TWI388925B - Dye-containing negative type curable composition, color filter and method of producing the same - Google Patents

Description

Negative hardening composition containing dye, color filter, and manufacturing method thereof

The present invention relates to a dye-containing negative-type hardenable composition suitable for forming a colored image for a color filter such as a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), and a dye-containing composition is used. A color filter of a negative-type hardenable composition and a method for producing the same.

A method of producing a color filter for a liquid crystal display element or a solid-state imaging element is conventionally known as a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method.

Among them, the pigment dispersion method is a method of producing a color filter by using a photolithographic method in which a pigment is dispersed in various photosensitive compositions by a Lithography method, and has a light or heat due to the use of a pigment. Wait for the advantage of stability. In addition, since photolithography is used, it has been gradually applied to a suitable method for producing a color filter for a large-screen, high-definition color display having high positional accuracy.

When a color filter is produced by a pigment dispersion method, a photosensitive composition can be applied onto a glass substrate by a spin coater or a roll coater, and dried to form a coating film, and the pattern of the coating film can be formed. The colored pixels are formed by exposure and development, and the color filters are obtained by repeating this operation for each color.

In the pigment dispersion method, a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are combined with an alkali-soluble resin has been proposed (for example, refer to Patent Documents 1 to 4).

Further, in recent years, color filters for solid-state imaging devices are expected to be further refined. However, in the conventional pigment dispersion system, it is difficult to further improve the resolution, and there is a problem that color unevenness occurs due to coarse particles of the pigment. Therefore, it cannot be applied to the use of a fine pattern such as a solid-state imaging element.

In order to solve such a problem, a technique of using a dye in place of a conventional pigment has been proposed (for example, refer to Patent Document 5). However, in general, the curable composition containing a dye has various problems such as light resistance, heat resistance, solubility, and coating uniformity, and has a problem of deterioration as compared with a curable composition using a pigment. In particular, in the case of a color filter for a solid-state imaging device, since a film thickness of 1.5 μm or less is required, it is necessary to add a large amount of coloring matter to the curable composition, whereby the adhesion to the substrate is insufficient. When sufficient hardening is obtained, even if the exposed portion is removed from the dye or the like, patterning property is remarkably difficult.

In addition, there is little technical knowledge for forming a fine pattern using a dye system, and only the disclosed examples have been used so far, and the area removed by development, that is, the residue of the unexposed area (non-image portion), is difficult. The formed fine pattern cross-sectional shape constitutes a good rectangular shape.

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

As described above, in applications such as solid-state imaging devices requiring high definition and uniform color, although a curable composition containing a dye is useful, there is still a problem of removing non-image portion residues and stably maintaining the color density of the dye. Or the improvement of the firmness such as heat resistance or light resistance of the color tone.

Accordingly, it is an object of the present invention to provide a dye-containing negative-type hardenable composition suitable for use with a dye, and more particularly to provide a high-sensitivity residue having no unexposed portion, a rectangular fine pattern, and heat resistance. A dye-containing negative-type hardenable composition excellent in light resistance and a color filter using the same. Further, it is also an object of the invention to provide a color filter excellent in pattern formation property and high in cost performance, in particular, a color filter for a solid-state imaging element and a method of manufacturing the same.

The specific technical means for solving this problem is as follows: <1> A negative-type curable composition containing a dye containing 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; and the (B) organic solvent-soluble dye contains at least the pigment represented by the formula (A) A quinacridone-based dye represented by the formula (1).

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

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ . S represents a sulfur atom, and R ⁵ represents an alkyl group which contains an oxygen atom in the form of an ether bond, and may have a hydroxyl group as a substituent. R ⁶ represents an alkyl group having a hydroxyl group. However, at least one of R ¹ to R ⁴ represents -S-R ⁵ . ]

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

[In the formula (B), M ¹ represents a ^{metal, R 1 0 1 ~ R 1} 1 6 each independently represents a hydrogen atom or a substituent of the group. ]

<3> The dye-containing negative-type hardening composition of <1> or <2>, wherein the (C) photopolymerization initiator is an anthraquinone compound.

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

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

<7> A method of producing a color filter, comprising: coating a negative-type curable composition containing the dyes of <1> to <5> on a carrier, and then performing exposure and development through a photomask The step of forming a pattern.

<8> A negative-type curable composition containing a dye, characterized by comprising at least: (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical a polymerizable monomer; and the (B) organic solvent-soluble dye containing at least one of the dyes represented by the formula (C1) and at least one of the quinophthalone-based dyes represented by the formula (1) One.

In the formula (C1), R _{C 1} represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a decyl group, a hydroxyl group, Aliphatic oxy, aryloxy, decyloxy, aminomethyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyl hydrazino, aminocarbamimidyl, amine sulfonamide Base, aliphatic oxycarbonylamine group, aryloxycarbonylamine group, aliphatic sulfonamide group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, Aminesulfonyl, sulfo, quinone or heterocyclic thio. Z _{C 1} represents a non-metal atomic group necessary for forming a 6-membered ring with a carbon atom, and the four Z _{C 1 's} 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 0 or an integer from 1 to 5, and four cns may be the same or different. However, one of cn represents an integer from 1 to 5, and several R _{C 1} in the molecule may be the same or different. Cr1, cr2, cr3 and cr4 represent 0 or 1, satisfying cr1+cr2+cr3+cr4 1.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ , R ¹ , R ² , R ³ and R At least one of ⁴ represents -S-R ⁵ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an ether bond oxygen atom in the form of 'R ⁵ may have a hydroxyl group as a substituent more. R ⁶ represents an alkyl group having a hydroxyl group.

<9> The dye-containing negative-type hardening composition of the <8>, wherein the (C) photopolymerization initiator is an anthraquinone compound.

<10> The dye-containing negative-type hardenable composition of <8> or <9>, wherein the (A) alkali-soluble binder has an unsaturated double bond in a side chain.

<11> The dye-containing negative-type hardenable composition of <8> to <10>, further comprising an organic solvent, wherein the organic solvent contains a cyclic ketone solvent.

<12> A color filter comprising at least one of a dye represented by the following formula (C1) and at least one of a quinophthalone dye represented by the following formula (C1).

In the color filter of the above <12>, it is preferable to use the negative-type curable composition containing the dye disclosed in any one of <8> to <11>.

In the formula (C1), R _{C 1} represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a decyl group, a hydroxyl group, Aliphatic oxy, aryloxy, decyloxy, aminomethyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyl hydrazino, aminocarbamimidyl, amine sulfonamide Base, aliphatic hydroxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonamide group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, Aminesulfonyl, sulfo, quinone or heterocyclic thio. Z _{C 1} represents a non-metal atomic group necessary for forming a 6-membered ring with a carbon atom, and the four Z _{C 1 's} 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 0 or an integer from 1 to 5, and four cns may be the same or different. However, one of cn represents an integer from 1 to 5, and several R _{C 1} in the molecule may be the same or different. Cr1, cr2, cr3 and cr4 represent 0 or 1, satisfying cr1+cr2+cr3+cr4 1.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ , R ¹ , R ² , R ³ and R At least one of ⁴ represents -S-R ⁵ . S represents a sulfur atom, R ⁵ represents an alkyl group having an oxygen atom in the form of an ether bond, and R ⁵ may have a hydroxyl group as a substituent. R ⁶ represents an alkyl group having a hydroxyl group.

<13> A method of producing a color filter, comprising: applying a negative-type curable composition containing the dye disclosed in any one of <8> to <11> on a carrier, and then passing through a reticle The step of forming a pattern image after exposure and development.

According to the present invention, it is possible to provide a negative-type curable composition containing a dye which is suitable for forming a dye-based curable composition, and in particular, can form a high-sensitivity and simultaneously unexposed area (non-image portion) a fine pattern having no residue and a cross-sectional shape of a good rectangle, excellent heat resistance and light resistance (particularly, when a pattern is formed by stepper exposure); and can provide one (especially by stepper exposure) a color filter having a high performance and excellent heat resistance and light resistance, which is composed of a high resolution (especially, a rectangular shape in a good cross section) and high resolution (especially for solid-state imaging elements) Color filter) and method of manufacturing the same.

Hereinafter, the dye-containing negative-type curable composition of the present invention and a color filter comprising a negative-type curable composition containing the dye and a method for producing the same will be described in detail.

<<Negative hardening composition containing dye>>

The dye-containing negative-type hardening composition of the present invention contains at least: (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical polymerizable single a dye-containing negative-type hardenable composition of the organic solvent and the (E) organic solvent; and the (B) organic solvent-soluble dye contains at least one of the dyes represented by the formula (A) to be described later and a later-described one The quinophthalone-based dye represented by the formula (1) (hereinafter, collectively referred to as such a quinophthalone-based dye is "the dye of the present invention").

Still another dye-containing negative-type hardening composition of the present invention contains at least one of a dye represented by the following formula (C1) as (A) an alkali-soluble binder and (B) an organic solvent-soluble dye; (1) at least one of the quinophthalone-based dyes (hereinafter collectively referred to as "the dye of the present invention"), (C) a photopolymerization initiator, and (D) a radical polymerizable monomer, generally speaking, It can be constituted by using (E) an organic solvent, and if necessary, it can further comprise other components, such as a crosslinking agent.

The dye-containing negative-type curable composition of the present invention can improve the heat resistance and light resistance of the formed pattern by using the dye of the present invention. Further, the dye-containing negative-type hardenable composition of the present invention can be expected to have high sensitivity, can form a rectangular pattern, and eliminate the residue of the unexposed portion.

The dye-containing negative-type hardenable composition of the present invention can be exposed by any one of a proximity method, a mirror projection method and a stepper method, in particular, using a stepping machine method (reduced projection exposure method using a reduced projection exposure machine) ) It is especially desirable to perform exposures. In such a stepper mode, the pattern is formed by changing the exposure amount in a stepwise manner, and when the stepper is exposed, the pattern rectangle of one of the effects of the present invention can be formed particularly well.

Further, for the exposure apparatus for exposure of the stepper, for example, an i-line stepping machine (trade name: FPA-3000i5+, manufactured by Canon Co., Ltd.) or the like can be used.

(A) alkali soluble binder

First, the alkali-soluble binder of the present invention will be described. When the alkali-soluble binder of the present invention is alkali-soluble, it is not particularly limited, and it is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder of the present invention is preferably a linear organic high molecular polymer, soluble in an organic solvent, and capable of being developed in a weakly alkaline aqueous solution. Such a linear organic polymer is a polymer having a carboxylic acid in a side chain, and examples thereof include, for example, JP-A-59-44615, JP-A-54-34327, and JP-A-58-12577. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, Malay disclosed in the patent specifications of No. 54-25957, JP-A-59-53836, and JP-A-59-71048 An acid copolymer, a partially esterified maleic acid copolymer or the like is particularly useful as an acidic cellulose derivative having a carboxylic acid in a side chain. In addition, an acid anhydride is added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, poly(2-hydroxyethyl (meth)acrylate), or polyethylene. Pyrrolidone or polyethylene oxide, polyvinyl alcohol and the like are also useful.

Further, as the alkali-soluble binder of the present invention, a polymer which is copolymerized with a monomer having a hydrophilic group can also be used. Examples of the monomer having the hydrophilic group include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glyceryl (meth)acrylate, and (meth)acrylamide. Acrylamide-N-methylol, propylene amide alkyl esters of grades 2 and 3, dialkylaminoalkyl (meth)acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N - ethylene caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or straight Chains of butyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, and the like.

Monomer having other hydrophilic groups, including tetrahydroindenyl, phosphoric acid, phosphate, 4-stage plating salt, epoxy ethyl chain, epoxy propyl chain, sulfonic acid or other salt, morpholine ethyl, etc. Body is also useful.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder of the present invention preferably has an unsaturated double bond in the side chain. The unsaturated double bond bonded to the side chain of the alkali-soluble binder of the present invention may, for example, be an allyl group, a (meth)acryl group, a vinyl group or the like, and is preferably an allyl group or a (meth) group. Propylene based. These unsaturated double bonds may be introduced after copolymerization having the unsaturated double bond unit, or may be introduced by a polymer reaction described later. An alkali-soluble binder having the unsaturated double bond in the side chain, for example, KS photoresist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industry Co., Ltd.), and the like.

Further, the alkali-soluble binder of the present invention is preferably a propylene-based resin among the various binders, and the propylene-based resin is more preferably benzyl (meth)acrylate or (meth) acrylate. A copolymer of a selected monomer such as hydroxyethyl acrylate or (meth) acrylamide, KS photoresist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Cyclomer P series.

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

The content of the alkali-soluble binder is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, particularly from 30 to 70% by mass, based on the viewpoint of developability and the like, and all solid components in the composition. ideal.

(B) Organic solvent soluble dye

The dye-containing negative-type curable composition of the present invention contains at least one of the dyes represented by the following formula (A) and at least one of the quinophthalone-based dyes represented by the following formula (1).

Pigment represented by the formula (A)

The dye-containing negative-type hardenable composition of the present invention contains at least one of the dyes represented by the following formula (A). This dye exhibits a good dark blue color tone with high transmittance characteristics, and has no precipitation over time in the form of a liquid preparation or a coated coating film, and is excellent in stability, and particularly excellent in heat or light.

In the general formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ and Z ⁴ represent a group of atoms of a 6-membered ring each independently forming an atom selected from a carbon atom and a nitrogen atom.

In the general formula (A), M ¹ represents a metal, and the metal includes: Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and the like, and Metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , 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 represent atomic groups necessary for forming a 6-membered ring composed of atoms selected from carbon atoms and nitrogen atoms independently. The 6-membered ring may be a saturated ring or an unsaturated ring; it may have no substituent or may have a substituent; in addition, condensation of other 5-membered or 6-membered rings may be carried out, in a 6-membered ring, Including benzene ring, cyclohexane ring and the like. The substituent having such a 6-membered ring may be a substituent described later. Further, in the case where the 6-membered ring has two or more substituents, the substituents may be the same or different.

The substituent of the 6-membered ring is a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), or an alkyl group (preferably a linear or branched chain having a carbon number of 1 to 48, more preferably 1 to 18). Or a cyclic alkyl group. For example, methyl, ethyl, propyl, isopropyl, butyl, t -butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecane Base, cetyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl (preferably carbon number 2 to 48, more preferably 2 to 18) An alkenyl group, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, or an aryl group (preferably an aryl group having a carbon number of 6 to 48, more preferably 6 to 12), for example, a phenyl group. , naphthyl), heterocyclic group (preferably a carbon number of 1 to 32, more preferably a heterocyclic group of 1 to 12. For example, 2-thiol, 4-pyridyl, 2-furyl, 2-pyrimidine Base, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazolyl-1-indenyl), decylalkyl (preferably carbon number 3 to 38, more silicon is a good group of 3 to 12, for example, alkyl trimethyl silicon, silicon alkyl triethyl, tributyl alkyl silicon, t -. butyldimethyl silicon Group, t -. Dimethyl silicone hexyl alkyl), hydroxy, cyano, nitro, alkoxy (more appropriate having 1 to 48 carbon atoms, more preferably an alkoxy group having 1 to 12 of example, methoxy, Ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t -butoxy, dodecyloxy, cycloalkoxy (eg, cyclopentyloxy, cyclohexyloxy) , aryloxy (preferably carbon number 6 to 48, more preferably 6 to 12 aryloxy group. For example, phenoxy, 1-naphthyloxy), heterocyclic oxy group (more preferably carbon number 1~) 32, more preferably a heterocyclic oxy group of 1 to 12. For example, 1-phenyltetrazole-5-oxyl, 2-tetrahydropyranyloxy), decyloxy (preferably a carbon number of 1 to 32) More preferably, it is a decyloxy group of 1 to 12. For example, trimethyl decyloxy, t -butyldimethyl decyloxy, diphenylmethyl decyloxy), decyloxy (preferably carbon) a number of 2 to 48, more preferably 2 to 12 decyloxy groups, for example, an acetoxy group, a trimethyl ethoxy group, a phenoxy group, a dodecyloxy group, an alkoxycarbonyl group (preferably An alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, an ethoxycarbonyloxy group, a t -butoxycarbonyloxy group, a cycloalkoxycarbonyloxy group (for example, cyclohexyloxycarbonyloxy) An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 18 carbon atoms, for example, a phenoxycarbonyloxy group) or an aminomethyloxy group (preferably A carbon number of 1 to 48, more preferably an amino group of 1 to 12, for example, N,N-dimethylaminomethyl methoxy, N-butylaminomethyl methoxy, N-benzene Aminomethyl methoxy group, N-ethyl-N-phenylaminomethyl methoxy group), amine sulfonyloxy group (preferably a sulfonamide having a carbon number of 1 to 32, more preferably 1 to 12) An oxy group, for example, N,N-diethylamine sulfonyloxy, N-propylamine sulfonyloxy), alkylsulfonyloxy (preferably a carbon number of 1 to 38, more preferably 1~) 12 alkylsulfonyloxy. For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy (preferably carbon number 6 to 32) More preferably, it is an arylsulfonyloxy group of 6-12. For example, phenylsulfonyloxy), fluorenyl (preferably a carbon number of 1 to 48, more preferably 1 to 12 fluorenyl groups. For example, methyl ketone, ethyl fluorenyl, propyl fluorenyl, phenyl fluorenyl, Tetradecanoyl, cyclohexyl), alkoxycarbonyl (preferably alkoxycarbonyl having 2 to 48 carbon atoms, more preferably 2 to 12), for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxy a carbonyl group, a cyclohexyloxycarbonyl group, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms, for example, a phenoxycarbonyl group) or an amine sulfonyl group (preferably having a carbon number of 1) More preferably, it is a sulfonyl group of 1 to 12. For example, amidoxime, N,N-diethylamine sulfonyl, N-ethyl-N-octylamine sulfonyl, N, N-dibutylamine sulfonyl, N-propylamine sulfonyl, N-phenylamine sulfonyl, N-methyl-N-phenylamine sulfonyl, N,N-dicyclohexylamine A sulfonyl group, an amine group (preferably an amino group having a carbon number of 32 or less, more preferably 12 or less. For example, an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, 2 -ethylhexylamino, cyclohexylamino), anilino (preferably 6 to 32 carbon atoms, more preferably 6 to 12 anilino groups. For example, anilino, N-methylanilino), hetero An amine group (preferably a carbon number of 1 to 32, more preferably a heterocyclic amine group of 1 to 12, for example, a 4-pyridylamino group) or a carboguanamine group (preferably having a carbon number of 2 to 48, more preferably a carbon amidino group of 2 to 12. For example, an acetamino group, a benzoguanamine group, a tetradecylguanidinium group, a trimethylacetamido group, a cyclohexaneguanidino group, a urea group (preferably a carbon number of 1 to 32, more preferably a ureido group of 1 to 12. For example, a urea group, an N,N-dimethylureido group, an N-phenylureido group, or a quinone imine group (more preferably a carbon number of 20) Hereinafter, it is more preferably a sub-imine group of 12 or less. For example, N-butyldithioimido group, N-phthalimido group, or alkoxycarbonyl group (preferably, carbon number 2 to 48) More preferably, it is an alkoxycarbonylamino group of 2 to 12. For example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t -butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamine group. , aryloxycarbonylamino group (preferably carbon number 7 to 32, more preferably 7 to 12 aryloxycarbonyl group. For example, phenoxycarbonylamino group), sulfonamide group (preferably carbon number 1) More preferably, it is a sulfonylamino group of 1 to 12. For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, hexadecylsulfonylamino, cyclohexylsulfonate Amidoxime) Amidino group (preferably a sulfonamide group having a carbon number of 1 to 48, more preferably 1 to 12. For example, N,N-dipropylamine sulfonamide, N-ethyl-N-12 Alkylamine sulfonamide, azo (preferably a carbon number of 1 to 48, more preferably 1 to 24 azo groups, for example, phenylazo, 3-pyrazolylazo) , alkylthio (preferably from 1 to 48 carbon atoms, more preferably from 1 to 12 alkylthio groups. For example, methylthio, ethylthio, octylthio, cyclohexylthio), arylthio (compared It is preferably a carbon number of 6 to 48, more preferably 6 to 12 arylthio groups. For example, phenylthio), heterocyclic thio (preferably a carbon number of 1 to 32, more preferably 1 to 12 of a heterocyclic sulfur For example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazoliumthio), alkylsulfinyl (preferably from 1 to 32, more preferably from 1 to 12) Alkyl sulfinylene. For example, dodecylsulfinyl), arylsulfinylene (preferably an arylsulfinylene group having a carbon number of 6 to 32, more preferably 6 to 12. For example, a phenyl sulfinylene group An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, Butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecanosulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl It is preferably an arylsulfonyl group having a carbon number of 6 to 48, more preferably 6 to 12. For example, a phenylsulfonyl group, a 1-naphthylsulfonyl group, an aminesulfonyl group (preferably having a carbon number of 32 or less) More preferably, it is an aminesulfonyl group of 16 or less. For example, amidoxime, N,N-dipropylaminesulfonyl, N-ethyl-N-dodecylaminesulfonyl, N-B a base-N-phenylamine sulfonyl group, an N-cyclohexylamine sulfonyl group, a sulfo group, a sulfonyl group (preferably a sulfonyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms). For example, Phenoxysulfonyl, octyloxysulfonyl, phenylsulfonyl), phosphinium decylamino (preferably a phosphinodecyl amide group having a carbon number of 1 to 32, more preferably 1 to 12) .E.g, Ethoxy acyl phosphine acyl group, a phosphino group, dioctyl acyl acyl group) and the like.

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

The formula (B), M ¹ is based synonymous to this formula M (A) of ^1, which is also preferably of the same shape.

The formula (B) of, ^{R 1 0 1 ~ R 1 1} 6 each independently represents a hydrogen atom or a substituent of the group, as shown in the substituted ^{R 1 0 1 ~ R 1 1} 6 group based on the same meaning as the general formula (A) The substituent of the 6-membered ring. Further, as shown in ^{R 1 0 1 ~ R 1 1} 6 of the substituent group for the case of substituents of functional groups may be, as shown in the substituents ^{R 1 0 1 ~ R 1 1} 6 may have the more general formula (A) In the case where the substituent of the 6-membered ring has two or more substituents, the plurality of substituents may be the same or different.

Hereinafter, examples of the substituent of the display shown (T1 ~ T139) the ^{R 1 0 1 ~ R 1 1} 6. However, it is not limited by these substituents in the present invention.

Next, a preferred range of the dye represented by the formula (A) will be described. The formula (A) is preferably represented by the formula (B).

The formula (B) is preferably such that the substituent at the α position (α disubstituted) has (R ^{1 0 1} and R ^{1 0 4} ), (R ^{1 0 5} and R ^{1 0 8} ), (R ¹ (Di-substituted beta]) ^{from 0} to ⁹ substituents of R ^{1 1 2)} and (R ^{1 1 3} and at least a set of combinations of substituents R ^{1 1 6)} of the, or beta] having (R ^{1 0 2} and At least one group of substituents of R ^{1 0 3} ), (R ^{1 0 6} and R ^{1 0 7} ), (R ^{1 1 0} and R ^{1 1 1} ), and (R ^{1 1 4} and R ^{1 1 5} ) Or a substitution of the alpha and beta positions (alpha position, beta position substitution) having (R ^{1 0 1} and R ^{1 0 3} and/or R ^{1 0 2} and R ^{1 0 4} ), (R ^{1 0 5} And R ^{1 0 7} and/or R ^{1 0 6} and R ^{1 0 8} ), (R ^{1 0 9} and R ^{1 1 1} and/or R ^{1 1 0} and R ^{1 1 2} ) and (R ^{1 1 3} and R At least one group of substituents of ^{1 1 5} and/or a combination of R ^{1 1 4} and R ^{1 16 6} ).

Wherein, as shown in the ^{R 1 0 1 ~ R 1 1} 6 of the substituent include: a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silicon group, a hydroxyl group, a cyano group, a nitro group, an alkoxy , aryloxy, heterocyclooxy, nonyloxy, decyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aminomethyloxy, sulfonyloxy, alkylsulfonyloxy , arylsulfonyloxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminomethylhydrazine, amine, anilino, carboguanamine, ureido, quinone, alkoxycarbonyl, Aryloxycarbonylamino, sulfonylamino, amidoxime, azo, alkylthio, arylthio, heterocyclothio, alkylsulfinylene, arylsulfinyl, alkyl Sulfonyl, arylsulfonyl, sulfonyl, sulfo, sulfonyl, phosphinylnonylamino.

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

Further, the formula (B) is more preferably: the α-substituent (monosubstituted) has (R ^{1 0 1} or R ^{1 0 4} ), (R ^{1 0 5} or R ^{1 0 8} ), (R ¹ At least one substituent of ^{0 9} or R ^{1 1 2} ) and (R ^{1 1 3} or R ^{1 16 6} ), or a β-substituent (monosubstituted) having (R ^{1 0 2} or R ^{1 0 3} ), a compound of at least one of (R ^{1 0 6} or R ^{1 0 7} ), (R ^{1 1 0} or R ^{1 1 1} ), and (R ^{1 1 4} or R ^{1 1 5} ).

In this case, preferred substituents include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, and a heterocyclic oxy group. , anthraceneoxy, aminomethyl methoxy, decyl, alkoxycarbonyl, aryloxycarbonyl, aminomethyl decyl, amine, anilino, carboguanamine, ureido, quinone imine, alkoxy Amine, aryloxycarbonyl, sulfonylamino, amidoxime, azo, alkylthio, arylthio, heterocyclic thio, alkyl sulfinylene, aryl sulfoxide a group, an alkylsulfonyl group, an arylsulfonyl group, an aminesulfonyl group, a sulfo group, a phosphinium amidino group, and M ¹ may, for example, be Zn, Pd, Cu, Ni, Co, TiO, VO, or the like. .

Furthermore, the formula (B) is preferably such that the α-position substituent has (R ^{1 0 1} or R ^{1 0 4} ), (R ^{1 0 5} or R ^{1 0 8} ), (R ^{1 0 9} or R ¹ At least three substituents of ^{1 2} ) and (R ^{1 1 3} or R ^{1 16 6} ), or a β-substituent having (R ^{1 0 2} or R ^{1 0 3} ), (R ^{1 0 6} or R ^{1 0 7),} the compound is at least three groups (R ^{1 1 0} or R ^{1 1 1)} and (R ^{1 1 4} or R ^{1 1 5)} substitutions.

In this case, preferred substituents include halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, fluorenyl group. , alkoxycarbonyl, aminomethyl decyl, amine, anilino, carboguanamine, ureido, quinone imine, alkoxycarbonylamine, aryloxycarbonylamine, sulfonamide, amidoxime An amine group, an azo group, an alkylsulfinylene group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an aminesulfonyl group, a sulfo group, and, in addition, M ¹ may be exemplified by Zn, Pd, Cu, Ni, Co, VO, and the like.

Furthermore, the formula (B) is preferably such that the α-position substituent has (R ^{1 0 1} or R ^{1 0 4} ), (R ^{1 0 5} or R ^{1 0 8} ), (R ^{1 0 9} or R ¹ At least three of the same substituents of ^{1 2} ) and (R ^{1 1 3} or R ^{1 1 6} ), or a substituent of the β-position having (R ^{1 0 2} or R ^{1 0 3} ), (R ^{1 0 6} or R ^{1 a} compound having at least three identical substituents of ( ^{7 1} ), (R ^{1 1 0} or R ^{1 1 1} ) and (R ^{1 1 4} or R ^{1 1 5} ), preferably a substituent: halogen atom, alkyl group , alkenyl, aryl, heterocyclic, cyano, alkoxy, aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminomethyl decyl, carboguanamine, ureido, oxime An amine group, an alkylsulfinylene group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an aminesulfonyl group or a sulfo group, and further, M ¹ is Zn, Pd, Cu, Ni, A compound such as Co or VO.

Furthermore, the formula (B) is preferably such that the α-position substituent has (R ^{1 0 1} or R ^{1 0 4} ), (R ^{1 0 5} or R ^{1 0 8} ), (R ^{1 0 9} or R ¹ At least three substituents of ^{1 2} ) and (R ^{1 1 3} or R ^{1 16 6} ), or a β-substituent having (R ^{1 0 2} or R ^{1 0 3} ), (R ^{1 0 6} or R ^{1 0} At least three substituents of ⁷ ), (R ^{1 1 0} or R ^{1 1 1} ) and (R ^{1 1 4} or R ^{1 1 5} ), the substituents of which are all the same compounds, and the substituents may be enumerated : halogen atom, alkyl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, aminomethyl fluorenyl group, alkyl sulfonyl group, aryl sulfonyl group, amine A sulfonyl group or a sulfo group, and M ¹ is a compound of Zn, Pd, Cu, Ni, Co or VO.

Preferably, the formula (B) is: the substituent at the alpha position has (R ^{1 0 1} or R ^{1 0 4} ), (R ^{1 0 5} or R ^{1 0 8} ), (R ^{1 0 9} or R ^{1 1 2} ) and (R ^{1 1 3} or R ^{1 1 6),} at least three substituents, or a substituent having β position (R ^{1 0 2} or ^{R 1 0 3), (R} 1 0 6 or R ^{1 0 7),} At least three substituents of (R ^{1 10 0} or R ^{1 1 1} ) and (R ^{1 1 4} or R ^{1 1 5} ), the substituents of which are all the same compound, and the substituent may be a halogen atom or an alkane. Base, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, aminomethyl decyl group, alkyl sulfonyl group, aryl sulfonyl group, amine sulfonyl group or sulfonate Base, M ¹ is a compound of Zn, Cu, Co or VO.

Specific examples of the dye (including the phthalocyanine dye represented by the formula (B)) represented by the formula (A) are shown below [exemplary compounds C-1 to C-88, Cb-1 to Cb-50, and , Cc-1~Cc-4]. However, the invention is not limited by these specific examples.

Next, the present invention further contains a negative-type curable composition of another dye, and the dye compound contains at least one of the dyes represented by the following formula (C1) and at least one of the quinophthalone-based dyes represented by the following formula (1). (Regarding the pigment of the present invention). Since at least two kinds of pigments relating to the present invention are contained, it is possible to form a pattern having a good rectangular cross section for removing the development residue of the unexposed areas compared to the conventional dye system composition, and it is possible to effectively enhance the formed pattern. Heat resistance and light resistance.

Pigment represented by the formula (C1)

The dye-containing negative-type curable composition of the present invention contains a dye represented by the following formula (C1) (hereinafter also referred to as "the phthalocyanine-based dye of the present invention"). This pigment (dye) exhibits a good blue hue with high transmittance characteristics, and does not have a liquid composition or a time-dependent precipitation in the state in which the applied coating film is formed, and is excellent in stability, especially for heat or light. Excellent tolerance.

Hereinafter, the phthalocyanine-based dye of the present invention will be described focusing on the details of each functional group of the formula (C1).

In the formula (C1), the aliphatic portion of the "aliphatic group" may be a straight chain, a branched chain or a cyclic group, or may be either saturated or unsaturated, for example, containing an alkyl group, an alkenyl group, or a ring. The alkyl group or the cycloalkenyl group may be unsubstituted or substituted with a substituent, and may be either a monocyclic ring or a condensed ring, and may be unsubstituted or substituted with a substituent. The "heterocyclic ring" is a heterocyclic ring having a hetero atom (for example, a nitrogen atom, a sulfur atom or an oxygen atom) in the ring, and may be either a saturated ring or an unsaturated ring, or may be a monocyclic ring or a condensed ring. Any of them may be unsubstituted or substituted with a substituent.

In the general formula (C1), the "substituent" may be a functional group which may be substituted, and examples thereof include an aliphatic group, an aryl group, a heterocyclic group, a decyl group, a fluorenylene group, and an azo group. Base, decyloxy, decylamino, aliphatic oxy, aryloxy, heterocyclic oxy, aliphatic oxycarbonyl, aryloxycarbonyl, heteroepoxycarbonyl, aminomethyl decyl, aliphatic sulfonyl, Arylsulfonyl, heterocyclosulfonyl, aliphatic sulfonyloxy, arylsulfonyloxy, heterocyclosulfonyloxy, sulfonyl, aliphatic sulfonamide, arylsulfonamide Base, heterocyclic sulfonylamino group, amine group, aliphatic amine group, heterocyclic amine group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, hetero oxycarbonylamine group, aliphatic sulfinyl group, aromatic Thiothiol group, aliphatic thio group, heterocyclic thio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, aminomethionine group, amine sulfonamide group, A halogen atom, an amine sulfonylaminomethyl sulfonyl group, an aminomethionyl sulfonyl sulfhydryl group, a dialiphatic oxyphosphinyl fluorenyl group, a diaryloxyphosphinyl fluorenyl group or the like.

In the formula (C1), R _{C 1} represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a decyl group, and a fat. Alkoxy, aryloxy, decyloxy, aminomethyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyl decylamino, aminocarbamimidyl, sulfonamide Base, aliphatic oxycarbonylamine, aryloxycarbonylamine, aliphatic sulfonamide, arylsulfonamide, aliphatic thio, aliphatic sulfonamide, arylthio, aliphatic sulfonyl An arylsulfonyl group, an amine sulfonyl group, a sulfo group, a quinone imine group or a heterocyclic thio group.

Examples of the halogen atom represented by R _{C 1} include a fluorine atom, a chlorine atom, and a bromine atom.

The aliphatic group represented by R _{C 1} may be unsubstituted or substituted, may be saturated or unsaturated, or may be cyclic, and is preferably a fat having a total carbon number of 1 to 15 Family base. For example, methyl, ethyl, vinyl, allyl, vinyl, isopropenyl, 2-ethylhexyl and the like.

The aryl group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an aryl group having 6 to 16 total carbon atoms, more preferably an aryl group having 6 to 12 total carbon atoms. For example, phenyl, 4-nitrophenyl, 2-nitrophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 2,4-dimethylphenyl, 2-methylphenyl , 4-methoxyphenyl, 2-methoxyphenyl, 2-methoxycarbonyl-4-nitrophenyl, and the like.

The heterocyclic group represented by R _{C 1} may be saturated or unsaturated, more preferably a heterocyclic group having 1 to 15 total carbon atoms, more preferably a heterocyclic group having 3 to 10 total carbon atoms. For example, a 3-pyridyl group, a 2-pyridyl group, a 2-pyrimidinyl group, a 2-pyrazinyl group, a 1-piperidinyl group, etc. are mentioned. Further, it may have a more substituent.

The aminomethyl fluorenyl group represented by R _{C 1} may be unsubstituted or substituted, preferably an aminomethyl fluorenyl group having a total carbon number of 1 to 16, more preferably 1 to 12 total carbon atoms. Aminomethyl thiol. For example, an aminomethyl fluorenyl group, a dimethylaminomethyl fluorenyl group, a dimethoxyethylaminocarbamyl group, and the like.

The aliphatic oxycarbonyl group represented by R _{C 1} may be unsubstituted or substituted, or may be either saturated or unsaturated, or may be cyclic, preferably having a total carbon number of 2 to 16. The aliphatic oxycarbonyl group is more preferably an aliphatic oxycarbonyl group having 2 to 10 carbon atoms in total. For example, methoxycarbonyl, butoxycarbonyl, and the like.

The aryloxycarbonyl group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an aromatic oxycarbonyl group having 7 to 17 total carbon atoms, more preferably an aryloxycarbonyl group having 7 to 15 total carbon atoms. . For example, phenoxycarbonyl and the like.

The thiol group represented by R _{C 1} may be an aliphatic carbonyl group or an arylcarbonyl group, and may represent an aliphatic carbonyl group, or may have a substituent, and may represent an arylcarbonyl group, or may have a substituent. It may be either saturated or unsaturated, and may be cyclic. The fluorenyl group is preferably a fluorenyl group having 2 to 15 total carbon atoms, more preferably 2 to 10 fluorenyl groups. For example, an ethyl fluorenyl group, a propyl fluorenyl group, a benzoinyl group, etc. are mentioned. Further, it may have a more substituent.

The aliphatic oxy group represented by R _{C 1} may be unsubstituted or substituted, may be saturated or unsaturated, or may be cyclic. The aliphatic oxy group is preferably an aliphatic oxy group having 1 to 12 carbon atoms in total, and more preferably an aliphatic oxy group having 1 to 10 carbon atoms in total. For example, a methoxy group, an ethoxyethoxy group, a phenoxyethoxy group, a thiophenoxyethoxy group, etc. are mentioned.

The aryloxy group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an aryloxy group having 6 to 18 carbon atoms in total, and more preferably an aryloxy group having 6 to 14 carbon atoms in total. . For example, a phenoxy group, a 4-methylphenoxy group, etc. are mentioned.

The decyloxy group represented by R _{C 1} may be unsubstituted or substituted, preferably a total of 2 to 14 carbon atoms in the total carbon number, more preferably 2 to 10 carbon atoms in total. . For example, an ethoxylated group, a methoxyethyl oxy group, a phenoxy group, etc. are mentioned.

The aminomethyl methoxy group represented by R _{C 1} may be unsubstituted or substituted, preferably an aminomethyl methoxy group having a total carbon number of 1 to 16, more preferably a total carbon number of 1~ 12 aminomethylmercaptooxy groups. For example, a dimethylaminomethyl methoxy group, a diisopropyl amine methyl methoxy group, etc. are mentioned.

The heterocyclic oxy group represented by R _{C 1} may be unsubstituted or substituted, preferably a heterocyclic oxy group having 1 to 15 total carbon atoms, more preferably 3 to 10 total carbon atoms. Epoxy group. For example, 3-furanyloxy group, 3-pyridyloxy group, N-methyl-2-piperidinyloxy group, etc. are mentioned.

The aliphatic oxycarbonyloxy group represented by R _{C 1} may be unsubstituted or substituted, may be saturated or unsaturated, or may be cyclic. The aliphatic oxycarbonyloxy group is preferably an aliphatic oxycarbonyloxy group having 2 to 16 total carbon atoms, more preferably an aliphatic oxycarbonyloxy group having 2 to 10 total carbon atoms. For example, a methoxycarbonyloxy group, a t-butoxycarbonyloxy group, etc. are mentioned.

The N-alkyl decylamino group represented by R _{C 1} may be unsubstituted or substituted, preferably N-alkylnonylamino group having a total carbon number of 3 to 15, more preferably a total carbon number 3 to 12 N-alkyl guanamine groups. For example, N-methyl decylamino group, N-ethoxyethyl benzoguanamine group, N-methylmethoxyethyl amide group, etc. are mentioned.

The aminocarbamamine group represented by R _{C 1} may be unsubstituted or substituted, preferably an aminocarbamamine group having a total carbon number of 1 to 16, more preferably a total carbon number of 1~ 12 aminocarbamamine groups. For example, N,N-dimethylaminocarbamylamino group, N-methyl-N-methoxyethylaminocarbamylamino group, etc. are mentioned.

The amine sulfonamide group represented by R _{C 1} may be unsubstituted or substituted, preferably a sulfonamide group having a total carbon number of 0 to 16, more preferably a total carbon number of 0 to 12 Amine sulfonamide. For example, N,N-dimethylamine sulfonamide group, N,N-diethylamine sulfonamide group, etc. are mentioned.

The aliphatic oxycarbonylamine group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an aliphatic oxycarbonyl group having 2 to 15 total carbon atoms, more preferably a total carbon number of 2~ 10 aliphatic oxycarbonylamine groups. For example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, etc. are mentioned.

The aryloxycarbonylamino group represented by R _{C 1} may be unsubstituted or substituted, preferably an aryloxycarbonyl group having 7 to 17 total carbon atoms, more preferably 7 to 15 total carbon atoms. Aryloxycarbonylamino group. For example, a phenoxycarbonylamino group, a 4-methoxycarbonylamino group, etc. are mentioned.

The aliphatic sulfonamide group represented by R _{C 1} may be unsubstituted or substituted, may be saturated or unsaturated, or may be cyclic. The aliphatic sulfonamide group is preferably an aliphatic sulfonamide group having a total carbon number of 1 to 12, more preferably an aliphatic sulfonamide group having a total carbon number of 1 to 8. For example, a methanesulfonamide group, a sulfonamide group, etc. are mentioned.

The arylsulfonylamino group represented by R _{C 1} may be unsubstituted or substituted, preferably an arylsulfonylamino group having a total carbon number of 6 to 15, more preferably a total carbon number of 6~ 12 arylsulfonylamino groups. For example, a benzenesulfonylamino group, a 4-toluenesulfonylamine group, etc. are mentioned.

The aliphatic thio group represented by R _{C 1} may be unsubstituted or substituted, may be saturated or unsaturated, or may be cyclic. The aliphatic sulfur group is preferably an aliphatic sulfur group having 1 to 16 carbon atoms in total, and more preferably an aliphatic sulfur group having 1 to 10 carbon atoms in total. For example, a methylthio group, an ethylthio group, an ethoxyethylthio group, etc. are mentioned.

The arylthio group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an arylthio group having 6 to 22 total carbon atoms, more preferably an arylthio group having 6 to 14 total carbon atoms. . For example, a phenylthio group, a 2-t-butylphenylthio group, etc. are mentioned.

The aliphatic sulfonyl group represented by R _{C 1} may be an unsubstituted or substituted group, preferably an aliphatic sulfonyl group having a total carbon number of 1 to 15, more preferably a total carbon number of 1 to 8 An aliphatic sulfonyl group. For example, a methylsulfonyl group, a butyl sulfonyl group, a methoxyethanesulfonyl group, etc. are mentioned.

The arylsulfonyl group represented by R _{C 1} may be unsubstituted or substituted, preferably an arylsulfonyl group having a total carbon number of 6 to 16, more preferably a total carbon number of 6 to 12 The arylsulfonyl group. For example, a benzenesulfonyl group, a 4-t-butylbenzenesulfonyl group, a 4-toluenesulfonyl group, a 2-toluenesulfonyl group, etc. are mentioned.

The amine sulfonyl group represented by R _{C 1} may be unsubstituted or substituted, preferably a sulfonyl group having a total carbon number of 0 to 16, more preferably an amine having a total carbon number of 0 to 12 Sulfonyl. For example, an aminesulfonyl group, a dimethylaminesulfonyl group, etc. are mentioned.

The quinone imine group represented by R _{C 1} may be further subjected to condensed ring, preferably a total of 3 to 22 fluorene imine groups, more preferably 3 to 15 fluorene imino groups. . For example, a quinone imino group, a ruthenium terephthalate group, etc. are mentioned.

The heterocyclic thio group represented by R _{C 1} may be unsubstituted or substituted, and is a 5 to 7 membered ring, preferably a heterocyclic thio group having 1 to 20 total carbon atoms, more preferably a total carbon. A number of 1 to 12 heterocyclic thio groups. For example, a 3-furylthio group, a 3-pyridylthio group, etc. are mentioned.

In the general formula (C1), Z _{C 1} represents a non-metal atomic group necessary for forming a 6-membered ring together with a carbon atom, and the four Z _{C 1 's} may be the same or different. The 6-membered ring formed may be either an aryl ring or a heterocyclic ring, or may be condensed, and the ring having a condensed ring may have a more substituent. For example, the 6-membered ring may be a benzene ring, a pyridine ring, a cyclohexene ring, a naphthalene ring or the like, and a form of a benzene ring is suitable.

In the formula (C1), M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. For example, the M may be exemplified by 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 ,} etc., are preferably in the form of VO, Zn, Mn, Cu, Ni, and Co.

In the 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). The cn of the four positions in the molecule may be the same or different, and one of cn represents an integer of 1 to 5, and in the case where the number of cn in the molecule is several, several R _{C 1} may be the same or different.

In addition, cr1, cr2, cr3 and cr4 represent 0 or 1, satisfying cr1+cr2+cr3+cr4 1. Among them, cr1+cr2+cr3+cr4 is preferably in the form of 3 or 4.

Among the dyes of the formula (C1), a dye represented by the following formula (C1-1) (related to the phthalocyanine dye of the present invention) is preferred because it can more effectively achieve the effects of the present invention.

In the above formula (C1-1), R _{C 2} represents a substituent, and the substituent is preferably a functional group which may be substituted, and examples thereof include the functional groups exemplified in the term "substituent". More preferably an aliphatic group, an aryl group, a heterocyclic group, an N-alkyl decylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a heteroepoxycarbonyl group, Aminomethyl fluorenyl, aliphatic sulfonyl, sulfonyl, aliphatic sulfonylamino, arylsulfonylamino, aliphatic amine, arylamine, aliphatic oxycarbonylamine, aryloxycarbonyl Amine group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aminocarbamoyl group, amine sulfonamide group, halogen atom, more preferably aliphatic group, N-alkyl group An amine group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an aliphatic thio group, an arylthio group, a sulfo group, a carboxyl group, or a halogen atom.

In the formula (C1-1), cp represents an integer of 0 to 4, preferably 0 or 1. However, cp+cr1, cp+cr2, cp+cr3, and cp+cr4 all represent integers from 0 to 4. There are several cases where R _{C 2} is present in the molecule, and several R _{C 2} may be the same or different.

Further, in the general formula (C1-1), R _{C 1} , M, cm, cn, and cr1, cr2, cr3 and cr4 are synonymous with the case of the general formula (C1), and the preferred embodiment is also identical.

Among the dyes of the formula (C1-1), a dye represented by the following formula (C1-2) (related to the phthalocyanine dye of the present invention) is preferred because it can more effectively achieve the effects of the present invention.

In the general formula (C1-2), R _{C 1} , R _{C 2} , M, cm, cn and cr1, cr2, cr3 and cr4 are respectively the same as the general formula (C1) and the general formula (C1-1). For the same meaning, the preferred form is also the same. Further, cq in the formula (C1-2) represents 0 or 1. Further, the phthalocyanine backbone is on the outer side of the tetraporphyrin backbone, has a structure in which four benzene rings are condensed, and has a site (carbon atom) to which four substituents can be attached to each benzene ring, and the formula (C1) -2) is bonded to a hydrogen atom at two positions (β-position) far from the porphyrin backbone of each benzene ring.

In the general formula (C1-2), the R _{C 1} is preferably a halogen atom, an aliphatic group, a cyano group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, or an aromatic group, based on the viewpoint that the effect of the present invention can be more effectively achieved. Oxycarbonyl, hydroxyl, aliphatic oxy, aminomethyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, aminocarbamimidyl, amine sulfonamide, aliphatic oxycarbonylamine, fat a sulfonamide group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, a quinone imine group or a sulfo group, Preferably, it is an aliphatic group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbonyloxy group, an aminomethylamino group, an amine sulfonamide group, an aliphatic oxycarbonyl group. a form of an amine group, an aliphatic sulfonamide group, an arylsulfonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, an aminesulfonyl group, a quinone imine group or a sulfo group, preferably an amine group Sulfhydryl, aliphatic oxycarbonyl, aliphatic oxy, aliphatic oxycarbonyloxy, aminocarbamimidyl, aliphatic oxycarbonylamine, arylsulfonyl, quinone or aliphatic sulfonate The form of the base.

Similarly, the R _{C 2} is preferably an aliphatic group, an N-alkyl guanylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, or a fat, based on the viewpoint that the effect of the present invention can be more effectively achieved. The form of a group of a thiol group, an arylthio group, a sulfo group, a carboxyl group or a halogen atom is more preferably in the form of an aliphatic group or a halogen atom. Similarly, the cq is preferably in the form of 0 based on the viewpoint that the effect of the present invention can be further achieved. Similarly, based on the viewpoint that the effect of the present invention can be further attained, the M is preferably in the form of VO, Mn, Co, Ni, Cu, Zn or Mg, more preferably in the form of VO, Co, Cu or Zn, and most preferably In the form of Cu, in addition, cm is preferably in the form of 0, cn is preferably in the form of 1 or 2, and cn is more preferably in the form of 1.

In view of the fact that the effect of the present invention can be further attained, in the formula (C1-2), the R _{C 1} is preferably a halogen atom, an aliphatic group, a cyano group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, or an aromatic group. Oxycarbonyl, hydroxyl, aliphatic oxy, aminomethyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, aminocarbamimidyl, amine sulfonamide, aliphatic oxycarbonylamine, fat a form of a sulfonamide group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, an oxime imide group or a sulfo group, M is preferably in the form of VO, Co, Cu or Zn, the cq is preferably 0, the cm is preferably in the form of 0, and the cn is preferably in the form of 1, and the R _{C 1 is more} preferably aliphatic. Base, aminomethyl decyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, aliphatic oxy group, aliphatic oxycarbonyloxy group, aminomethionine group, amine sulfonamide group, aliphatic oxycarbonyl group, fat a form of a sulfonamide group, an arylsulfonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, an aminesulfonyl group, a quinone imine group or a sulfo group, and the M is more preferably VO, Co or Cu. Or the form of Zn, the cq is more Is 0, the 0 cm more preferably is in the form of, more preferably is in the form of the 1 cn.

In particular, similarly, from the viewpoint of the effects of the present invention, the R _{C 1 is} preferably an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, an aminocarbamoyl group, an aliphatic oxycarbonyl group, or a fat. The form of a sulfonyl group, an arylsulfonyl group or a quinone imine. The M is preferably in the form of Cu, and the cq is preferably 0, and the cm is preferably in the form of 0, and the cn is preferably in the form of 1.

Specific examples of the dyes (dyes) represented by the general formulae (C1) to (C1-2) (exemplary compounds C'-1 to C'-59) are shown below. However, the invention is not limited by these specific examples.

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, and the synthesis of the dye C-1 of the exemplified compound will be described in detail.

(Synthesis of Intermediate) 100 ml of dimethyl hydrazine was added to 25.0 g (0.144 mol) of 3-nitro-p-phthalocyanine and 34.7 g (0.159 mol) of thio-propionic acid at room temperature. After stirring 2-ethylhexyl ester. Further, 17.0 g of sodium carbonate was added in a small amount each time, and after completion of the addition, the mixture was stirred at room temperature for 2 hours, and the reaction was terminated. The obtained reaction solution was poured into 500 ml of water, and then extracted with 300 ml of ethyl acetate. Then, 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.

To 50 g (0.144 mol) of the intermediate A and 1.0 g of sodium tungstate, 200 ml of ethanol and 1 ml of acetic acid were added, followed by heating and stirring. Next, 36.5 g (0.288 mol) of a 30% aqueous hydrogen peroxide solution was dropped into the solution. After completion of the dropwise addition, the reaction was further heated at 65 to 70 ° C for 4 hours, and the reaction was terminated. After completion of the reaction, 10 g of sodium sulfite and 700 ml of water were added by cooling at room temperature, and the mixture was stirred at room temperature to precipitate crystals. This crystal was filtered, washed with water, recrystallized from 200 ml of methanol, and purified to obtain 32.5 g of Intermediate B (yield 60%).

(Synthesis of Pigment C-1) In this manner, 150 ml of butanol was added to the obtained 34.4 g (0.081 mol) of intermediate B and 6.7 g (0.070 mol) of ammonium carbonate at 50 ° C. Heat and stir. Next, 4.7 g (0.035 mol) of copper (II) chloride was added to the solution, and the mixture was heated to 100 to 110 ° C and stirred for 7 hours. After completion of the reaction, the butanol was distilled off, and the residue was dissolved in chloroform, and separated and purified by a cerium oxide gel column chromatography (eluent: chloroform/methanol = 10/1) to obtain 25 g. Powdered Pigment C-1 (yield 72.7%).

The maximum absorption wavelength (λ _{m a x} ) and the molar absorption coefficient (ε) of the obtained dye in ethyl acetate were measured by using a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation, Japan). Thereafter, the maximum absorption wavelength λ _{m a x} was 706.8 nm, and the molar absorption coefficient ε was 55,600.

Further, other exemplary compounds other than the dye C-1 can be synthesized by the same method as described above.

Next, a synthesis example of the dye (dye) represented by the above formula (C1) will be described in detail with reference to the following scheme, and the synthesis of the dye C-1 of the exemplified compound will be described in detail.

(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 the solution was cooled to 5 ° C during stirring. Further, 9 ml of a 30% aqueous hydrogen peroxide solution was added dropwise while maintaining the internal temperature at 25 °C. Further, the mixture was stirred at 30 ° C for 30 minutes, and cooled again to 5 ° C. After 15 ml of concentrated hydrochloric acid was added dropwise with stirring, 200 ml of water was further added thereto, and the mixture was stirred at 25 ° C for 1 hour. Then, the precipitated crystals were filtered, washed thoroughly with water, and dried to obtain 24.7 g of a white crystal intermediate product B (yield: 99.5%).

(Synthesis of Intermediate Products C, D and E) Next, 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 by the reaction, and refluxed. Next, 25 ml of thionium chloride was added dropwise over 10 minutes. Further, the solution was heated under reflux for 1 hour, and then concentrated under reduced pressure to give a viscous liquid. On the other hand, 10 ml of dimethylacetamide and 100 ml of acetonitrile were added to 38.0 g (0.235 mol) of diethoxyethylamine, and while stirring at 10 ° C, the viscous was dropped over 15 minutes. The liquid was kept at 15 ° C on one side. After further stirring for 30 minutes, the solution was poured into a mixed solution of 100 ml of water and 100 ml of ethyl acetate, and the ethyl acetate phase was separated, and washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and ethyl acetate was removed under reduced pressure to give an intermediate product C of a pale yellow viscous liquid.

Next, 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 under reflux, and a solution of 10 ml of sulfuric acid diluted with 40 ml of water was added dropwise thereto over 20 minutes. Then, the mixture was further heated and stirred for 30 minutes, and then cooled, and the insoluble matter was filtered. Further, 50 ml of a saturated saline solution and 100 ml of ethyl acetate were added to the obtained solution to carry out liquid separation, and then 100 ml of water was used to wash the secondary ethyl acetate phase. Further, magnesium sulfate was used to dry the ethyl acetate phase, and ethyl acetate was distilled off under reduced pressure to obtain an intermediate product D of a pale yellow viscous liquid.

Next, under stirring in a nitrogen atmosphere, 70 ml of dimethylacetamide and 15 g (0.108 mol) of potassium carbonate were added to the intermediate product D, and further stirred at 20 ° C, except for one side. 19.7 g (0.113 mol) of 3-nitro-p-phthalocyanine and maintained at 25 ° C or less. After further stirring the solution for 30 minutes, 300 ml of water was poured under stirring, and the obtained crystal was filtered, and the crystal was washed with water. The crystals obtained 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 intermediate product E (yield: 72.6%) of white crystals.

(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 in the middle of 34.4 g (0.081 mol). The product E was heated and stirred for 7 hours. Thereafter, the butanol was distilled off under reduced pressure, and the obtained solid was purified by a cerium oxide gel column chromatography to obtain 25 g of a dye C-1 powder (yield: 72.7%). Determination of the maximum absorption wavelength (λ _{m a x} ) and the molar absorption coefficient (ε) in ethyl acetate of the obtained dye by using a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation, Japan) Thereafter, the maximum absorption wavelength λ _{m a x} was 706.8 nm, and the molar absorption coefficient ε was 55,600.

Further, the other exemplary compound can be synthesized in the same manner by changing to a desired compound by a dye according to the purpose.

a quinophthalone dye represented by the formula (1)

The compound represented by the following formula (1) is a compound which simultaneously satisfies the high light resistance and high heat resistance which have never been obtained, and if necessary, can be freely dissolved in water or a solvent.

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ . S represents a sulfur atom, and R ⁵ represents an alkyl group which contains an oxygen atom in the form of an ether bond, and may have a hydroxyl group as a substituent. R ⁶ represents an alkyl group having a hydroxyl group. However, at least one of R ¹ to R ⁴ represents -S-R ⁵ .

Further, in the formula (1), R ⁵ is preferably an alkyl group having 2 to 16 carbon atoms in total of 1 to 6 oxygen atoms in the form of an ether bond, and R ² and R ³ are preferably -S- R ⁵ , R ¹ and R ⁴ are preferably a hydrogen atom or a halogen atom. Further, one of the structural features of the quinophthalone-based dye represented by the formula (1) of the present invention is at least one of an alkyl group having an ether bond on the benzene ring of the quinone side of the quinacridone backbone.

In the above formula (1), the halogen atom represented by R ¹ to R ⁴ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.

When 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, especially in the form of an ether bond 2~ The alkyl group having 4 to 12 carbon atoms in total is particularly desirable. Wherein, the alkyl group may be a straight chain or a branched chain, or may have a moiety forming a ring.

Examples of the R ⁵ include 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, methoxyethoxyethyl, and ethoxyethoxyethyl. , 3-ethoxypropyl, 2-ethoxy-1-methylpropyl, 3-propoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 4-methoxy Butyl, 4-butoxybutyl, 6-methoxyhexyl, 6-ethoxyhexyl, 2,3-dimethoxypropyl, 2,3-diethoxypropyl, 2, 3-dipropoxypropyl, 2,3-diisopropoxypropyl, 2,3-dibutoxypropyl, 2,3-dicyclohexyloxypropyl, 2,3-di ( 2-ethoxyethoxy)propyl, 2,3-bis(2-ethoxyethoxyethoxy)propyl, 2-(2-ethoxyethoxyethoxy)-3 -(2-propoxyethoxyethoxy)propyl, 2-(2-ethoxyethoxy)-3-(2-ethoxyethoxyethoxy)propyl, 2, 3-bis(1,3-dioxol-2-ylethoxy)propyl, (2,2'-dimethyl-1,3-dioxolane-4-indole Methyl, (2-ethyl-2-methyl-1,3-dioxolan-4-indolyl)methyl, (2,2'- Diethyl-1,3-dioxol-4-indolyl)methyl, (2-propyl-1,3-dioxolan-4-indolyl)methyl, (2 , 2'-dipropyl-1,3-dioxolan-4-indolyl)methyl, (2-butyl-1,3-dioxol-4-yl)A , (2-pentyl-1,3-dioxolan-4-indolyl)methyl, 2-(tetrahydroindenyloxy)ethyl, 2-(1,3-dioxa) Cyclopentane-2-mercaptomethyloxy)ethyl, 2-(1,3-dioxolan-2-ylethyloxy)ethyl, 2-(1,3-di) Oxolane-2-mercaptoethyloxy)propyl, 2-(1,3-dioxolan-2-ylmethyloxy)propyl, 2-(tetrahydropyridyl)喃-2-methyloxy)ethyl, 2-(1,3-dioxan-2-indolylethyloxy)ethyl, 2-(1,3-dioxan-2-indoleyl Ethyloxy)propyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, 2-(hydroxyethoxy)propyl, 2-hydroxy-3-methoxypropyl, 2- Hydroxy-3-ethoxypropyl, 2-hydroxy-3-butoxypropyl, 2-hydroxy-3-(ethoxyethoxy)propyl, and the like.

When R ¹ to R ⁴ are -S-R ⁶ , R ⁶ is preferably an alkyl group having 2 to 12 carbon atoms and having a total carbon number of 1 to 4 hydroxyl groups, and particularly containing 1~ based on the optical density of the dye. The total carbon number of the three hydroxyl groups is preferably from 2 to 8 alkyl groups.

Examples of the R ⁶ include 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-1-methylpropyl, 4-hydroxyl Butyl, 2,3,4-trihydroxybutyl, 2,3,4,5-tetrahydroxypentyl, 6-hydroxyhexyl, 11-hydroxyundecyl, 12-hydroxydodecyl and the like.

In the quinophthalone type dye and the tautomer thereof represented by the formula (1), the total number of oxygen atoms in the ether bond contained in R ¹ to R ⁴ is preferably from 1 to 16, based on solubility and pigment optics. The concentration point of view is especially ideal for 2~12.

Further, the total number of oxygen atoms contained in R ¹ to R ⁴ contained in the oxygen atom contained in the hydroxyl group is preferably 2 to 24, particularly preferably 3 to 16.

Further, from the viewpoint of the dye absorption property, the quinophthalone-based dye and the tautomer thereof represented by the formula (1) are preferably those having a structure in which -S-R ⁵ has been introduced in R ² and/or R ³ .

Though the quinophthalone-based dye represented by the formula (1) (the following compound (1) has a tautomer of a structure such as the compound (1') and (1")) shown below, Isomers are also included in the scope of the invention.

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

(Method for Producing Quinone-Based Pigment of the Formula (1)) Hereinafter, a method for producing a quinophthalone-based dye (quinacridone compound) represented by the formula (1) of the present invention will be described. An overview of the representative manufacturing methods (first and second manufacturing methods) is as follows.

First manufacturing method

The first manufacturing method is to first use 1 to 16 moles of the base compound (B) in an organic solvent with respect to 1 mole of the following compound (A) to make the following compounds with 1 to 8 moles; (B), the reaction is carried out at 20 to 200 ° C for 1 to 8 hours.

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

HS-R ⁵ (B)

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

In this case, N-methylpyrrolidone, DMI, cyclobutyl hydrazine, DMF, DMAC, toluene, ethyl acetate or the like is used as the organic solvent, and potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or the like is used as the alkali compound. After the reaction, the reaction solution is poured into water, extracted with an organic solvent such as ethyl acetate, washed with water, and concentrated, and if necessary, purified by a column chromatography to obtain the desired formula (1). The quinacridone dye shown.

Second manufacturing method

The second production method is to first use 1 to 16 moles of the base compound (B) in an organic solvent with respect to 1 mole of the following compound (A) to make it with 1 to 8 moles of the following compound ( C), the reaction is carried out at 20 to 200 ° C for 1 to 24 hours.

HS-R ⁶ (C)

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

Next, the solution was poured into water, neutralized with dilute hydrochloric acid or acetic acid, etc., filtered, and washed with water to give the following compound (D). At this time, the organic solvent used for the reaction is the same as that of the base compound, and is used by the user using the first production method.

[In the compound (D), R ⁷ and R ⁸ represent the same as the compound (A), and R ⁶ represents the same as the formula (1). In addition, a-c represents 0~3, b represents 0~3, and c represents 1~4. However, (a-c)+c+b=4. ]

Next, the compound (D) is subjected to 1~ at a temperature of 20 to 200 ° C by using 1 to 24 moles of the alkali compound in an organic solvent and simultaneously using 1 to 24 moles of the following compound (E). After 24 hours of reaction, the quinophthalone type dye represented by the formula (1) of the object can be obtained. The organic solvent is used in the same manner as the base compound in the first production method.

Z-R ⁹ (E)

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

Further, the compound (D) and the compound (E) can be reacted with a two-phase system using a phase transfer catalyst and an aqueous alkali solution in an organic solvent, and a quinone represented by the formula (1) can be produced in the same manner. Ketone pigment. The organic solvent used in the reaction is the same as that used by the first manufacturing method. Examples of the aqueous alkali solution include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. Further, as the phase transfer catalyst, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogensulfate or the like can be used.

Further, in the case where the R ⁶ of the compound (D) is an alkyl group having an α,β-dihydroxy group, dehydration reflux is carried out by using an acid catalyst such as the following compound (F) and p -toluenesulfonic acid in an organic solvent; The quinophthalone type dye represented by the formula (1) of the object can be obtained.

[In the compound (F), R ^{1 0} represents a hydrogen atom or an alkyl group, R ^{1 1} represents an alkyl group, and R ^{1 0} and R ^{1 1} may be bonded to each other to form a ring. ]

In the dye-containing negative-type curable composition of the present invention, one or several kinds of the dyes represented by the formula (A) and one of the quinophthalone-based dyes represented by the formula (1) can be used in combination. In addition, it is possible to further combine and use a conventional xanthene dye or a triarylmethane dye, if necessary.

Although the total concentration of the dye-containing negative-type hardenable composition of the present invention differs depending on the molecular weight and the molar absorptivity, it is preferably from 0.5 to 80% by mass based on the total solid content of the composition. More preferably, it is 10 to 60% by mass.

In addition, when the dye represented by the formula (A) and the quinophthalone-based dye represented by the formula (1) are mixed and then toned, the amount of the dye added in a small amount to be added is added. It is preferably at least 10% or more of all the amount of pigment added. More preferably 10~80%.

The dye according to the present invention is applied to a solid-state imaging device such as a CCD or a CMOS, or a color filter for recording and reproducing color images of a display such as an LCD or a PDP, or for producing such a color filter. a hardening composition. In the case of producing a color filter, it is possible to use two or more kinds of the dyes of the present invention, that is, the dyes represented by the formula (C1) and the quinophthalone-based dyes represented by the formula (1). Any one of the forms of the coloring matter can be produced, and, for example, it can be produced by appropriately setting the following steps: preparing a curable composition containing the dye of the present invention, and preparing the prepared composition. Coating or the like, and forming a pattern by exposure, development, or the like.

(C) Photopolymerization initiator

Next, the photopolymerization initiator will be described. The photopolymerization initiator is contained in the dye-containing negative-type curable composition of the present invention together with a radical polymerizable monomer to be described later. The photopolymerization initiator is not particularly limited as long as it polymerizes the radical polymerizable monomer, but is preferably selected based on characteristics, initial efficiency, absorption wavelength, availability, cost, and the like. .

The photopolymerization initiator may, for example, be at least one active halide selected from a halomethyl oxadiazole compound and a halomethyl- s -triazole compound, a 3-aryl-substituted coumarin compound, and Luo A phenanthrene dimer, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron coordination compound, a salt thereof, an anthraquinone compound, and the like.

The active halide of the halomethyl oxadiazole compound may, for example, be a 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound disclosed in Japanese Patent Publication No. Sho 57-6096. Or 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-( p -cyanostyryl)-1,3,4 - Oxadiazole, 2-trichloromethyl-5-( p -methoxystyryl)-1,3,4-oxadiazole, and the like.

The active halide of the halomethyl- s -triazole-based compound may, for example, be a vinyl halomethyl- s -triazole compound disclosed in Japanese Patent Publication No. Sho 59-1281, which is disclosed in Japanese Patent Laid-Open No. 2-(Naphtho-1-indenyl)-4,6-halomethyl- s -triazole compound and 4-( p -aminophenyl)-2,6-dihalo-methyl, 53-133428 A s -triazine compound or the like.

The active halide of the halomethyl- s -triazole compound, specifically, 2,4-bis(trichloromethyl)-6- p -methoxystyryl- s -triazine, 2,6-bis(trichloromethyl)-4-(3,4-methylenedihydroxyphenyl)-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-indenyl) -4,6-bistrichloromethyl- s -triazine, 2-(4-methoxynaphtho-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2- (4-ethoxynaphthyl-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(4-butoxynaphthyl-1-indenyl)-4,6 -bistrichloromethyl- s -triazine, 2-[4-(2-methoxyethyl)naphtho-1-indenyl]-4,6-bistrichloromethyl- s -triazine, 2-[4-(2-ethoxyethyl)naphtho-1-indenyl]-4,6-bistrichloromethyl- s -triazine, 2-[4-(2-butyl) Oxyethyl)naphtho-1-indenyl]-4,6-bistrichloromethyl- s -triazine, 2-(2-methoxynaphthen-1-yl)-4,6- Bis-trichloromethyl- s -triazine, 2-(6-methoxy-5-methylnaphtho-2-indenyl)-4,6-bistrichloromethyl- s -triazine, 2- (6-methoxynaphtho-2-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(5-methoxynaphthen-1-yl)-4,6 -bistrichloromethyl- s -triazine, 2-(4,7-dimethoxynaphthyl-1-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-( 6-ethoxynaphtho-2-indenyl)-4,6-bistrichloromethyl- s -triazine, 2-(4,5-dimethoxynaphthen-1-yl)-4 ,6-bistrichloromethyl- s -triazine, 4-[ p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(trichloromethyl) -s - Triazine, 4-[ o -methyl- p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ p- N,N-bis(chloroethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -methyl- p- N,N-di( Chloroethyl)amine benzene ] -2,6-bis (trichloromethyl) - s - triazine, 4- (p -N- chloroethyl aminophenyl) -2,6-bis (trichloromethyl) - s - triazine , 4-( p -N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-[ p -N,N-di(phenyl)amine Phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-( p -N-chloroethylcarbonylaminephenyl)-2,6-di(trichloromethyl) -s - Triazine, 4-[ p -N-( p -methoxyphenyl)carbonylamine phenyl]-2,6-di(trichloromethyl) -s -triazine, 4-[ m -N,N - bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -bromo- p- N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -chloro- p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]- 2,6-bis(trichloromethyl) -s -triazine, 4-[ m -fluoro- p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(three Chloromethyl) -s -triazine, 4-[ o -bromo- p- N,N-bis(ethoxycarbonylmethyl)aminephenyl]-2,6-di(trichloromethyl) -s - triazine, 4- [o - - p -N, N- bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) - s - triazine, 4- [o - fluoro - p -N, N- Bis(ethoxycarbonylmethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -bromo- p- N,N-bis(chloroethyl)amine Phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ o -chloro- p- N,N-bis(chloroethyl)aminephenyl]-2,6-di (trichloromethyl) -s -triazine, 4-[ o -fluoro- p- N,N-bis(chloroethyl)aminephenyl]-2,6-di(trichloromethyl) -s - Triazine, 4-[ m -bromo- p- N,N-bis(chloroethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-[ m -chloro - p- N,N-bis(chloroethyl)amine phenyl]-2,6-di(trichloromethyl) -s -triazine, 4-[ m -fluoro- p- N,N-di( Chloroethyl)amine phenyl]-2,6-bis(trichloromethyl) -s -triazine, 4-( m -bromo- p -N-ethoxycarbonylmethylamine phenyl)-2,6- Bis(trichloromethyl) -s -triazine, 4-( m -chloro- p -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -fluoro- p -N-B Oxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( o -bromo- p -N-ethoxycarbonylmethylamine phenyl)-2,6-di (trichloromethyl) -s -triazine, 4-( o -chloro- p -N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4 -( o -fluoro- p -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -bromo- p -N-chloroethylamine Phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( m -chloro- p -N-chloroethylamine phenyl)-2,6-bis(trichloromethyl) - s -triazine, 4-( m -fluoro- p -N-chloroethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( o -bromo- p - N-chloroethylamine phenyl)-2,6-bis(trichloromethyl) -s -triazine, 4-( o -chloro- p -N-chloroethylamine phenyl)-2,6-di ( Trichloromethyl) -s -triazine, 4-( o -fluoro- p -N-chloroethylamine phenyl)-2,6-di(trichloromethyl) -s -triazine, and the like.

In addition, the photopolymerization initiator can also effectively use the TAZ series of Midori Chemical Co., Ltd. (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ- 113, TAZ-123), T series manufactured by PANCHIM Co., Ltd. (for example, T-OMS, T-BMP, T-R, T-B), and Irugacure series manufactured by Ciba Speciality Chemical Co., Ltd. (for example, Irugacure 651, Irugacure 184, Irugacure 500, Irugacure 1000, Irugacure 149, Irugacure 819, Irugacure 261), Darocure series (eg, Darocure 1173), 4,4'-bis(diethylamino)benzophenone, 2-(O-benzoquinone) )-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetamidine)-1-[9-ethyl-6-(2-methylbenzene) Mercapto)-9H-carbazole-3-indenyl]ethanone, 2-benzyl-2-ylamino-4-phenylmorphophenylpropyl ketone, 2,2'-dimethoxy 2-phenylacetophenone, 2-( o -chlorophenyl)-4,5-diphenylimidazole dimer, 2-( o -fluorophenyl)-4,5-diphenylimidazole Polymer, 2-( o -methoxyphenyl)-4,5-diphenylimidazole dimer, 2-( p -methoxy Phenyl)-4,5-diphenylimidazole dimer, 2-( p -dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethyl Oxyphenyl)-4,5-diphenylimidazole dimer, 2-( p -methylhydrothiophenyl)-4,5-diphenylimidazole dimer, benzoin isopropyl Ether, etc.

Among these, the photopolymerization initiator of the present invention is preferably a quinone compound. The lanthanide compound, for example, especially 2-(O-benzoquinone)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetamidine) 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazol-3-indenyl]ethanone is particularly preferred.

Further, for such photopolymerization initiators, a sensitizer or a photostabilizer may be used in combination.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-fluorenone, 2-bromo- 9-fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2- t -butyl-9,10-fluorene, 2, 6-Dichloro-9,10-fluorene, xanthone, 2-methylxanthone, 2-methoxyxanthone, thiazinone, 2,4-diethylxanthone, anthraquinone Pyridone, 10-butyl-2-chlorothioxanthone, benzoin, benzoin, p- (dimethylamino)phenyl- p -methylstyrylone, benzophenone, P- (dimethylamino)benzophenone, (or michlerone), p- (diethylamino)benzophenone, benzoin, or the like, or Japanese Patent Publication No. Sho 51-48516 A benzothiazole compound or the like or Tinuvin 1130, Tinuvin 400 or the like is disclosed.

In the dye-containing negative-type hardening composition of the present invention, other conventional photopolymerization initiators may be used in addition to the photopolymerization initiator.

In particular, the vicinal polyketal-uronic aldehyde compound disclosed in the specification of U.S. Patent No. 2,367,660, the alpha-carbonyl compound disclosed in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, the disclosure of which is incorporated herein by reference. U.S. Patent No. 2,448,828, the disclosure of which is incorporated herein by reference. A compound, a combination of a triaryl imidazole dimer/ p -aminophenyl ketone disclosed in the specification of U.S. Patent No. 3,549,367, the benzothiazole compound/trihalide disclosed in Japanese Patent Publication No. Sho 51-48516 A s -triazine compound or the like.

The total content of the photopolymerization initiator is preferably from 0.01 to 50% by mass, more preferably from 1 to 30% by mass, particularly preferably from 1 to 20%, based on the solid content (mass) of the radically polymerizable monomer to be described later. % is particularly ideal. When the content of the photopolymerization initiator is in the range of 0.01 to 50% by mass, the polymerization reaction can be easily carried out, and the film strength can be sufficiently improved. Further, the content of the lanthanoid compound is preferably 30% by mass or more, and more preferably 50% by mass or more based on the total amount of the photopolymerization initiator.

(D) Free polymerizable monomer

Next, the radical polymerizable monomer will be described. The radical polymerizable monomer used in the present invention is preferably a compound having at least one ethylenic double bond capable of undergoing addition polymerization and having a boiling point of 100 ° C or more under normal pressure. The negative composition of the present invention can be constituted by simultaneously containing the photopolymerization initiator or the like.

Examples of the radical polymerizable monomer include polyethylene mono(meth)acrylate, propylene glycol (meth)acrylate, (meth)acrylate, and phenoxy group (meth)acrylate. Monofunctional acrylate or methacrylate such as ethyl ester; polyethylene glycol di(meth)acrylate, trimethylolethyl tris(meth)acrylate, neopentyl glycol di(meth)acrylate An ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, Trimethylolpropane tris(propylene oxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, addition of ethylene oxide or propylene oxide to polyfunctionals such as glycerol or trimethylolethane After the alcohol, the (meth) acrylate is used; and the urethane acrylates disclosed in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and JP-A-51-37193 Published in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Polyester acrylates; is a polyfunctional epoxy resin and a mixture of acrylic (meth) acrylate, reaction product of ethylene acrylic acid esters or methacrylic esters and of these. Further, examples thereof include photopolymerizable monomers and oligomers disclosed in Japanese Unexamined Patent Publication No. 7,300-308. The radically polymerizable monomer of the present invention is preferably a polyfunctional (meth)acryl-based compound.

The content of the radical polymerizable monomer is preferably from 1 to 60% by mass, more preferably from 10 to 50% by mass, based on all the solid components in the composition. When the content of the radical polymerizable monomer is in the range of 1 to 60% by mass, the hardenability of the exposed portion is sufficient, and the elution resistance of the unexposed portion can be improved.

(E) organic solvent

When the dye-containing negative-type hardenable composition of the present invention is prepared, generally, at least one of organic solvents can be used. The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the negative-type hardenable composition containing the dye, and it is particularly preferable to consider the solubility, coatability, and stability of the alkali-soluble binder. Alternatively, in the present invention, a preferred cyclic ketone solvent is exemplified.

In the preparation of the dye-containing negative-type hardenable composition of the present invention, it is preferred to use a mixed solvent containing at least two kinds of organic solvents, and more preferably a combination of a cyclic ketone solvent and a cyclic ketone solvent. The form of a mixed solvent of an organic solvent. Further, it may be a form in which a cyclic ketone solvent is used alone.

The cyclic ketone solvent may, for example, be cyclopentanone, cyclohexanone or cycloheptanone, and particularly preferably cyclohexanone.

Preferred examples of the organic solvent other than the cyclic ketone solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl amide, isoamyl acetate, and acetic acid. Butyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, oxygen Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; methyl 3-oxypropionate, 3-oxopropionic acid alkyl esters such as ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and 3-ethoxypropionic acid Ester, ethyl 3-ethoxypropionate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl ester, methyl 2-oxy-2-methylpropanoate, 2-oxyl Ethyl 2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-carbonylbutyrate, ethyl 2-carbonylbutyrate, etc.; ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; aromatic hydrocarbons, for example, toluene, xylene, etc. .

Among them, the other organic solvent used in combination with the cyclic ketone solvent is preferably ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. Ester; especially ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate is particularly preferred.

When the cyclic ketone solvent is used in combination with another organic solvent to form a mixed solvent, the amount of the cyclic ketone solvent is preferably 40% by mass or more, and more preferably 60% by mass or more based on the total amount of the mixed solvent.

In the present invention, the concentration of all the solid components of the dye-containing negative-type hardenable composition of the present invention is preferably from 5 to 80% by mass, more preferably from 5 to 60, based on the coating property. The amount of mass % is particularly preferably 10 to 50% by mass.

Crosslinker

In the present invention, a sufficiently high-hardening film can be obtained by using a sufficient amount of a crosslinking agent. Hereinafter, the crosslinking agent will be described.

The crosslinking agent which can be used in the present invention is not particularly limited as long as it can be subjected to film hardening by a crosslinking reaction, for example, (a) an epoxy resin; (b) via a methylol group or an alkoxy group a melamine compound, a melamine compound, a glycoluril compound or a urea compound substituted with at least one functional group selected from a methoxymethyl group; (c) via a methylol group, an alkoxymethyl group and a hydrazine group A phenol compound, a naphthol compound or a hydroxy oxime compound in which at least one functional group selected by a methyl group is substituted.

The (a) epoxy resin may be any one having an epoxy group and having crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diepoxypropyl ether, and butyl. Diol diglycidyl ether, hexanediol diepoxypropyl ether, dihydroxybiphenyl diglycidyl ether, diepoxypropyl phthalate, N,N-diepoxypropyl aniline A low molecular compound containing a divalent epoxy propyl group; similarly, trimethylolpropane triepoxypropyl ether, trishydroxymethylphenol triepoxypropyl ether, TrisP-PA triepoxypropyl ether a low molecular compound containing a trivalent epoxypropyl group represented by the same; similarly, pentaerythritol tetraepoxypropyl ether, tetramethylol bisphenol A tetraepoxypropyl ether, etc. a low molecular weight compound; a low molecular compound containing a polyvalent epoxy propyl group such as dipentaerythritol pentaepoxypropyl ether or dipentaerythritol hexa-epoxypropyl ether; polyepoxypropyl (meth)acrylic acid Epoxy represented by ester, 2,2-bis(hydroxymethyl)-1-butanol, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, etc. High propyl Sub compound.

The number of hydroxymethyl, alkoxymethyl, and decyloxymethyl groups contained in the crosslinking agent (b) has been substituted, and the melamine compound is in the range of 2 to 6, a glycoluril compound, and a melamine. The case of the compound or the urea compound is 2 to 4, the case of the melamine compound is preferably 5 to 6, and the case of the glycoluril compound, the melamine diamine compound or the urea compound is preferably 3 to 4.

Hereinafter, the melamine compound, the melamine compound, the glycoluril compound, and the urea compound of (b) are collectively referred to as (b) a compound containing a methylol group, an alkoxymethyl group or a decyloxymethyl group. .

The compound containing a hydroxyl group in (b) is obtained by heating an 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 an alcohol. . The oxiranylmethyl group-containing compound of the above (b) is obtained by mixing and stirring a compound containing a methylol group (b) and hydrazine chloride in the presence of a basic catalyst.

Specific examples of the compound (b) having the substituent are listed below.

Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, 1 to 5 methylol groups, methoxymethylated compounds or mixtures thereof, hexamethoxy A compound in which one to five methylol groups of hexyl melamine, hexamethoxymethyl melamine, and hexamethylol melamine are methoxyoxymethylated or a mixture thereof.

Examples of the melamine compound include hydroxymethyl melamine, tetramethoxymethyl melamine, and hydroxymethyl melamine. Methyl-methylated compound or a mixture thereof, tetramethoxyethyl melamine, tetramethoxymethyl melamine, tetramethylol melamine ~3 hydroxymethyl groups are methoxyoxymethylated compounds or mixtures thereof.

The glycoluril compound may, for example, be a compound obtained by methoxymethylation of 1 to 3 methylol groups of tetramethylol glycoluril, tetramethoxymethyl glycoluril or tetramethylol glycoluril or A mixture thereof, a methoxymethyl group of 1 to 3 methylol groups of tetramethylol glycoluril, a mixture thereof, or a mixture thereof.

Examples of the urea compound include a compound of tetramethylol urea, tetramethoxymethyl urea, hydroxymethyl group of 1,4-hydroxymethyl urea, methoxymethylated or a mixture thereof, and four Methoxyethyl urea and the like.

The compounds of these (b) may be used singly or in combination.

The crosslinking agent of (c), that is, the phenol compound, naphthol compound or hydroxy hydrazine compound substituted with at least one substituent selected by a methylol group, an alkoxymethyl group and a fluorenyloxymethyl group is the same In the case of the crosslinking agent (b), the miscibility with the surface coating photoresist is suppressed by thermal crosslinking while further increasing the film strength. Hereinafter, these compounds are collectively referred to as compounds related to (c) (containing a methylol group, an alkoxymethyl group or a decyloxymethyl group).

The number of hydroxymethyl, decyloxymethyl or alkoxymethyl groups contained in the crosslinking agent (c) is at least two per molecule, based on the viewpoint of thermal crosslinkability and preservation stability. It is preferred to be a compound in which all of the 2-position and 4-position of the naphthol compound of the backbone are substituted. Further, the naphthol compound and the hydroxyquinone compound which are the backbone are preferably compounds which are substituted at all ortho and para positions of the OH group. The 3- or 5-position of the phenol compound may be unsubstituted or may have a substituent.

In addition to the ortho position of the OH group, the naphthol compound may be unsubstituted or may have a substituent.

The compound containing a methylol group according to (c) is used as a raw material by using a compound having a hydrogen atom at the 2- or 4-position of the phenolic OH group as sodium hydroxide, potassium hydroxide, ammonia, and tetraoxane. It is obtained by reacting with formalin in the presence of a basic catalyst such as a hydrazine hydroxide.

The alkoxymethyl group-containing compound of the above (c) is subjected to a methylol group-containing compound according to (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid in an alcohol. Heated up.

The oxime-containing methyl group-containing compound of the above (c) is obtained by reacting a compound containing a methylol group (c) with ruthenium chloride in the presence of a basic catalyst.

The backbone compound of the crosslinking agent (c) may, for example, be an unsubstituted phenol compound, a naphthol, a hydroxy hydrazine compound or the like in the ortho or para position of the phenolic OH group. For example, various isomeric forms of phenol and cresol may be used. Bisphenol, 4,4'-dihydroxyl, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A, etc. Biphenyl, TrisP-PA (manufactured by Honshu Nippon Chemical Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyindole, and the like.

Specific examples of the crosslinking agent (c) include, for example, trishydroxymethylphenol, tris(methoxymethyl)phenol, and 1 to 2 methylol groups of trimethylolphenol. a methoxymethylated compound, a methoxymethylated compound of oxymethylated compound, trimethylol-3-methylphenol, tris(methoxymethyl)-3-cresol, 2 , dimethylol cresol such as 6-dimethylol-4-methylphenol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A 1~3 a methoxymethylated compound, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4'-dihydroxybiphenyl, TrisP-PA a methoxymethylated compound of hexamethylol, a hexamethoxymethyl group of TrisP-PA, a hydroxymethyl group of hexamethylol of TrisP-PA, bishydroxymethylnaphthalene Alcohol, etc.

Further, examples of the hydroxy hydrazine compound include 1,6-dihydroxymethyl-2,7-dihydroxyindole and the like, and a compound containing a decyloxymethyl group, for example, a hydroxymethyl group-containing compound A compound in which a part or all of a methylol group of a compound is subjected to a methoxyoxymethylation or the like.

Among these compounds, preferred are, for example, trishydroxymethylphenol, bishydroxymethyl- p -cresol, tetramethylol bisphenol A, and TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.). The hexamethylol or a phenolic compound in which the methylol group is replaced by an alkoxymethyl group and both a methylol group and an alkoxymethyl group.

The compounds of these (c) may be used singly or in combination.

The total content of the dye-containing negative-type curable composition of the crosslinking agent varies depending on the type of the substrate, and the solid content (mass) of the curable composition is based on the viewpoint of improving the hardenability. It is preferably from 1 to 70% by mass, more preferably from 5 to 50% by mass, particularly preferably from 7 to 30% by mass.

Thermal polymerization inhibitor

In the dye-containing negative-type hardenable composition of the present invention, in addition to the above, it is preferred to further add a thermal polymerization inhibitor in advance. For example, hydroquinone, p -methoxyphenol, di- t -butyl- p -cresol, pyrogallol, t -butyl catechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6- t -butylphenol), 2,2'-methylenebis(4-methyl-6- t -butylphenol), 2-hydrothiobenzimidazole, and the like are useful.

<various additives>

In the dye-containing negative-type hardenable composition of the present invention, if necessary, various additives such as a filler, a polymer compound other than the above, a surfactant, a adhesion promoter, an antioxidant, and ultraviolet absorption may be incorporated. Agent, anti-coagulant, etc.

Specific examples of the various additives include fillers such as glass and alumina; and polymer compounds other than adhesive resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactant such as ionic, cationic or anionic; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-amino group Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, 3-sulfopropoxypropyltrimethoxydecane, 3-glycidoxypropyldimethoxydecane, 2-(3,4 sulfooxycyclohexyl)ethyltrimethoxydecane , 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, etc. Adhesion promoter; 2,2-thiobis(4-methyl-6- t -butylphenol), 2,6-di- t -butylphenol, etc.; 2-(3- t -butyl-5- An ultraviolet absorber such as methyl-2-hydroxyphenyl)-5-chloroaniline triazole or alkoxybenzone; and an anti-coagulant such as sodium polyacrylate.

Further, in order to promote the alkali solubility of the non-hardened portion, it is desirable that the dye-containing negative-type curable composition of the present invention is further improved in developability, and an organic carboxylic acid, preferably a molecular weight of 1,000, can be carried out in the composition. The following addition of a low molecular weight organic carboxylic acid.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; oxalic acid and propylene; Diacid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, A An aliphatic dicarboxylic acid such as succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as tris-trimethylbenzene, propylene-1,2,3-tricarboxylic acid or camphoric acid ; aromatic monocarboxylic acid such as benzoic acid, toluic acid, p-isopropylbenzoic acid, dimethylphenyl acid, 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, p-phenylene Aromatic polycarboxylic acid such as formic acid, trimellitic acid, trimesic acid, pyromellitic acid, pyromellityl, etc.; phenylacetic acid, α-methylphenylacetic acid, hydrogenated cinnamic acid, α-glycolic acid , phenyl succinic acid, α-phenyl acrylate, cinnamic acid, cinnamic acid methyl, benzyl cinnamate, cinnamyl acetic acid, coumaric acid, 2,4-dihydroxycinnamic acid, etc. Acid.

<<Color filter and its manufacturing method>>

Next, the color filter of the present invention will be described in detail by its manufacturing method.

In the method for producing a color filter of the present invention, the dye-containing negative-type curable composition of the present invention is used.

By applying a dye-containing negative-type curable composition of the present invention to a carrier by a coating method such as spin coating, flow coating, or roll coating, a photosensitive composition layer is formed and passed through a predetermined mask pattern. The thin layer is exposed to light and developed by a developing solution to form a negative colored pattern (image forming step). Further, if necessary, a hardening step of hardening the colored pattern formed by heating and/or exposure may be included.

In the present invention, it is preferable to perform exposure by exposure of the stepper at the time of the exposure.

In the production of a color filter, a color filter formed of a desired color tone can be produced by repeating only the image forming step (and the necessary hardening step) of the desired number of tones. At this time, the light or radiation used, especially the ultraviolet rays such as the g-line, the h-line, and the i-line are particularly preferable.

For example, the carrier may be a soda lime glass for a liquid crystal display element, a hard glass (Pyrex; registered trademark) glass, a quartz glass, or a transparent conductive film attached to the glass, or a photoelectric conversion for a photographic element or the like. The element substrate, for example, a germanium substrate or the like, or a complementary metal oxide film semiconductor (CMOS) or the like. These substrates can also form a black matrix driver that isolates each pixel.

Further, if necessary, an undercoat layer may be provided on the carrier in order to improve adhesion to the upper thin layer, prevent diffusion of the substance, or planarize the surface of the substrate.

Any developer may be used as the developer, as long as it dissolves the unhardened portion of the dye-containing negative-type hardenable composition of the present invention, and does not dissolve the composition of the irradiated portion. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used. The organic solvent may be exemplified by the organic solvent used in the preparation of the dye-containing negative-type hardenable composition of the present invention.

The alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium The basic compound such as hydroxide, choline, pyrrole, piperidine or 1,8-dioxabicyclo[5.4.0]-7-undecene has a dissolved concentration of 0.001 to 10% by mass, preferably 0.01 to 0.01%. An alkaline aqueous solution of 1% by mass. Further, in the case of using a developing solution obtained from such an alkaline aqueous solution, it is usually washed with water after development.

The color filter of the present invention can be used for a solid-state imaging element such as a liquid crystal display element or a CCD, and is particularly suitable for a CCD element or CMOS having a high resolution of more than 1,000,000 pixels. The color filter of the present invention can be used, for example, as a color filter disposed between each of the pixel light receiving portions constituting the CCD and the microlens for collecting light.

Example

Hereinafter, the present invention will be more specifically described based on the examples, and the present invention is not limited by the following examples. Also, as long as there is no special statement, "parts" are based on quality.

Example 1

1) Preparation of Negative Hardening Composition Containing Dyes The dye-containing negative-type hardening composition of the present invention is prepared by mixing and dissolving each compound using the composition shown below.

Composition ● Ethyl lactate (organic solvent) 67.3g ● Resin C 7.9g (benzyl methacrylate / methacrylic acid copolymer (= 60 / 40 [mr ratio])) ● monomer A 4.8g (free radical Polymerizable monomer: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) ● This exemplified compound C-1 (pigment represented by the formula (A)) 6.6 g ● This specific example number 39 (general formula (1) ) quinacridone-based coloring matter) 2.2 g ● Photopolymerization initiator 2.1 g (trade name: TAZ-107, manufactured by Midori Chemical Co., Ltd.)

2) The underlying coated ruthenium wafer substrate was formed on a ruthenium wafer substrate, and a photoresist solution (trade name: CT-2000L, manufactured by Fujifilm Arch Co., Ltd., Japan) was applied as a film thickness by a spin coater. 2 μm, heat-dried at 220 ° C for 1 hour to form a cured film (undercoat layer) to obtain a bottomed coated germanium wafer substrate.

3) Exposure and development of a negative-type curable composition containing a dye (image formation step) The dye-containing negative-type hardenable composition obtained in the above 1) is obtained by a spin coater. The undercoat layer of the underlying wafer substrate was applied to a film thickness of 1 μm, and pre-baked at 100 ° C for 120 seconds to obtain a sample on which a photoresist layer was formed on the substrate.

Example 2~10

The negative curing property of the dye-containing dye was prepared in the same manner as in Example 1 except that the respective compositions contained in the dye-containing negative-type curable composition of Example 1 were changed to the compositions shown in Table 1 below. Each sample was formed as a composition.

Comparative example 1

The dye-containing negative was prepared in the same manner as in Example 1 except that the composition contained in the dye-containing negative-type hardenable composition of Example 1 was changed to the composition shown in Table 1 below. Each sample was formed by forming a hardening composition.

【Table 1】

※Alkali Soluble Adhesive ●Resin A: Trade name ACA250, manufactured by Daicel Chemical Industry Co., Ltd. (Compound name: methacrylic acid-4-propenyloxymethyl-2-hydroxycyclohexyl ester/alkyl methacrylate copolymer ●) Resin B: trade name ACA300, manufactured by Daicel Chemical Industry Co., Ltd. (Compound name: 4-acryloxy-4-methylcyclohexyl methacrylate/alkyl methacrylate copolymer) ● Resin C: benzyl methacrylate / methacrylic acid copolymer (= 60 / 40 [mr ratio])

* Radical polymerizable monomer ● Monomer A: manufactured by Nippon Kayaku Co., Ltd., DPHA (main component: dipentaerythritol hexaacrylate)

* Organic solvent-soluble dye ● The symbol of the organic solvent-soluble dye column (except the comparative example) is an exemplary compound number corresponding to the dye represented by the general formula (A) and a quinophthalone-based dye represented by the general formula (1). The specific example number. ●VB-2620: Orient Chemical Industry Co., Ltd.

※Photopolymerization initiator ● "TAZ-107": manufactured by Midori Chemical Co., Ltd. ●肟A: 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1, 2-octanedione [manufactured by Ciba Speciality Chemicals Co., Ltd.] ●肟B: 1-(O-Ethylindole)-1-[9-ethyl-6-(2-methylbenzoinyl)-9H -Aminomethylmercapto-3-indenyl]ethanone [Ciba Speciality Chemicals Co., Ltd.]

4) Evaluation (1) Sensitivity For the samples formed in the respective examples and comparative examples, the i-line reduction projection exposure apparatus was used, and the exposure amount was changed by using a 365 nm wavelength through a mask having a length of 2 μm × a width of 2 μm. Irradiation of the coated film. After the irradiation, a developing solution (100% of a product name: CD-2000, manufactured by Fujifilm Arch Co., Ltd., Japan) was used, and development was carried out at 23 ° C for 60 seconds. Subsequently, the mixture was rinsed for 20 seconds in a water flow method, and then spray-dried to obtain a pattern image. The image formation was confirmed by an optical microscope and SEM photographing by a usual method.

At this time, the exposure amount of the image pattern having a length of 2 μm × 2 μm in width and the width of the gap between the image patterns was set to an appropriate exposure amount, and the exposure amount was set as the sensitivity. The smaller the value, the better the sensitivity. The results are shown in Table 2 below.

(2) Outline In the above (1), the cross section of the pattern was observed by an SEM image with respect to the image pattern formed at an appropriate exposure amount. At this time, a person who has a good rectangular profile is evaluated as "○", a person whose head is slightly round is evaluated as "△", and a person whose head is completely round is evaluated as "X". The results are shown in Table 2 below.

(3) Unexposed part of the residue In the above (1), the cross section of the pattern was observed by an SEM image with respect to the image pattern formed at an appropriate exposure amount. At this time, those who did not observe the residue at all in the unexposed portion were evaluated as "○", and those who had not observed the residue in the unexposed portion were evaluated as "△", and those who were not exposed in the exposed portion were evaluated as "△". "X". The results are shown in Table 2 below.

(4) Heat resistance The dye-containing negative-type hardenable composition obtained in the above 1) was coated on a glass substrate prepared by another method to have a film thickness of 1 μm. The glass substrate on which the coating film was formed was placed on a hot plate at 200 ° C for 1 hour, and then the measurement of the spectral change was carried out by a spectrophotometer (trade name: MS-1500, manufactured by Shimadzu Corporation, Japan). From such a measured value, ΔE*ab was calculated by a color analysis program as an evaluation of heat resistance. The results are shown in Table 2 below.

(5) Light resistance The dye-containing negative-type curable composition obtained in the above 1) was coated on a glass substrate prepared by another method to have a film thickness of 1 μm. After the coating film was irradiated for 20 hours (200,000 lux.h) by a sputum irradiation weathering meter (trade name: SX75, manufactured by Suga Test Instruments Co., Ltd.), a spectrophotometer (product name: MS-1500, manufactured by Shimadzu, Japan) was used. The company's company made a measurement of the spectroscopic change. From such a measured value, ΔE*ab was calculated by a color analysis program as an evaluation of light resistance. The results are shown in Table 2 below.

In the examples in which the dye represented by the formula (A) and the quinophthalone-based dye represented by the formula (1) are used in the table 2, the heat resistance and the light resistance are excellent, and the sensitivity is excellent. The rectangular shape of the pattern was also good, and no residue was observed in the unexposed portion. On the other hand, in the comparative example using the dye other than the pigment of the present invention, the heat resistance and the light resistance were remarkably deteriorated, and the squareness of the sensitivity and the pattern were both deteriorated, and further, the residue was observed in the unexposed portion.

Examples 11 to 19 and Comparative Example 2

1) Preparation of Negative Hardening Composition Containing Dyes The constituent compounds shown in Table 3 below were mixed and dissolved to prepare the dye-containing negative-type hardening compositions (1) to (9) of the present invention and comparative Modulation of a negative-type hardenable composition (10) containing a dye.

【table 3】

The details of the compositions (A) to (D) in Table 1 are as follows.

※Alkali Soluble Adhesive ●Resin A: Trade name ACA250, manufactured by Daicel Chemical Industry Co., Ltd. (Compound name: methacrylic acid-4-propenyloxymethyl-2-hydroxycyclohexyl ester/alkyl methacrylate copolymer ●) Resin B: trade name ACA300, manufactured by Daicel Chemical Industry Co., Ltd. (Compound name: 4-acryloxy-4-methylcyclohexyl methacrylate/alkyl methacrylate copolymer) ● Resin C: benzyl methacrylate / methacrylic acid copolymer (= 60 / 40 [mr ratio])

* Radical polymerizable monomer ● Monomer A: manufactured by Nippon Kayaku Co., Ltd., DPHA (main component: dipentaerythritol hexaacrylate)

* Organic solvent-soluble dyes are disclosed in the organic solvent-soluble dyes of Examples 11 to 19, and the exemplified compounds of the formula (C1) are represented by the formula (1). This exemplified compound of the quinophthalone type pigment.

※Photopolymerization initiator ● "TAZ-107": manufactured by Midori Chemical Co., Ltd. ●肟A: 2-(O-phenylhydrazinyl)-1-[4-(phenylthio)phenyl]-1, 2-octanedione [Ciba Speciality Chemicals Co., Ltd.] ●肟B: 1-(O-Ethylindole)-1-[9-ethyl-6-(2-methylbenzoinyl)-9H -aminomethylmethyl-3-indenyl]ethane [manufactured by Ciba Speciality Chemicals Co., Ltd.]

2) The base wafer to which the undercoating was applied was fabricated on a ruthenium wafer substrate, and a photoresist CT-2000L solution (manufactured by Fujifilm Arch Co., Ltd., Japan) was applied to a film thickness of 2 μm by a spin coater. The film was dried by heating at ° C for 1 hour to form a cured film (undercoat layer).

3) Exposure and development of a negative-type curable composition containing a dye (image formation step), respectively, the dye-containing negative-type hardenable composition obtained in 1) is sequentially applied by a spin coater to 2) The undercoat layer of the obtained undercoat glass substrate was applied to a film thickness of 1 μm, and prebaked at 100 ° C for 120 seconds.

Next, the i-line reduction projection exposure apparatus was used to irradiate the coating film by changing the exposure amount by using a mask having a line width of 2 μm at a wavelength of 365 nm. After the irradiation, development was carried out using a developing solution of 60% of CD-2000 (manufactured by Fujifilm Arch Co., Ltd., Japan) at 23 ° C for 60 seconds. Then, after rinsing for 20 seconds by a water flow method, it was spray-dried to obtain a pattern image (color filter). The image formation was confirmed by an optical microscope and SEM photographing by a usual method.

4) Evaluation The following evaluations were performed for each pattern image obtained by using the dye-containing negative-type hardenable compositions (1) to (10). The results of the evaluation are shown in Table 4 below.

(1) In the pattern having a sensitivity of 2 μm, the exposure amount in which the width of the dot and the gap is 1:1 is set to an appropriate exposure amount, and the exposure amount is set as the sensitivity. The smaller the value is, the higher the sensitivity is, and the display sensitivity is good.

(2) The outline of the cross-sectional shape of the pattern image is visually observed from the SEM image of the appropriate exposure amount of (1), and the outline of the cross-section of the image is evaluated as "○", and the head is slightly rounded. The person evaluated as "△", and the person whose head is clearly rounded is evaluated as "×".

(3) Unexposed part of the residue The SEM image of the appropriate exposure amount of (1) was used to visually observe the pattern image, and the unexposed portion was evaluated as "○", and the unexposed portion was slightly observed. Practically, the allowable person is evaluated as "△", and the unobserved portion is clearly observed as "x".

(4) Heat resistance The negative-type curable composition containing a dye was applied to a glass substrate prepared by another method to a thickness of 1 μm, and each coating film was brought into contact with a hot plate at 200 ° C on the glass substrate side. And put it for 1 hour. Then, the spectrophotometer MS-1500 (manufactured by Shimadzu Corporation, Japan) was used to measure the spectral change, and ΔE*ab was calculated by a color analysis program. The calculated value is set as an index for evaluating heat resistance. The smaller value shows excellent heat resistance.

(5) Light resistance The negative-type curable composition containing a dye was applied to a glass substrate prepared by another method to a thickness of 1 μm, and each was irradiated with a sputum irradiation weathering meter SX75 (manufactured by Suga Test Instruments Co., Ltd.). The film was coated for 20 hours (200,000 lux.h). Then, the spectrophotometer MS-1500 (manufactured by Shimadzu Corporation, Japan) was used to measure the spectral change, and ΔE*ab was calculated by a color analysis program, and the calculated value was used as an index for evaluating light resistance. The smaller value shows excellent light resistance.

As shown in Table 4, in the examples in which the phthalocyanine-based dye and the quinophthalone-based dye of the present invention were used in combination, high sensitivity was obtained, and a pattern profile having a good rectangular cross section was formed in the exposed portion, and the unexposed portion was formed. There is no development residue. Further, the formed pattern image shows excellent heat resistance and light resistance. On the other hand, in the comparative example in which the dye of the present invention is not used in combination, the sensitivity is deteriorated, and the cross-sectional shape of the formed pattern image is also slightly rounded, and a good rectangular shape cannot be formed. Development residue was observed in the unexposed portion. Further, from the viewpoint of heat resistance and light resistance, the formed pattern image is also greatly deteriorated.

Claims (13)

A negative-type hardening composition containing a dye, comprising at least: (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical polymerizable monomer; (E) an organic solvent; and the (B) organic solvent-soluble dye contains at least one of the dyes represented by the following formula (A) and a quinophthalone-based dye represented by the following formula (1): [In the formula (A), M ¹ represents a metal group, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently, and represent a group of 6-membered ring formed by atoms selected from a carbon atom and a nitrogen atom] [In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ ; S represents a sulfur atom, and R ⁵ represents an oxygen atom in the form of an ether bond; Further, the alkyl group may have a hydroxyl group as a substituent; R ⁶ represents an alkyl group having a hydroxyl group; however, at least one of R ¹ to R ⁴ represents -S-R ⁵ ]. The dye-containing negative-type hardenable composition according to the first aspect of the invention, wherein the dye represented by the formula (A) is a phthalocyanine dye represented by the following formula (B): [In the general formula (B), M ¹ represents a ^{metal, R 1 0 1 ~ R 1} 1 6 each independently represent a hydrogen atom or a substituent]. A dye-containing negative-type hardening composition according to claim 1 or 2, wherein the (C) photopolymerization initiator is an anthraquinone compound. A dye-containing negative-type hardenable composition according to claim 1 or 2, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain. A dye-containing negative-type hardenable composition according to claim 1 or 2, wherein the (E) organic solvent contains a cyclic ketone solvent. A color filter comprising the dye-containing negative-type hardenable composition according to any one of claims 1 to 5. A method for producing a color filter, comprising: coating a negative-type hardenable composition containing a dye according to any one of claims 1 to 5 on a carrier, and then exposing and developing through a mask And the step of forming a pattern. A negative-type hardening composition containing a dye, comprising at least: (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical polymerizable monomer; And the (B) organic solvent-soluble dye contains at least one of the dyes represented by the following formula (C1) and at least one of the quinophthalone-based dyes represented by the following formula (1): [In the formula (C1), R _{C 1} represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a fluorenyl group, a hydroxy group. , an aliphatic oxy group, an aryloxy group, a decyloxy group, an aminomethyl methoxy group, a heterocyclic oxy group, an aliphatic oxycarbonyloxy group, an N-alkyl decylamino group, an aminocarbamamino group, an amine sulfonium sulfonate Amine, aliphatic oxycarbonylamine, aryloxycarbonylamine, aliphatic sulfonamide, arylsulfonamide, aliphatic thio, arylthio, aliphatic sulfonyl, arylsulfonyl a sulfonyl group, a sulfo group, a fluorenylene group or a heterocyclic thio group; Z _{C 1} represents a non-metal atom group necessary for forming a 6-membered ring together with a carbon atom, and the four Z _{C 1 's} 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, and cn represents an integer of 0 or 1 to 5, four a cn may be the same or different; however, one of the cn represents an integer of 1 to 5, the number of molecules in the R _{C 1} may be the same or different; cr1, cr2, cr3 and cr4 represent 0 or 1, satisfy cr1 cr2 + cr3 + cr4 1] [In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ , R ¹ , R ² , R ³ and At least one of R ⁴ represents -S-R ⁵ ; S represents a sulfur atom, R ⁵ represents an alkyl group having an oxygen atom in the form of an ether bond, and R ⁵ may have a hydroxyl group as a substituent; R ⁶ represents an alkyl group having a hydroxyl group. base]. A dye-containing negative-type hardening composition according to item 8 of the patent application, wherein the (C) photopolymerization initiator is an anthraquinone compound. A dye-containing negative-type hardenable composition according to claim 8 or 9, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain. A dye-containing negative-type hardenable composition according to claim 8 or 9, which further contains an organic solvent containing a cyclic ketone solvent. A color filter comprising at least one of a dye represented by the following formula (C1) and at least one of a quinophthalone dye represented by the following formula (C1): [In the formula (C1), R _{C 1} represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an aminomethyl fluorenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a fluorenyl group, a hydroxy group. , an aliphatic oxy group, an aryloxy group, a decyloxy group, an aminomethyl methoxy group, a heterocyclic oxy group, an aliphatic oxycarbonyloxy group, an N-alkyl decylamino group, an aminocarbamamino group, an amine sulfonium sulfonate Amine, aliphatic hydroxycarbonylamine, aryloxycarbonylamine, aliphatic sulfonamide, arylsulfonylamine, aliphatic thio, arylthio, aliphatic sulfonyl, arylsulfonyl a sulfonyl group, a sulfo group, a fluorenylene group or a heterocyclic thio group; Z _{C 1} represents a non-metal atom group necessary for forming a 6-membered ring together with a carbon atom, and the four Z _{C 1 's} 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, and cn represents an integer of 0 or 1 to 5, four The cn may be the same or different; however, one of cn represents an integer from 1 to 5, and a plurality of R _{C 1} in the molecule may be the same or different; cr1, cr2, cr3 and cr4 represent 0 or 1, satisfying c R1+cr2+cr3+cr4 1] [In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, -S-R ⁵ or -S-R ⁶ , R ¹ , R ² , R ³ and At least one of R ⁴ is -S-R 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 have a hydroxyl group as a substituent; R ⁶ represents an alkyl group having a hydroxyl group. base]. A method of producing a color filter, comprising: coating a negative-type hardenable composition containing a dye according to any one of claims 8 to 11 on a carrier, and then exposing and developing through a mask And the step of forming a pattern.