tri (methoxymethyl) phenol, a trimethol phenol, and a trimetholol Dimethes, such as the compound which methoxymethylated 1-2 methyrol groups, such as a 3-cresol, a tri (methoxymethyl) -3-cresol, and a trimethol-3-cresol, and a 2, 6- dimethol-4- cresol A compound obtained by methoxymethylation of 1 to 3 methrol groups of tyrolcresol, tetramethol bisphenol A, tetramethoxymethyl bisphenol A, tetramethol bisphenol A, tetramethyrol-4,4'-bishydroxybiphenyl, 1 to 5 methols of tetramethoxymethyl-4,4'-bishydroxybiphenyl, hexametholol of TrisP-PA, hexamethoxymethyl of TrisP-PA, and hexametholol of TrisP-PA The compound which methoxymethylated the group, bishydroxymethyl naphthalenediol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene and the like, and examples of the acyloxymethyl group-containing compound include, for example, The compound etc. which carried out the acyloxymethylation of the metyrol group in part or all are mentioned.

Preferred among these compounds are hexametholol or trimethylol phenol, bishydroxymethyl-p-cresol, tetramethol bisphenol A, and TrisP-PA (manufactured by Honshu Kagaku Kogyo Co., Ltd.) or these metirol groups. The phenol compound substituted by both an alkoxy methyl group and a metyrol group and the alkoxy methyl group is mentioned.

The compounds according to these (c) may be used alone or in combination.

As total content in the dye-containing negative curable composition of the said crosslinking agent, although it changes with a raw material, 1-70 mass% is preferable with respect to solid content (mass) of the said curable composition from a viewpoint of improving curability, 50 mass% is more preferable, and 7-30 mass% is especially preferable.

Thermal polymerization inhibitor

In addition to the above, it is preferable to add the thermal-polymerization inhibitor to the dye-containing negative curable composition of this invention. For example hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

<Various additives>

In the dye-containing negative curable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like can be blended, if necessary.

Specific examples of the various additives include fillers such as glass and alumina; Polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactants such as nonionic, cationic and anionic systems; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And aggregation inhibitors such as sodium polyacrylate.

In addition, in order to promote alkali solubility of the non-hardened portion and to further improve the developability of the dye-containing negative curable composition of the present invention, the composition is preferably an organic carboxylic acid, preferably a low molecular weight organic carr having a molecular weight of 1000 or less. An acid can be added.

Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetate, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid, sheet Aliphatic dicarboxylic acids such as laconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconic acid and canforonic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, cumalic acid, and unbelic acid. .

<< color filter and manufacturing method thereof >>

Next, the color filter of this invention is demonstrated in detail through the manufacturing method.

In the manufacturing method of the color filter of this invention, the dye-containing negative curable composition of this invention mentioned above is used.

The dye-containing negative curable composition of the present invention is applied onto a support by a coating method such as rotary coating, flexible coating, roll coating, or the like to form a radiation sensitive composition layer, and the layer is exposed through a predetermined mask pattern. The negative color pattern is formed by developing with a developer (image forming step). Moreover, you may include the hardening process which hardens the formed coloring pattern by heating and / or exposure as needed.

In this invention, it is preferable to perform exposure by the above-mentioned stepper exposure at the time of the said exposure.

In the production of a color filter, by repeating the above-described image forming step (and curing step as necessary) by the desired number of colors, a color filter having a desired color can be produced. As light or radiation used at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used.

Examples of the support include soda glass, pyrex (registered trademark) glass, quartz glass and a transparent conductive film attached thereto, and photoelectric conversion element substrates used in imaging devices, for example, silicon substrates. Etc., complementary metal oxide semiconductor (CMOS), etc. are mentioned. These board | substrates may be provided with the black stripe which isolate | separates each pixel.

Further, on these supports, a primer layer may be formed, if necessary, in order to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the substrate surface.

As the developing solution, any one can be used as long as it dissolves the uncured portion of the dye-containing negative curable composition of the present invention and the irradiated portion does not dissolve. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, for example. The concentration of the alkaline compounds such as seed, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001-10% by mass, preferably 0.01-1% by mass. The alkaline aqueous solution which melt | dissolves so that it will become preferable is preferable. Moreover, when the developing solution which consists of such alkaline aqueous solution is used, it wash | cleans with water after developing in general.

The color filter of the present invention can be used for solid-state image pickup devices such as liquid crystal display devices and CCDs, and is particularly preferable for high resolution CCD devices and CMOS devices, which exceed one million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises CCD, and the microlens for condensing.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it is beyond the scope of the present invention. In addition, "part" is a mass reference | standard unless there is particular notice.

[Example 1]

1) Preparation of dye-containing negative curable composition

Each compound was mixed and dissolved with the composition shown below, and the dye-containing negative curable composition of this invention was prepared.

〔Furtherance〕

? Ethyl lactate (organic solvent)…? 67.3 g

Resin C (benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])… 7.9 g

Monomer A (radical polymerizable monomer: dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Co., Ltd.). 4.8 g

? Example compound C-1 (pigment represented by general formula (A))... 6.6 g

? Specific Example No. 39 (quinophthalone dye represented by General Formula (1)). 2.2 g

? Photopolymerization initiator (brand name: TAZ-107, product of Midorigaku Co., Ltd.)… 2.1 g

2) Fabrication of Silicon Wafer Substrate with Primer Layer

A resist solution (trade name: CT-2000L, manufactured by Fuji Film Arch Co., Ltd.) was applied to a silicon wafer substrate using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to form a cured film (primer). Layer) to form a silicon wafer substrate on which a primer layer was formed.

3) Exposure and development of dye-containing negative curable composition (image forming process)

The dye-containing negative curable composition obtained in the above 1) was applied onto the silicon wafer substrate on which the primer layer obtained in the above 2) was formed by using a spin coater and prebaked at 100 ° C. for 120 seconds. The sample in which the resist layer was formed on the board | substrate was produced.

[Examples 2-10]

In Example 1, the dye-containing negative curable composition was prepared in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 1 below, and each sample was prepared. Formed.

[Comparative Example 1]

In Example 1, the dye-containing negative curable composition for comparison was prepared in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 1 below. A sample was formed.

(Table 1)

※ Alkali-soluble binder

Resin A: ACA250, Daicel Kagaku Kogyo Co., Ltd.

(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)

Resin B: Brand name ACA300, Daicel Kagaku Kogyo Co., Ltd. product

(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)

Resin C: Benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])

* Radical polymerizable monomer

Monomer A: Nihon Kayaku Co., Ltd., DPHA (main ingredient: dipentaerythritol hexaacrylate)

Organic solvent soluble dye

The symbol (except the comparative example) of the column of the organic solvent soluble dye is an exemplary compound number of the pigment | dye represented by General formula (A), and the specific example of the quinophthalone pigment | dye represented by General formula (1) Corresponds to the number.

? VB-2620: Orien Kagaku Kogyo Co., Ltd.

※ Photopolymerization initiator

? TAZ-107: Midori Kagaku Co., Ltd.

? Oxime A: 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione [product made by Chiba Specialty Chemicals Co., Ltd.]

? Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone [product of Chiba Specialty Chemicals Co., Ltd.]

4) Evaluation

(1) sensitivity

About the sample formed in each Example and the comparative example, the exposure amount was irradiated to the coating film through the mask of 2 micrometers of length x 2 micrometers in wavelength of 365 nm using the i line | wire reduction projection exposure apparatus. After irradiation, it developed at 23 degreeC for 60 second using the developing solution (brand name: CD-2000, 100%, Fuji Film Arch Co., Ltd. product). Then, after rinsing with running water for 20 seconds, it spray-dried and obtained the pattern image. Image formation was confirmed by a conventional method by an optical microscope and SEM photograph observation.

At this time, the exposure amount which the width | variety of the pixel pattern of length 2 micrometers x 2 micrometers, and the said pixel pattern becomes 1: 1 was made into the appropriate exposure amount, and the exposure amount was made into the sensitivity. The smaller the number, the higher the sensitivity. The results are shown in Table 2 below.

(2) Profile

In the said (1), the pattern cross section was observed with the SEM image about the pixel pattern formed at the appropriate exposure amount. At this time, the thing of a favorable rectangular profile was evaluated as "(circle)", the thing of a slightly round top (rounded head) shape was evaluated as "(triangle | delta)", and the thing of a round top shape was evaluated as "x" completely. The results are shown in Table 2 below.

(3) unexposed miners

In the said (1), the pattern cross section was observed with the SEM image about the pixel pattern formed at the appropriate exposure amount. At this time, the thing which shows no residue at all in an unexposed part is evaluated as "(circle)", and it evaluates as "(triangle | delta)" that the residue is seen a little in the unexposed part, but there is no problem in practical use, and shows that the residue is surely seen in an unexposed part "x". Evaluated. The results are shown in Table 2 below.

(4) heat resistance

On the glass substrate separately prepared, the dye-containing negative curable composition obtained in said 1) was apply | coated so that it might become 1 micrometer in film thickness. The glass substrate with a coating film was left to stand on a 200 degreeC hotplate for 1 hour, and the spectral change was measured using the spectrophotometer (brand name: MS-1500, Shimadzu Corporation). From these measured values, (DELTA) E * ab was computed by the color analysis program, and it was set as evaluation of heat resistance. The results are shown in Table 2 below.

(5) light resistance

The dye-containing negative curable composition obtained in the above 1) was applied onto a separately produced glass substrate so as to have a film thickness of 1 μm, and the coating film was applied to a xenon irradiated water meter (brand name: SX75, manufactured by Sugashi Kenki Co., Ltd.) for 20 hours. It was investigated (200,000 lux), and the spectral change was measured after that using the spectrophotometer (brand name: MS-1500, the Shimadzu Corporation). From these measured values, (DELTA) E * ab was computed by the color analysis program, and it was set as evaluation of light resistance. The results are shown in Table 2 below.

Table 2

In the Example using the pigment | dye represented by General formula (A) and the quinophthalone pigment | dye represented by General formula (1) from said Table 2, it is excellent in heat resistance and light resistance, and is excellent in sensitivity, and The rectangularity was also good, and no residue was seen in the unexposed part. On the other hand, in the comparative example which used pigment | dyes other than the pigment | dye in this invention, heat resistance and light resistance were remarkably inferior, the sensitivity and rectangularity of a pattern were bad, and the residue was seen in the unexposed part.

[Examples 11 to 19 and Comparative Example 2]

1) Preparation of dye-containing negative curable composition

The compounds of the composition shown in following Table 3 were mixed and dissolved, and the dye-containing negative curable compositions (1)-(9) of this invention and the dye-containing negative curable composition (10) of the comparative were prepared.

Table 3

The detail of composition (A)-(D) in the said Table 3 is as follows.

※ Alkali-soluble binder

Resin A: ACA250 (made by Daicel Kagaku Kogyo Co., Ltd.)

(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)

Resin B: ACA300 (made by Daicel Kagaku Kogyo Co., Ltd.)

(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)

Resin C: Benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])

* Radical polymerizable monomer

Monomer A: Nihon Kayaku Co., Ltd., DPHA (main ingredient: dipentaerythritol hexaacrylate)

＊ Organic solvent soluble dye

Symbol of the exemplary compound described in the column of the organic-solvent-soluble dye of Examples 11-19 is the above-mentioned exemplary compound of the pigment represented by general formula (C1), A specific example number is a quinoph represented by general formula (1) It is an exemplary compound mentioned above of a talon pigment.

※ Photopolymerization initiator

? TAZ-107: Midori Kagaku Co., Ltd.

? Oxime A: 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione [product made by Chiba Specialty Chemicals Co., Ltd.]

? Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone [product of Chiba Specialty Chemicals Co., Ltd.]

2) Fabrication of glass substrate with primer layer

A resist CT-2000L solution (manufactured by Fuji Film Arch Co., Ltd.) was applied onto a silicon wafer substrate using a spin coater to have a thickness of 2 μm, and dried at 220 ° C. for 1 hour to form a cured film (primer layer). did.

3) Exposure and development of dye-containing negative curable composition (image forming process)

Each of the dye-containing negative curable compositions obtained in the above 1) was applied in order, using a spin coater on the primer layer of the glass substrate on which the primer layer obtained in the above 2) was formed, so that the film thickness was 1 占 퐉. Prebaked for 120 seconds.

Subsequently, the exposure amount was changed and irradiated to the coating film through the mask of a line width of 2 micrometers with a wavelength of 365 nm using the i line | wire reduction projection exposure apparatus. After irradiation, the film was developed under conditions of 23 ° C. for 60 seconds using a 60% CD-2000 (manufactured by Fujifilm Arch Co., Ltd.) solution. Then, after rinsing with running water for 20 seconds, it spray-dried and obtained the pattern shape (color filter). Formation of the image was confirmed by a conventional method by an optical microscope and SEM photograph observation.

4) Evaluation

The following evaluation was performed about each pattern image obtained using dye containing negative type curable composition (1)-(10). The evaluation results are shown in Table 4 below.

(1) sensitivity

In the 2 micrometer wide pattern, the exposure amount which the width | variety of a dot and a space becomes 1: 1 was made into the appropriate exposure amount, and the exposure amount was made into the sensitivity. The smaller the value is, the higher the sensitivity is, and the better the sensitivity is.

(2) Profile

The SEM image at the appropriate exposure amount of (1) observes the cross-sectional shape of the pattern by the naked eye, and it is called "(circle)" that the profile of an image cross section is favorable, and is a slightly round top (round head) shape. The thing was called "(triangle | delta)", and the round top shape thing was certainly called "x".

(3) Non-exposure residue

The pattern image was visually observed by the SEM image at the appropriate exposure amount of (1), and it was called "(circle)" that no residue was seen at all in the non-exposed part. The thing was called "(triangle | delta)", and the thing which surely showed the residue to a non-exposed part was made into "x".

(4) heat resistance

Each of the dye-containing negative curable compositions on a separately produced glass substrate was coated with a film thickness of 1 μm, and each coating film was placed on a 200 ° C. hot plate so as to be in contact with the glass substrate and left for 1 hour. And the spectral change was measured using the spectrophotometer MS-1500 (made by Shimadzu Corporation), and (DELTA) E * ab was computed with the color analysis program. The calculated value was used as an index for evaluating heat resistance. The smaller the value, the better the heat resistance.

(5) light resistance

Each dye-containing negative curable composition was applied on a separately prepared glass substrate at a film thickness of 1 μm, and each coating film was irradiated with xenon irradiated water meter SX75 (manufactured by Sugashi Kenki Co., Ltd.) for 20 hours (200,000 LUX? H). )did. After that, the spectral change was measured using the spectrophotometer MS-1500 (manufactured by Shimadzu Seisakusho Co., Ltd.), ΔE * ab was calculated by a color analysis program, and the calculated value was used as an index for evaluating light resistance. The smaller the value, the better the light resistance.

Table 4

As shown in Table 4, in the embodiment in which the phthalocyanine-based dye and the quinophthalone-based dye according to the present invention are used in combination, high sensitivity is obtained, and a pattern profile having a good rectangular cross section is formed in the exposed portion, and developed in the non-exposed portion. There was no residue, and the formed pattern image showed excellent heat resistance and light resistance. On the other hand, in the comparative example in which the pigment | dye which concerns on this invention was not used together, the sensitivity was inferior compared with an Example, and the cross-sectional shape of the formed pattern shape was also rounded, and it was not able to comprise in a favorable rectangular shape, and the development residue remained in the non-exposed part. Discarded. In addition, the formed pattern image fell large also in the point of heat resistance and light resistance.

According to the present invention, it is a curable composition suitable for forming a dye system, specifically, has a high sensitivity, is a rectangular shape having no residue in a non-exposed area (non-image portion) and having a good cross-sectional shape, and excellent in heat fastness and light fastness. Providing a dye-containing negative curable composition which enables the formation of a fine pattern (especially when patterned by stepper exposure), and the pattern (especially when patterned by stepper exposure) is sharp (especially in cross-sectional shape) It is possible to provide a color filter (particularly a color filter for a solid state image pickup device) having a high rectangular shape, high resolution, and excellent heat and light fastness, and a manufacturing method thereof.

Claims (13)

(A) Alkali-soluble binder, (B) Organic solvent-soluble dye, (C) Photoinitiator, (D) Radical polymerizable monomer, (E) At least a dye-containing negative curable composition containing an organic solvent, The organic solvent-soluble dye (B) contains at least one of the dyes represented by the following general formula (A) and at least one of the quinophthalone dyes represented by the following general formula (1). Dye-containing negative curable composition.

[In general formula (A), M <^1> represents metals, Z <^1> , Z <^2> , Z <^3> , and Z <^4> respectively independently represent the atomic group which forms the 6-membered ring which consists of atoms chosen from a carbon atom and a nitrogen atom. ]

[In General Formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -SR ^5, or -SR ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. Provided that at least one of R ¹ to R ⁴ represents -SR ⁵ ] The dye-containing negative curable composition according to claim 1, wherein the dye represented by the general formula (A) is a phthalocyanine dye represented by the following general formula (B).

[In General Formula (B), M ¹ represents metals, and R ¹⁰¹ to R ¹¹⁶ each independently represent a hydrogen atom or a substituent.] The dye-containing negative curable composition according to claim 1 or 2, wherein the photopolymerization initiator (C) is an oxime compound. The dye-containing negative curable composition according to claim 1 or 2, wherein the alkali-soluble binder (A) is a resin having an unsaturated double bond in the side chain. The dye-containing negative curable composition according to claim 1 or 2, wherein the organic solvent (E) contains a cyclic ketone solvent. The color filter formed using the dye-containing negative curable composition of Claim 1 or 2. A method for producing a color filter, comprising applying a dye-containing negative curable composition described in claim 1 or 2 onto a support, then exposing through a mask, and developing to form a pattern. The dye-containing negative curable composition containing (A) an alkali-soluble binder, (B) an organic solvent soluble dye, (C) a photoinitiator, and (D) a radical polymerizable monomer, The said (B) organic solvent soluble Dye-containing negative type curable composition characterized by the dye containing 1 or more types of pigment | dye represented by following General formula (C1), and 1 or more types of quinophthalone type pigment | dye represented by following General formula (1).

[In Formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, or an aryl. Oxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group , An aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a six-membered ring together with a carbon atom, and four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents the integer of 0 or 1-5, and four cn may be same or different. However, one of the cn a plurality of Rc ₁ represents an integer of 1-5, the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1 and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

[In General formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom, a halogen atom, -SR <^5> or -SR <^6> , and at least 1 of R <^1> -R <^4> is -SR <^5> . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and R ⁵ may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group.] 9. The dye-containing negative curable composition according to claim 8, wherein the photopolymerization initiator (C) is an oxime compound. The dye-containing negative curable composition according to claim 8 or 9, wherein the alkali-soluble binder (A) is a resin having an unsaturated double bond in the side chain. The dye-containing negative curable composition according to claim 8 or 9, further comprising an organic solvent, wherein the organic solvent contains a cyclic ketone solvent. A color filter comprising at least one kind of dye represented by the following general formula (C1) and at least one kind of quinophthalone dye represented by the following general formula (1).

[In Formula (C1), Rc ₁ is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxy group, an aliphatic oxy group, or an aryl. Oxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group , An aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a six-membered ring together with a carbon atom, and four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents the integer of 0 or 1-5, and four cn may be same or different. However, one of the cn a plurality of Rc ₁ represents an integer of 1-5, the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1 and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

[In General formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom, a halogen atom, -SR <^5> or -SR <^6> , and at least 1 of R <^1> -R <^4> is -SR <^5> . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and R ⁵ may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group.] A method for producing a color filter comprising the step of applying the dye-containing negative curable composition according to claim 8 or 9 onto a support, exposing through a mask, and developing to form a pattern image.