JP4384582B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to 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 image pickup device (CCD, CMOS, etc.), and the dye-containing negative. The present invention relates to a color filter using a mold curable composition and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. In addition, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  In recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there is a problem that color unevenness occurs due to the coarse particles of the pigment. For this reason, it was not suitable for uses requiring a fine pattern such as a solid-state imaging device.

  In order to solve such a problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 5). However, in general, a curable composition containing a dye is inferior to a curable composition using a pigment in terms of various properties such as light resistance, heat resistance, solubility, and coating uniformity. there were. In particular, in the case of a color filter manufacturing application for a solid-state image sensor, a film thickness of 1.5 μm or less is required, so that a large amount of dye must be added to the curable composition, and thereby adhesion to the substrate can be improved. There have also been problems that pattern formation is extremely difficult, such as insufficientness, insufficient curing, and loss of dye even in exposed areas.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375

  Accordingly, an object of the present invention is to provide a dye-containing negative curable composition suitable for using a dye. Specifically, the dye-containing negative curable composition has high sensitivity, no residue in an unexposed portion, and a rectangular fine pattern. It is an object of the present invention to provide a dye-containing negative curable composition capable of forming a pattern and excellent in heat fastness and light fastness, and a color filter using the same. At the same time, it is an object of the present invention to provide a color filter which is excellent in pattern formability and has high cost performance, in particular, a color filter for a solid-state imaging device and a manufacturing method thereof.

Specific means for solving the above problems are as follows.
<1> A dye containing at least an (A) alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a radical polymerizable monomer, and (E) an organic solvent. A negative curable composition, wherein the organic solvent-soluble dye (B) is at least one dye represented by the following general formula (A) and a quinophthalone dye represented by the following general formula (1) A negative-type curable composition containing a dye.

〔一般式（Ａ）中、Ｍ¹は金属類を表し、Ｚ¹、Ｚ²、Ｚ³、およびＺ⁴は各々独立に、炭素原子および窒素原子より選ばれる原子で構成された６員環を形成する原子群を表す。〕

[In General Formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a 6-membered ring composed of atoms selected from a carbon atom and a nitrogen atom. Represents the atomic group to be formed. ]

〔一般式（１）中、Ｒ¹〜Ｒ⁴は各々独立して、水素原子、ハロゲン原子、−Ｓ−Ｒ⁵または−Ｓ−Ｒ⁶を表す。Ｓは硫黄原子を表し、Ｒ⁵は酸素原子をエーテル結合の形で含むアルキル基を表し、更に置換基としてヒドロキシ基を有してもよい。Ｒ⁶はヒドロキシ基を有するアルキル基を表す。ただしＲ¹〜Ｒ⁴のうち少なくとも１つは−Ｓ−Ｒ⁵を表す。〕

[In General Formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ . ]

  <2> The dye-containing negative curable composition according to <1>, wherein the coloring matter represented by the general formula (A) is a phthalocyanine coloring matter represented by the following general formula (B): .

〔一般式（Ｂ）中、Ｍ¹は金属類を表し、Ｒ¹⁰¹〜Ｒ¹¹⁶は各々独立して、水素原子または置換基を表す。〕

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

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

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

  <5> The dye-containing negative curable composition according to <1> to <4>, wherein the organic solvent (E) contains a cyclic ketone solvent.

  <6> A color filter comprising the dye-containing negative curable composition according to <1> to <5>.

  <7> A color comprising the steps of applying the dye-containing negative curable composition of the above <1> to <5> onto a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method of a filter.

  According to the present invention, a highly sensitive and rectangular pattern can be formed (particularly when a pattern is formed by stepper exposure), and there is no residue in an unexposed portion, and the dye has excellent heat fastness and light fastness. A negative-type curable composition can be provided. Further, according to the present invention, it is possible to provide a color filter excellent in pattern formability and high cost performance, and a manufacturing method thereof.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described 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, (E A dye-containing negative curable composition containing at least an organic solvent, wherein the organic solvent-soluble dye (B) is described later with at least one of the pigments represented by the general formula (A) described later. It is characterized by containing a quinophthalone dye represented by the general formula (1) (hereinafter, these may be collectively referred to as “the dye in the present invention”). The dye-containing negative curable composition of the present invention can improve the heat fastness and light fastness of a pattern formed using the dye in the present invention. Furthermore, the dye-containing negative curable composition of the present invention can achieve high sensitivity, can form a rectangular pattern, and can eliminate a residue in an unexposed portion.

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, and in particular, a stepper method (reduction using a reduction projection exposure machine). It is preferable to perform exposure by a projection exposure method. Such a stepper method forms a pattern by performing exposure while varying the exposure amount in stages, and the pattern rectangularity, which is one of the effects of the present invention, is particularly obtained when such stepper exposure is performed. Can be good.
As an exposure apparatus used for the stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

-(A) Alkali-soluble binder-
First, the alkali-soluble binder in the present invention will be described. 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 developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, etc., and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  In addition, as the alkali-soluble binder in the present invention, a polymer obtained by copolymerizing a monomer having 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-methylol acrylamide, secondary and tertiary alkyl acrylamide, Dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) ) Acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other useful monomers having a hydrophilic group include tetrahydrofurfuryl group, phosphoric acid, phosphoric acid ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salts, and monomers containing morpholinylethyl group. is there.

  The alkali-soluble binder in the present invention preferably has an unsaturated double bond in the side chain in order to improve the 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 the unit having the unsaturated double bond or may be introduced later by a polymer reaction. As the alkali-soluble binder having an unsaturated double bond in the side chain, for example, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are suitable. Used for.

  The alkali-soluble binder in the present invention is preferably an acrylic resin among the various binders, and examples of the acrylic resin include benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth). A copolymer made of a monomer selected from acrylamide and the like, KS-resist 106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P-series and the like are preferable.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and is preferably 2000 to 1 × 10 ⁵ . A polymer is more preferable, and a 5000 to 5 × 10 ⁴ polymer is particularly preferable.

  The content of the alkali-soluble binder is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass with respect to the total solid content in the composition from the viewpoint of developability and the like. preferable.

-(B) Organic solvent soluble dye-
The dye-containing negative curable composition of the present invention comprises at least one dye represented by the following general formula (A) and at least one quinophthalone dye represented by the following general formula (1). contains.

-Dye represented by formula (A)-
The dye-containing negative curable composition of the present invention contains at least one pigment represented by the following general formula (A). This dye exhibits a good cyan hue with high transmittance characteristics, has no stability over time when it is in the form of a liquid preparation or a coated film, and is particularly resistant to heat and light. Have

In the general formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently form a 6-membered ring composed of an atom selected from a carbon atom and a nitrogen atom. Represents an atomic group to be

In the general formula (A), M ¹ represents a metal, and examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. And metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

In the general formula (A), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom necessary for forming a 6-membered ring composed of an atom selected from a carbon atom and a nitrogen atom. Represents a group. The 6-membered ring may be a saturated ring or an unsaturated ring, may be unsubstituted or may have a substituent, and another 5-membered or 6-membered ring may be condensed. It may be. The 6-membered ring includes a benzene ring, a cyclohexane ring and the like. Examples of the substituent of the 6-membered ring include the substituents described later. Further, when the 6-membered ring has two or more substituents, these substituents may be the same or different.

  Examples of the substituent of the 6-membered ring include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a straight chain or branched chain having 1 to 48 carbon atoms, more preferably 1 to 18 carbon atoms, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl , 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18. For example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group of 6 to 48, more preferably 6 to 12. For example, phenyl, na Til), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group 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,

An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms. For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy Group (for example, cyclopentyloxy, cyclohexyloxy)), 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 a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy group (preferably 1 carbon atom). ~ 32, more preferably 1-12 silyloxy groups. Methylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetoxy, pivaloyloxy, benzoyloxy, dodeca Noyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group ( Eg cyclohexyloxycarbonyloxy)),

An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12. For example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (preferably Is a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably 1 to 38 carbon atoms, more preferably An alkylsulfonyloxy group having 12 to 12. For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy group (preferably having 6 to 32 carbon atoms, more preferably 6 to 12 arylsulfonyloxy group). Such as phenylsulfonyloxy),

An acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having a carbon number) An alkoxycarbonyl group having 2 to 48, more preferably 2 to 12. For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having a carbon number of 7 to 32, more preferably An aryloxycarbonyl group having 7 to 12. For example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, carbamoyl, N, N-diethylcarbamoyl, - Ethyl -N- octylcarbamoyl, N, N- dibutylcarbamoyl, N- propylcarbamoyl, N- phenylcarbamoyl, N- methyl -N- phenylcarbamoyl, N, carboxymethyl carbamoyl into N- dicyclohexylamine),

An amino group (preferably an amino group having 32 or less carbon atoms, more preferably 12 or less. For example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino A group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms. For example, anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms). A heterocyclic amino group of, for example, 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetamide, benzamide, tetradecanamide, pivaloylamide, Cyclohexaneamide), ureido group (preferably having 1 to 32 carbon atoms) More preferred is a ureido group having 1 to 12. For example, ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably an imide group having 20 or less carbon atoms, more preferably 12 or less). For example, N-succinimide and N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, methoxycarbonylamino, ethoxycarbonylamino, t- Butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably A sulfamoylamino group having 1 to 12. For example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 48 carbon atoms, more preferably Is an azo group of 1 to 24. For example, Phenylazo, 3-pyrazolylazo), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having a carbon number) It is an arylthio group having 6 to 48, more preferably 6 to 12. For example, phenylthio), a heterocyclic thio group (preferably a C1-C32, more preferably 1 to 12 heterocyclic thio group. For example, 2 -Benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms. For example, dodecanesulfinyl group), arylsulfinyl Group (preferably having 6 to 32 carbon atoms, more preferably Or an arylsulfinyl group having 6 to 12, such as phenylsulfinyl, or an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methylsulfonyl, ethylsulfonyl, Propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl),

An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms. For example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 16 carbon atoms). And the following sulfamoyl groups (for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), A sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms Sufi is alkanoylamino group. For example, diethoxy phosphino yl, di-octyloxy phosphinoylamino amino), and the like.

Among the dyes represented by the general formula (A), a phthalocyanine dye represented by the following general formula (B) is particularly preferable.

In the general formula (B), M ¹ has the same meaning as M ¹ in formula (A), is the same a preferred embodiment thereof.
In the general formula (B), R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is a 6-membered member in the general formula (A) described above. It is synonymous with the substituent which a ring has. Moreover, when the substituent represented by R ^{101 to} R ¹¹⁶ is a substitutable group, the substituent represented by R ^{101 to} R ¹¹⁶ further has a 6-membered ring in the general formula (A) described above. It may have a substituent, and when it has two or more substituents, the plurality of substituents may be the same or different.

Examples (T-1 to T139) of the substituents represented by R ^{101 to} R ¹¹⁶ are shown below. However, the present invention is not limited to these.

Next, a preferable range of the dye represented by the general formula (A) will be described. The general formula (A) is preferably represented by the general formula (B).
In the general formula (B), (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁶ ) has a substituent in at least one of the combinations, or is substituted at the β position (β disubstituted) as (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ), (R ¹¹⁰ and R ¹¹¹ ), and (R ¹¹⁴ and R ¹¹⁵ ) having a substituent in at least one combination, or α-position and β-position substituents (α-position, β-position substituents), 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 It is preferable that at least one combination of ¹¹³ and R ¹¹⁵ and / or R ¹¹⁴ and R ¹¹⁶ ) has a substituent.

Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, and an aryl group. Oxy group, heterocyclic 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, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, Al Thio group, an arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, and a phosphinoylamino group.
Examples of M ¹ include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, and VO.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ ) are used as α-substituted (mono-substituted). Or a substituent at at least one of R ¹¹⁶ ), or a β-substituted product (mono-substituted product) as (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ^111). ) And (R ¹¹⁴ or R ¹¹⁵ ).
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, carbonamido 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, phosphino Arylamino group and the like, the ^{M 1, Zn, Pd, Cu} , Ni, Co, TiO, VO , and the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) out of or having at least three substituents, or a β-position substitution product, (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 at least 3 of these.
Preferred substituents in this case include a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxy group Carbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylsulfinyl group, Examples thereof include an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a sulfo group, and M ¹ includes Zn, Pd, Cu, Ni, Co, VO, and the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) or have the same substituent at least three out, or as a β-position substitution product (R ¹⁰² or R ^103), (R ¹⁰⁶ or R ^107), (R ¹¹⁰ or R ^111), and (R ¹¹⁴ or R ¹¹⁵ ) Having the same substituent on at least three of them, and preferred substituents are halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, hetero Ring oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group, imide group, sulfonamido group, alkylsulfinyl group, arylsulfinyl group, al A compound having a kill sulfonyl group, an aryl sulfonyl group, a sulfamoyl group, or a sulfo group, wherein M ¹ is Zn, Pd, Cu, Ni, Co, VO or the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) out of or having at least three substituents, or a β-position substitution product, (R ¹⁰² or R ^103), (R ¹⁰⁶ or R ^107), (R ¹¹⁰ or R ^111), and (R ¹¹⁴ or R ¹¹⁵⁾ At least three of them, and the substituents are all the same compound, and the substituent is a halogen atom, an alkyl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, heterocyclic oxy group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group or a sulfo group,, M ¹ is Zn, Pd, Cu, Ni, Co or VO, etc., the Is that compound.

Most preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) out of or having at least three substituents, or a β-position substitution product, (R ¹⁰² or R ^103), (R ¹⁰⁶ or R ^107), (R ¹¹⁰ or R ^111), and (R ¹¹⁴ or R ¹¹⁵⁾ At least three of them have the same substituent, and the substituents are all the same compound, and the substituent is a halogen atom, an alkyl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a hetero group ring oxy group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group or a sulfo group, is the compound M ¹ is Zn, Cu, Co or VO, etc.,

  Specific examples of the dye represented by the general formula (A) (including the phthalocyanine dye represented by the general formula (B)) [Exemplary compounds C-1 to C-88, Cb-1 to Cb-50, And Cc-1 to Cc-4]. However, the present invention is not limited to these.

-Synthesis example-
Next, a synthesis example of the dye represented by the general formula (A) or (B) will be described in detail with reference to the following scheme A by taking as an example the synthesis of the dye C-1 as the exemplified compound.

(1) Synthesis of Intermediate 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 the mixture was stirred at room temperature. . To this was further added 17.0 g of sodium carbonate little by little, and after completion of the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The resulting reaction solution was poured into 500 ml of water and extracted with 300 ml of ethyl acetate. Then, the ethyl acetate phase was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 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 with heating. Next, 36.5 g (0.288 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise to this solution. After completion of the dropwise addition, the reaction was completed by further heating and stirring at 65 to 70 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of sodium sulfite and 700 ml of water were added, and the mixture was stirred at room temperature to precipitate crystals. The crystals were filtered, washed with water, purified by recrystallization with 200 ml of methanol, and 32.5 g of intermediate B was obtained (yield 60%).

(2) Synthesis of Dye C-1 150 ml of butanol was added to 34.4 g (0.081 mol) of intermediate B obtained as described above and 6.7 g (0.070 mol) of ammonium carbonate and heated at 50 ° C. Stir. Next, 4.7 g (0.035 mol) of cupric chloride was added thereto, heated to 100 to 110 ° C. and stirred for 7 hours. After completion of the reaction, butanol was distilled off, the residue was dissolved in chloroform, separated and purified by silica gel column chromatography (eluent: chloroform / methanol = 10/1), and 25 g of powdered dye C-1 was obtained. Obtained (yield 72.7%).

When the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max It was 706.8 nm, molar extinction coefficient ε55,600.

  In addition, it can synthesize | combine by the method similar to the above about other exemplary compounds other than the above-mentioned pigment | dye C-1.

-Quinophthalone dye represented by the general formula (1)-
The compound represented by the following general formula (1) is a compound that satisfies both high light resistance and high heat resistance, both of which have not been conventionally used, and can be freely dissolved in water or a solvent if necessary. .

In the general formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ .

In yet Formula (1), it is preferred that R ⁵ is an alkyl group having 2 to 16 carbon atoms in total containing one to six oxygen atoms in the form of ether linkages, R ² and R ³ -S- R ⁵ and R ¹ and R ⁴ are preferably a hydrogen atom or a halogen atom. One of the structural features of the quinophthalone dye represented by the general formula (1) in the present invention is that it has at least one alkyl group having an ether bond on the benzene ring on the phthaloyl side of the quinophthalone skeleton.

In the said General formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom represented by R < ¹ > -R < ⁴ >, Preferably, they are a chlorine atom and a bromine atom.
In the case where R ^{1 to} R ⁴ are —S—R ⁵ , R ⁵ is preferably an alkyl group having 1 to 6 oxygen atoms in the form of an ether bond and having 2 to 16 carbon atoms in total, particularly an oxygen atom. Alkyl groups having 2 to 12 carbon atoms in total in the form of 2 to 4 ether bonds are preferred. Here, the alkyl group may be linear or branched, and may have a ring-forming part.

Examples of R ⁵ include 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-ethoxyhexyl 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-diethyl-1,3-dioxolane-4- Yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2,2-dipropyl-1,3-dioxolan-4-yl) methyl group, (2-propyl-1, - dioxolan-4-yl) methyl group, (2-pentyl-1,3-dioxolan-4-yl) methyl group,

2- (tetrahydrofurfuryloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylethyloxy) ethyl group, 2- (1,3-dioxolan-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, and the like.

In case R ¹ to R ⁴ is -S-R ^6, preferably 1 to 4 comprises a total alkyl group having 2 to 12 carbon a hydroxy group as R ^6, in terms of the optical density of the dye, hydroxy An alkyl group having 1 to 3 groups and 2 to 8 carbon atoms in total is particularly preferable.

Examples of R ⁶ include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-1-methylpropyl group, 4-hydroxybutyl group, Examples include 2,3,4-trihydroxybutyl group, 2,3,4,5-tetrahydropentyl group, 6-hydroxyhexyl group, 11-hydroxyundecanyl group, 12-hydroxydodecanyl group and the like.

In the quinophthalone dye represented by the general formula (1) and tautomers thereof, the total number of oxygen atoms as ether bonds contained in R ^{1 to} R ⁴ is preferably 1 to 16, and the solubility is high. From the viewpoint of the optical density of the dye and 2 to 12, it is particularly preferable.
In addition, the total number of oxygen atoms contained in R ^{1 to} R ⁴ including the oxygen atom contained in the hydroxy group is preferably 2 to 24, and particularly preferably 3 to 16.
In addition, the quinophthalone dye represented by the general formula (1) and the tautomer thereof have a structure in which —S—R ⁵ is introduced into R ² and / or R ³ in view of the absorption characteristics of the dye. preferable.

  The quinophthalone dye represented by the general formula (1) (the following compound (1)) has tautomers having structures such as the following compounds (1 ′) and (1 ″). Tautomers are also included in the scope of the present invention.

  Hereinafter, specific examples (specific examples 1 to 227) of the quinophthalone dye (quinophthalone compound) represented by the general formula (1) in the present invention are shown in the table. However, these specific examples do not limit the scope of the compounds in the present invention.

(Method for producing quinophthalone dye represented by formula (1))
A method for producing a quinophthalone dye (quinophthalone compound) represented by the general formula (1) in the present invention will be described below. The outline of the typical production method (first and second production methods) is as follows.

-First manufacturing method-
As the first production method, first, in an organic solvent, 1 to 16 mols of the following compound (B) is used with 1 to 16 mols of the alkali compound with respect to 1 mol of the following compound (A). In addition, the reaction is performed at 20 to 200 ° C. for 1 to 8 hours.

〔化合物（Ａ）中、Ｒ⁷はハロゲン原子を表し、Ｒ⁸は水素原子を表す。ａはＲ⁷の導入個数を表し、１〜４の整数を表す。ｂはＲ⁸の導入個数を表し、０〜３の整数を表わす。但し、ａ＋ｂは４である。〕

[In the compound (A), R ⁷ represents a halogen atom, and R ⁸ represents a hydrogen atom. a represents the number of introduced R ⁷ and represents an integer of 1 to 4. b represents the number of introduced R ⁸ and represents an integer of 0 to 3. However, a + b is 4. ]

HS-R ⁵ (B)
[In the compound (B), R ⁵ is the same as in the general formula (1). ]

  At this time, as the organic solvent, N-methylpyrrolidone, DMI, sulfolane, DMF, DMAC, toluene, ethyl acetate and the like are used, and as the alkaline compound, potassium carbonate, calcium carbonate, sodium hydroxide and potassium hydroxide are used. Etc. are 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 then purified by column chromatography as necessary. Can be obtained.

-Second manufacturing method-
As a second production method, first, an alkali compound is used in an organic solvent in an amount of 1 to 16 moles per 1 mole of the compound (A), and 20 to 20 moles of the following compound (C). The reaction is carried out at ˜200 ° C. for 1 to 24 hours.

HS-R ⁶ (C)
[In the compound (C), R ⁶ represents the same as in general formula (1). ]

  Next, the solution is discharged into water, neutralized with dilute hydrochloric acid or acetic acid, collected by filtration and washed with water to obtain the following compound (D). At this time, as the organic solvent and the alkali compound used in the reaction, those similar to those used in the first production method are used.

〔化合物（Ｄ）中、Ｒ⁷とＲ⁸とは前記化合物（Ａ）におけるものと同様ものを表し、Ｒ⁶は一般式（１）におけるものと同様のものを表す。また、ａ−ｃは０〜３を表し、ｂは０〜３を表し、ｃは１〜４を表す。但し、（ａ−ｃ）＋ｃ＋ｂは４である。〕

[In the compound (D), R ⁷ and R ⁸ represent the same as those in the compound (A), and R ⁶ represents the same as that in the general formula (1). Moreover, a-c represents 0-3, b represents 0-3, c represents 1-4. However, (a−c) + c + b is 4. ]

  Next, the compound (D) is reacted at 20 to 200 ° C. for 1 to 24 hours together with 1 to 24 mol of the following compound (E) using 1 to 24 mol of an alkali compound in an organic solvent. The target quinophthalone dye represented by the general formula (1) is obtained. As the organic solvent and the alkali compound, those similar to those used in the first production method are used.

Z-R 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. . ]

Further, 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 represented by the general formula (1) is similarly obtained. System dyes can be produced. As the organic solvent used in the reaction, the same organic solvent as used in the first production method is used. Examples of the alkaline aqueous solution include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. As the phase transfer catalyst, tetrabutylammonium bromide, tetramethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, etc. are used.
When R ⁶ of the compound (D) is an alkyl group having an α, β-dihydroxy group, the following compound (F) and an acid catalyst such as p-toluenesulfonic acid are dehydrated and refluxed in an organic solvent. Thus, the intended quinophthalone dye represented by the general formula (1) can be obtained.

〔化合物（Ｆ）中、Ｒ¹⁰は、水素原子またはアルキル基を表し、Ｒ¹¹はアルキル基を表し、Ｒ¹⁰とＲ¹¹とは互いに結合して環を形成していてもよい。〕

[In the compound (F), R ¹⁰ represents a hydrogen atom or an alkyl group, R ¹¹ represents an alkyl group, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. ]

  In the dye-containing negative curable composition of the present invention, one or more of the dyes represented by the general formula (A) described above and the quinophthalone dye represented by the general formula (1) described above These may be used in combination with one or more of the above, and a known xanthene dye or triarylmethane dye may be used in combination as required.

  The total concentration of the coloring matter in the dye-containing negative curable composition of the present invention varies depending on the molecular weight and molar extinction coefficient, but is preferably 0.5 to 80% by mass with respect to the total solid components of the composition. -60 mass% is more preferable.

  In addition, in the case of mixing and toning the dye represented by the general formula (A) and the quinophthalone dye represented by the general formula (1), the addition of the dye to be added in the smallest amount among the dyes to be added The amount is preferably at least 10% or more, more preferably 10 to 80%, of the total amount of dye added.

-(C) Photopolymerization initiator-
Next, the photopolymerization initiator will be described. A photoinitiator is contained with the below-mentioned radically polymerizable monomer in the dye-containing negative curable composition of the present invention. The photopolymerization initiator is not particularly limited as long as it can polymerize the radical polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 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-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-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 (ethoxycarbonyl) Methyl) 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- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-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) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -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 (trichloro Methyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -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 (trichloro) Methyl) -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-fluoro -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-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, as the photopolymerization initiator, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ, manufactured by Midori Chemical Co., Ltd.) -123), T series manufactured by PANCHIM (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, manufactured by Ciba Specialty Chemicals) Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1 2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4 -Morpholinobyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -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 useful.

  Among these, as a photoinitiator in this invention, an oxime type compound is preferable. Examples of the oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 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, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyl Examples include tyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. Can be mentioned.

In addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound / trimethyl disclosed in Japanese Patent Publication No. 51-48516 And halomethyl-s-triazine compounds.

  The total content of the photopolymerization initiator is preferably 0.01% by mass to 50% by mass and more preferably 1% by mass to 30% by mass with respect to the solid content (mass) of the radical polymerizable monomer described later. 1% by mass to 20% by mass is particularly preferable. When the content of the photopolymerization initiator is in the range of 0.01 to 50% by mass, the polymerization is easy to proceed, and the film strength can be sufficiently improved. Moreover, when using together the said oxime type compound and another photoinitiator, 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) Radical polymerizable monomer-
Next, the radical polymerizable monomer will be described. As the radical polymerizable monomer used in the present invention, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. By containing with the above-mentioned photoinitiator etc., the composition of this invention can be comprised in a negative type.

  Examples of the radical polymerizable monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane and then (meth) acrylated after addition of ethylene oxide or propylene oxide; Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, Polyester acrylates described in JP-B Nos. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof; Can be mentionedFurthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be mentioned. The radical polymerizable monomer in the present invention is preferably a polyfunctional (meth) acrylic compound.

  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 still more preferable that it is 10-50 mass%. When the content of the radical polymerizable monomer is in the range of 1 to 60% by mass, the curability of the exposed portion is sufficient, and the elution resistance of the unexposed portion can be improved.

-Crosslinking agent-
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of (b) may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group, or an acyloxymethyl group) according to (b).

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

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ Bishydroxybiphenyl, hexamethylol form of TrisP-PA, hexamethoxymethyl form of TrisP-PA, compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol form of TrisP-PA, bishydroxymethylnaphthalenediol, etc. Is mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the dye-containing negative curable composition varies depending on the material, but from the viewpoint of improving curability, it is 1 to 70 with respect to the solid content (mass) of the curable composition. % By mass is preferable, 5 to 50% by mass is more preferable, and 7 to 30% by mass is particularly preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present 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-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

-(E) Organic solvent-
The organic solvent that can be used in the present invention is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but in particular, the solubility and coating property of the dye and binder. In view of safety, it is preferably selected, 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. Furthermore, it is also preferable to use a cyclic ketone solvent alone.

  When a mixed solvent in which two or more organic solvents are mixed is used, the mixed solvent is preferably a mixed solvent of a cyclic ketone solvent and another organic solvent. Examples of the cyclic ketone solvent include cyclopentanone, cyclohexanone, cycloheptanone, and the like, and cyclohexanone is particularly preferable.

  Examples of the solvent other than the cyclic ketone include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

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 and xylene are preferred.

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

  When the cyclic ketone solvent and another organic solvent are mixed, the content of the cyclic ketone solvent in the total amount of the mixed solvent is preferably 40% by mass or more, and more preferably 60% by mass or more. .

  The amount of the organic solvent used in the present invention is preferably such that the total solid concentration of the dye-containing negative curable composition of the present invention is 5 to 80% by mass from the viewpoint of coatability, and 5 to 60. More preferably, it is more preferably 10 to 50% by weight.

<Various additives>
In the dye-containing negative curable composition of the present invention, various additives, for example, a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An anti-aggregation agent or the like can be blended.

  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; nonionic, cationic And anionic surfactants: 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-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the non-cured part is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used.
The dye-containing negative curable composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is formed into a predetermined mask pattern. And a negative coloring pattern is formed by developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.
In the present invention, the exposure is preferably performed by the above-described stepper exposure.

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

Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing negative curable composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution 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.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

1) Preparation of dye-containing negative curable composition Each compound was mixed and dissolved in the composition shown below to prepare the dye-containing negative curable composition of the present invention.
〔composition〕
・ Ethyl lactate (organic solvent) 67.3g
・ Resin C 7.9g
(Benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])
・ Monomer A 4.8g
(Radically polymerizable monomer: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
・ Exemplary Compound C-1 6.6 g
(Dye represented by formula (A))
・ Specific example number 39 2.2g
(Quinophthalone dye represented by the general formula (1))
・ 2.1g of photopolymerization initiator
(Product name: TAZ-107, manufactured by Midori Chemical Co., Ltd.)

2) Production of silicon wafer substrate with undercoat layer A silicon wafer substrate was coated with a resist solution (trade name: CT-2000L, manufactured by Fuji Film Arch Co., Ltd.) using a spin coater so as to have a film thickness of 2 μm. Heat-dried at 1 degreeC for 1 hour, the cured film (undercoat layer) was formed, and the silicon wafer board | substrate with an undercoat layer was produced.

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition obtained in 1) above was applied onto the silicon wafer substrate with the undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1 μm, and 100 ° C. Was pre-baked for 120 seconds to prepare a sample in which a resist layer was formed on the substrate.

[Examples 2 to 10]
In Example 1, a 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. Each sample was formed.

[Comparative Example 1]
In Example 1, a dye-containing negative curable composition for comparison was used 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. Was prepared to form a sample.

※アルカリ可溶性バインダー
・樹脂Ａ：商品名 ＡＣＡ２５０、ダイセル化学工業（株）製
（化合物名：メタクリル酸−４−アクリロイルオキシメチル−２−ヒドロキシシクロヘキシルエステル／メタクリル酸アルキル共重合体）
・樹脂Ｂ：商品名 ＡＣＡ３００、ダイセル化学工業（株）製
（化合物名：メタクリル酸−４−アクリロイルオキシメチル−２−ヒドロキシシクロヘキシルエステル／メタクリル酸アルキル共重合体）
・樹脂Ｃ：ベンジルメタクリレート／メタクリル酸共重合体（＝６０／４０〔モル比〕）
※ラジカル重合性モノマー
・モノマーＡ：日本化薬（株）製、ＤＰＨＡ（主成分：ジペンタエリスリトールヘキサアクリレート）
※有機溶剤可溶性染料
・有機溶剤可溶性染料の欄の記号（比較例を除く）は、一般式（Ａ）で表わされる色素の例示化合物番号、および、一般式（１）で表わされるキノフタロン系色素の具体例番号に対応する。
・ＶＢ−２６２０：オリエント化学工業（株）製
※光重合開始剤
・「ＴＡＺ−１０７」：みどり化学（株）製
・オキシムＡ：２−（Ｏ−ベンゾイルオキシム）−１−［４−（フェニルチオ）フェニル］−１，２−オクタンジオン〔チバ・スペシャルティ・ケミカルズ（株）製〕
・オキシムＢ：１−（Ｏ−アセチルオキシム）−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタノン〔チバ・スペシャルティ・ケミカルズ（株）製〕

* Alkali-soluble binder / resin A: Trade name ACA250, manufactured by Daicel Chemical Industries, Ltd.
(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
-Resin B: Product name ACA300, manufactured by Daicel Chemical Industries, Ltd.
(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
Resin C: benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])
* Radically polymerizable monomer / Monomer A: Nippon Kayaku Co., Ltd., DPHA (main component: dipentaerythritol hexaacrylate)
* Symbols in the column of organic solvent-soluble dyes / organic solvent-soluble dyes (excluding comparative examples) are the example compound numbers of the dyes represented by the general formula (A) and the quinophthalone dyes represented by the general formula (1). Corresponds to a specific example number.
-VB-2620: manufactured by Orient Chemical Industries Co., Ltd. * Photopolymerization initiator-"TAZ-107": manufactured by Midori Chemical Co., Ltd.-Oxime A: 2- (O-benzoyloxime) -1- [4- (phenylthio) ) Phenyl] -1,2-octanedione [Ciba Specialty Chemicals Co., Ltd.]
Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone [manufactured by Ciba Specialty Chemicals Co., Ltd.]

4) Evaluation (1) Sensitivity For the samples formed in each of the examples and comparative examples, using an i-line reduction projection exposure apparatus, the exposure amount was passed through a coating film at a wavelength of 365 nm through a mask of 2 μm length × 2 μm width. Irradiated. After the irradiation, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 100%, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. The image formation was confirmed by an ordinary method using an optical microscope and SEM photograph observation.
At this time, the exposure amount at which the width of the pixel pattern of 2 μm in length × 2 μm in width and the space between the pixel patterns was 1: 1 was determined as the appropriate exposure amount, and the exposure amount was defined as the sensitivity. Smaller numbers are preferable because of higher sensitivity. The results are shown in Table 2 below.

(2) Profile In (1) above, the pattern cross section of the pixel pattern formed at the appropriate exposure amount was observed with an SEM image. At this time, a good rectangular profile is evaluated as “◯”, a slightly round top (round head) shape is evaluated as “△”, and a completely round top shape is evaluated as “×”. It was evaluated. The results are shown in Table 2 below.

(3) Unexposed part residue In said (1), the pattern cross section was observed in the SEM image about the pixel pattern formed at the time of appropriate exposure amount. At this time, the case where no residue was found in the unexposed area was evaluated as “◯”, the case where the residue was slightly recognized in the unexposed area was evaluated as “△”, and the case where there was no practical problem was evaluated as “△”. Those in which residues were clearly observed in the part were evaluated as “x”. The results are shown in Table 2 below.

(4) Heat resistance On the glass substrate produced separately, the dye containing negative curable composition obtained by said 1) was apply | coated so that it might become a film thickness of 1 micrometer. The glass substrate on which the coating film was formed was left on a hot plate at 200 ° C. for 1 hour, and then the spectral change was measured using a spectrophotometer (trade name: MS-1500, manufactured by Shimadzu Corporation). From this measured value, ΔE ^* ab was calculated by a color analysis program to evaluate heat resistance. The results are shown in Table 2 below.

(5) Light resistance On a separately prepared glass substrate, the dye-containing negative curable composition obtained in 1) above was applied to a film thickness of 1 μm, and the applied film was applied to a xenon irradiation weather meter (trade name: SX75, manufactured by Suga Test Instruments Co., Ltd.) for 20 hours (200,000 lux · h), and then spectral change using a spectrophotometer (trade name: MS-1500, manufactured by Shimadzu Corporation) It was measured. From this measured value, ΔE ^* ab was calculated by a color analysis program to evaluate light resistance. The results are shown in Table 2 below.

  From Table 2, in the examples using the dye represented by the general formula (A) and the quinophthalone dye represented by the general formula (1), the heat resistance and light resistance are excellent, and the sensitivity is excellent. The rectangularity of the pattern was also good, and no residue was confirmed in the unexposed area. On the other hand, in the comparative example using the dye other than the dye in the present invention, the heat resistance and the light resistance are remarkably inferior, both the sensitivity and the rectangularity of the pattern are bad, and further, the residue is left in the unexposed area. Was recognized.

Claims (7)

Dye-containing negative curing comprising at least: (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. The organic solvent-soluble dye (B) contains at least one dye represented by the following general formula (A) and a quinophthalone dye represented by the following general formula (1) A dye-containing negative curable composition characterized by comprising:

[In General Formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a 6-membered ring composed of atoms selected from a carbon atom and a nitrogen atom. Represents the atomic group to be formed. ]

[In General Formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R 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 a metal, and R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent. ]   The dye-containing negative curable composition according to claim 1 or 2, wherein the (C) photopolymerization initiator is an oxime compound.   The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain.   The dye-containing negative curable composition according to any one of claims 1 to 4, wherein the (E) organic solvent contains a cyclic ketone solvent.   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 5.   It includes a step of applying the dye-containing negative curable composition according to any one of claims 1 to 5 on a support, exposing through a mask, and developing to form a pattern. A method for producing a color filter.