JP4384585B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a color filter used in a liquid crystal display device or a solid-state imaging device, a dye-containing color filter, and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

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

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 1 to 4). reference).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In view of such a problem, a technique for using a dye instead of a pigment has been proposed (for example, see Patent Document 5). However, a curable composition using a dye has a problem that it is generally inferior to a pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity.

Furthermore, in particular, in the case of use for producing a color filter for a solid-state imaging device, a film thickness of 1.5 μm or less is required, so that a large amount of a dye must be added to the composition, and therefore the film is in close contact with the substrate. In addition, there is a problem that the pattern forming property is remarkably deteriorated, for example, the degree of curing becomes insufficient, or the dye is lost in an exposure region (image portion) forming a filter. In addition, there is little knowledge about the technology related to the formation of a fine pattern of a system using a dye, and in the examples disclosed so far, there is no residue in a region to be developed and removed, that is, a non-exposed region (non-image portion), In addition, it is difficult to form the cross-sectional shape of the formed fine pattern into a favorable rectangular shape.
JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP 54-63903 A

  As described above, although a curable composition containing a dye is useful in applications such as a solid-state imaging device that requires high definition and uniform color, it eliminates residues in non-image areas and reduces the color density and hue of the dye. Improvement of fastness such as heat resistance and light resistance that can be stably maintained has been a problem.

  The present invention has been made in view of the above, and is a curable composition suitable for constituting a dye system. Specifically, it has high sensitivity and has a residue in a non-exposed area (non-image area). A dye-containing negative curable composition that can form a fine pattern with excellent heat fastness and light fastness, and a sharp pattern (especially good cross-sectional shape) The purpose of the present invention is to provide a cost-effective color filter (particularly a color filter for solid-state imaging devices) that has a high resolution with a rectangular shape and is excellent in heat fastness and light fastness, and a manufacturing method thereof. The challenge is to achieve.

Specific means for achieving the above object are as follows.
<1> A dye-containing negative curable composition containing at least (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical polymerizable monomer. The (B) organic solvent-soluble dye contains at least one dye represented by the following general formula (C1) and at least one quinophthalone dye represented by the following general formula (1). The dye-containing negative curable composition is characterized.

In the general formula (C1), Rc ₁ represents a halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group Group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxy Carbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, or heterocyclic ring Represents a thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a 6-membered ring together with carbon atoms, and the four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents 0 or an integer of 1 to 5, and four cns may be the same or different. However, one of the cn represents an integer of 1 to 5, a plurality of Rc ₁ in the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

In the general 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 , and R ¹ , R ^At least one of ² , R ³ , and 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group.

<2> The dye-containing negative curable composition according to <1>, wherein the (C) photopolymerization initiator is an oxime compound.
<3> The dye-containing negative curable composition according to <1> or <2>, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain.
<4> The dye-containing negative curable composition according to any one of <1> to <3>, further including an organic solvent, wherein the organic solvent includes a cyclic ketone solvent.

  <5> A color filter comprising at least one dye represented by the following general formula (C1) and at least one quinophthalone dye represented by the following general formula (1). The color filter according to <5> is preferably formed using the dye-containing negative curable composition according to any one of <1> to <4>.

The same manner as described above for the general formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, Acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group , Aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group Or a heterocyclic thio group It is. Zc ₁ represents a nonmetallic atom group necessary for forming a 6-membered ring together with carbon atoms, and the four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents 0 or an integer of 1 to 5, and four cns may be the same or different. However, one of the cn represents an integer of 1 to 5, a plurality of Rc ₁ in the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1.

In the general formula (1), as described above, 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group.

  <6> A step of applying the dye-containing negative curable composition according to any one of the above <1> to <4> onto a support, exposing through a mask, and developing to form a pattern image. It is a manufacturing method of the color filter characterized by having.

  According to the present invention, it is a curable composition suitable for constituting a dye system. Specifically, it has high sensitivity, and there is no residue in a non-exposed area (non-image area) and the cross-sectional shape is good. Providing a dye-containing negative curable composition that is capable of forming a fine pattern that is excellent in heat fastness and light fastness (particularly when patterned by stepper exposure), and A color filter (especially solid when the pattern is formed by stepper exposure) with a sharp pattern (especially a rectangle with a good cross-sectional shape) and high resolution, excellent heat fastness and light fastness (especially solid color filter) An image sensor color filter) and a manufacturing method thereof can be provided.

Hereinafter, the dye-containing negative curable composition of the present invention, the color filter, and the production method thereof will be described in detail.
[Dye-containing negative curable composition]
The dye-containing negative curable composition of the present invention comprises, as (A) an alkali-soluble binder and (B) an organic solvent-soluble dye, at least one dye represented by the following general formula (C1) and a general formula ( 1) at least one of the quinophthalone dyes (hereinafter sometimes referred to collectively as “the dye according to the present invention”), (C) a photopolymerization initiator, and (D) a radically polymerizable monomer. Generally, it can be configured using (E) an organic solvent, and can be configured using another component such as a crosslinking agent as required.

  The dye-containing negative curable composition of the present invention particularly improves the fastness to heat and light (thermal fastness and light fastness) of the pattern when the pattern is formed by using the pigment according to the present invention. be able to. Furthermore, it is effective in increasing the sensitivity and can reduce the development residue in the non-exposed area forming the non-image area more than before, and thus is useful for forming a high-definition pattern with a high resolution and a rectangular cross section. In addition to the above, it exhibits a good hue and can also achieve high transmittance characteristics.

In the dye-containing negative curable composition of the present invention, the exposure may be performed by any of the proximity method, the mirror projection method, and the stepper method. In particular, a stepper method (a reduction projection exposure apparatus is used). It is preferable to perform the exposure by the reduced projection exposure method). In this stepper method, a pattern is formed by performing exposure while varying the exposure amount stepwise, and when the stepper exposure is performed, the rectangularity of the pattern, which is one of the effects of the present invention, is particularly good. Can be.
As an exposure apparatus used for the stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

(A) Alkali-soluble binder The dye-containing negative curable composition of the present invention contains at least one alkali-soluble binder. The alkali-soluble binder according to the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, and the like, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol Etc. are also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include those obtained by copolymerization using acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. .

  In addition to the above, as a monomer having a hydrophilic group, a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or its salt site, a morpholinoethyl group Monomers containing these are also useful.

  Moreover, as an alkali-soluble binder which concerns on this invention, what has an unsaturated double bond in a side chain from a viewpoint of improving crosslinking efficiency is preferable. As an unsaturated double bond couple | bonded with the side chain of the alkali-soluble binder which concerns on this invention, an allyl group, a (meth) acryl group, an allyloxyalkyl group etc. are mentioned, for example, An allyl group, (meth) acryl group Is preferred. These unsaturated double bonds may be introduced by copolymerizing the unit having the unsaturated double bond, or may be introduced later by a polymer reaction. Examples of the alkali-soluble binder having an unsaturated double bond include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Of the various alkali-soluble binders described above, acrylic resins are preferred, and the acrylic resin is a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. Of these, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

The alkali-soluble binder is preferably a polymer having a mass average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.

  The content of the alkali-soluble binder in the dye-containing negative curable composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 70% with respect to the total solid content of the composition. Mass% is particularly preferred.

(B) Organic Solvent-Soluble Dye The dye-containing negative curable composition of the present invention is represented by the following general formula (1) and at least one dye represented by the following general formula (C1) as a pigment compound. It contains at least one kind of quinophthalone dye (the dye according to the present invention). Since it contains at least two pigments according to the present invention, it is possible to form a pattern having a good rectangular cross section with high sensitivity and eliminating development residues in non-exposed areas, compared to conventional dye-based compositions, The heat fastness and light fastness of the pattern after formation can be effectively improved.

-Dye Represented by General Formula (C1)-
The dye-containing negative curable composition of the present invention contains at least one pigment represented by the following general formula (C1) (hereinafter also referred to as “phthalocyanine dye according to the present invention”). This pigment (dye) exhibits a good cyan hue with high transmittance characteristics, and is excellent in stability with no precipitation over time when it is in the form of a liquid preparation or a coated film, especially against heat and light. Excellent resistance.

Hereinafter, the phthalocyanine dye according to the present invention will be described focusing on details of each group of the general formula (C1).
In the general formula (C1), “aliphatic” means that the aliphatic moiety is linear, branched, or cyclic and may be either saturated or unsaturated. For example, an alkyl group, an alkenyl group, a cyclo It includes an alkyl group and a cycloalkenyl group, and may be unsubstituted or substituted with a substituent. “Aryl” may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent. “Heterocycle” means that the heterocycle portion has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be either a saturated ring or an unsaturated ring. And a condensed ring, which may be unsubstituted or substituted with a substituent.

  In the general formula (C1), the “substituent” may be any substitutable group, and examples thereof include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an imide group, an azo group, an acyloxy group, and an acylamino group. Group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, Aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, hetero Ring amino group, aliphatic oxycarbonylamino group, arylo Sicarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, heterocyclic thio, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group , Aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, etc. be able to.

In the general formula (C1), Rc ₁ represents a halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group Group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxy Carbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, or heterocyclic ring Represents a thio group.

Examples of the halogen atom represented by Rc ₁ include a fluorine atom, a chlorine atom, and a bromine atom.
The aliphatic group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and has a total carbon number of 1 ~ 15 aliphatic groups are preferred. Examples thereof include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, and a 2-ethylhexyl group.

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

The heterocyclic group represented by Rc _1, may be saturated or unsaturated, heterocyclic group having a total carbon number of 1 to 15 is preferred, a total heterocyclic group having 3 to 10 carbon atoms More preferred. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group, 1-piperidyl group and the like can be mentioned. Furthermore, you may have a substituent.

Examples of the carbamoyl group represented by Rc _1, may have a substituent be unsubstituted, total carbamoyl group having a carbon number of 1 to 16 is preferred, a total carbamoyl group having 1 to 12 carbon atoms is more preferred. For example, a carbamoyl group, a dimethylcarbamoyl group, a dimethoxyethylcarbamoyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and may contain total carbon. A C2-C16 aliphatic oxycarbonyl group is preferable, and a C2-C10 aliphatic oxycarbonyl group is more preferable. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.

The aryloxycarbonyl group represented by Rc _1, which may be the unsubstituted or substituted by a substituent, an aryloxycarbonyl group preferably having a total carbon number of 7 to 17, carbon atoms in total 7-15 aryloxy A carbonyl group is more preferred. For example, a phenoxycarbonyl group etc. are mentioned.

Acyl group represented by Rc ₁ may be an aryl group be aliphatic carbonyl group may have a substituent if it represents an aliphatic carbonyl group, an arylcarbonyl group May further have a substituent, may be saturated or unsaturated, and may be cyclic. The acyl group is preferably an acyl group having 2 to 15 carbon atoms, and more preferably an acyl group having 2 to 10 carbon atoms. For example, acetyl group, pivaloyl group, benzoyl group and the like can be mentioned. Furthermore, you may have a substituent.

The aliphatic oxy group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. As the aliphatic oxy group, an aliphatic oxy group having 1 to 12 carbon atoms is preferable, and an aliphatic oxy group having 1 to 10 carbon atoms is more preferable. For example, a methoxy group, an ethoxyethoxy group, a phenoxyethoxy group, a thiophenoxyethoxy group, and the like can be given.
The aryloxy group represented by Rc _1, may have a substituent be unsubstituted, an aryloxy group having a carbon number of 6 to 18 is preferable, an aryloxy group having a carbon number of 6 to 14 More preferred. For example, a phenoxy group, 4-methylphenoxy group, etc. are mentioned.

The acyloxy group represented by Rc ₁ may be unsubstituted or substituted, and is preferably an acyloxy group having 2 to 14 carbon atoms, and more preferably an acyloxy group having 2 to 10 carbon atoms. For example, an acetoxy group, a methoxyacetoxy group, a benzoyloxy group, etc. are mentioned.
The carbamoyloxy group represented by Rc _1, may have a substituent be unsubstituted, total carbamoyloxy group having a carbon number of 1-16 is preferable, total carbamoyloxy group having 1 to 12 carbon atoms More preferred. Examples thereof include a dimethylcarbamoyloxy group and a diisopropylcarbamoyloxy group.

The heterocyclic oxy group represented by Rc ₁ may be unsubstituted or substituted, and is preferably a heterocyclic oxy group having 1 to 15 carbon atoms in total, and a heterocyclic ring having 3 to 10 carbon atoms in total. An oxy group is more preferable. For example, 3-furyloxy group, 3-pyridyloxy group, N-methyl-2-piperidyloxy group and the like can be mentioned.
The aliphatic oxycarbonyloxy group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. As an aliphatic oxycarbonyloxy group, a C2-C16 aliphatic oxycarbonyloxy group is preferable, and a C2-C10 aliphatic oxycarbonyloxy group is more preferable. Examples thereof include a methoxycarbonyloxy group and (t) butoxycarbonyloxy group.

The N- alkylacylamino group represented by Rc _1, may have a substituent be unsubstituted, N- alkyl acylamino group having a total carbon number of 3 to 15 are preferred, 3 to the total number of carbon atoms 12 N-alkylacylamino groups are more preferred. For example, N-methylacetylamino group, N-ethoxyethylbenzoylamino group, N-methylmethoxyacetylamino group and the like can be mentioned.
The carbamoylamino group represented by Rc ₁ may be unsubstituted or substituted, and is preferably a carbamoylamino group having 1 to 16 carbon atoms in total, and a carbamoylamino group having 1 to 12 carbon atoms in total. More preferred. Examples thereof include an N, N-dimethylcarbamoylamino group and an N-methyl-N-methoxyethylcarbamoylamino group.
The sulfamoylamino group represented by Rc ₁ may be unsubstituted or substituted, and is preferably a sulfamoylamino group having 0 to 16 carbon atoms, and having 0 to 12 carbon atoms in total. A sulfamoylamino group is more preferred. Examples thereof include an N, N-dimethylsulfamoylamino group and an N, N-diethylsulfamoylamino group.

The aliphatic oxycarbonylamino group represented by Rc ₁ may be unsubstituted or substituted, and is preferably an aliphatic oxycarbonylamino group having 2 to 15 carbon atoms in total, having 2 to 2 carbon atoms in total. Ten aliphatic oxycarbonylamino groups are more preferred. For example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, etc. are mentioned.
The aryloxycarbonylamino group represented by Rc _1, which may be the substituted or unsubstituted, preferably an aryloxy carbonyl amino group having 7 to 17 carbon atoms, the total carbon number of 7 to 15 of An aryloxycarbonylamino group is more preferred. For example, a phenoxycarbonylamino group, 4-methoxycarbonylamino group, etc. are mentioned.

The aliphatic sulfonylamino group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. As the aliphatic sulfonylamino group, an aliphatic sulfonylamino group having 1 to 12 carbon atoms is preferable, and an aliphatic sulfonylamino group having 1 to 8 carbon atoms is more preferable. Examples thereof include a methanesulfonylamino group and a butanesulfonylamino group.
As the arylsulfonylamino group represented by Rc _1, which may be the substituted or unsubstituted, preferably arylsulfonylamino group having a total carbon number of 6 to 15, total arylsulfonyl having a carbon number of 6 to 12 An amino group is more preferable. Examples thereof include a benzenesulfonylamino group and a 4-toluenesulfonylamino group.

The aliphatic thio group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. As the aliphatic thio group, an aliphatic thio group having 1 to 16 carbon atoms is preferable, and an aliphatic thio group having 1 to 10 carbon atoms is more preferable. Examples thereof include a methylthio group, an ethylthio group, and an ethoxyethylthio group.
The arylthio group represented by Rc ₁ may be unsubstituted or substituted, and is preferably an arylthio group having 6 to 22 carbon atoms, and preferably an arylthio group having 6 to 14 carbon atoms. For example, a phenylthio group, 2-t-butylthio group, etc. are mentioned.

The aliphatic sulfonyl group represented by Rc ₁ may be unsubstituted or substituted, and is preferably an aliphatic sulfonyl group having 1 to 15 carbon atoms, and an aliphatic group having 1 to 8 carbon atoms. A sulfonyl group is more preferred. For example, a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like can be given.
The arylsulfonyl group represented by Rc _1, may have a substituent be unsubstituted, total arylsulfonyl group having a carbon number of 6 to 16 is preferably, total arylsulfonyl group having a carbon number of 6 to 12 More preferred. Examples thereof include a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group and the like.

The sulfamoyl group represented by Rc ₁ may be unsubstituted or substituted, preferably a sulfamoyl group having 0 to 16 carbon atoms, and more preferably a sulfamoyl group having 0 to 12 carbon atoms. For example, a sulfamoyl group, a dimethylsulfamoyl group, etc. are mentioned.
The imide group represented by Rc ₁ may be further condensed, preferably an imide group having 3 to 22 carbon atoms, and more preferably an imide group having 3 to 15 carbon atoms. For example, a succinimide group, a phthalimide group, and the like can be given.
The heterocyclic thio group represented by Rc ₁ may be unsubstituted or substituted, and is preferably a 5- to 7-membered ring having 1 to 20 carbon atoms in total, A heterocyclic thio group having 1 to 12 carbon atoms in total is preferred. For example, 3-furylthio group, 3-pyridylthio group and the like can be mentioned.

In the general formula (C1), Zc ₁ represents a group of nonmetallic atoms necessary for forming a 6-membered ring with a carbon atom, and the four Zc ₁ may be the same or different. The formed 6-membered ring may be either an aryl ring or a heterocyclic ring, may be condensed, and the condensed ring may further have a substituent. Examples of the 6-membered ring include a benzene ring, a pyridine ring, a cyclohexene ring, a naphthalene ring, and the like, and an embodiment that is a benzene ring is preferable.

In the general formula (C1), M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Examples of M include VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , and SnCl _2. , SiCl ₂ , GeCl ₂ , Si (OH) ₂ , H _{2 and the} like, and VO, Zn, Mn, Cu, Ni, and Co are preferable.

In the general formula (C1), cm represents 0, 1 or 2 (preferably 0), and cn represents 0 or an integer of 1 to 5 (preferably 0 or 1). The four cns in the molecule may be the same or different, but one of cn represents an integer of 1 to 5, and when there are a plurality of cns in the molecule, the plurality of Rc ₁ are the same or different from each other. May be.
Cr1, cr2, cr3, and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1. Among these, an embodiment in which cr1 + cr2 + cr3 + cr4 is 3 or 4 is preferable.

  Among the dyes represented by the general formula (C1), a dye represented by the following general formula (C1-1) (phthalocyanine dye according to the present invention) from the viewpoint of more effectively achieving the effects of the present invention. Is preferred.

In the general formula (C1-1), Rc ₂ represents a substituent, and the substituent may be any group that can be substituted, and examples include the groups listed in the above-mentioned “Substituent” section. Preferably, aliphatic group, aryl group, heterocyclic group, N-alkylacylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl Group, carbamoyl group, aliphatic sulfonyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic thio group , Arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, carbamoylamino group, sulfamoylamino group, halogen atom, more preferably aliphatic group, N-alkylacylamino group, aliphatic oxy group , Aliphatic oxycarbonyl group, aliphatic sulfo Group, an aliphatic thio group, an arylthio group, a sulfo group, a carboxyl group, a halogen atom.

In said general formula (C1-1), cp represents the integer of 0-4, Preferably it is 0 or 1. However, cp + cr1, cp + cr2, cp + cr3, and cp + cr4 all represent integers of 0 to 4. If Rc ₂ is more present in the molecule, a plurality of Rc ₂ may be the same or different.
Incidentally, Rc ₁ in the general formula (C1-1), M, cm, cn and cr1, cr2, cr3, and cr4 has the same meaning as the general formula (C1) definitive, preferable embodiments thereof are also the same.

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

In the general formula _{(C1-2), Rc 1, Rc} 2, M, cm, cn and cr1, cr2, cr3, and cr4, have the same meanings as in the formula (C1) and (C1-1) The preferred embodiment is also the same. Moreover, cq in general formula (C1-2) represents 0 or 1. The phthalocyanine skeleton has a structure in which four benzene rings are condensed outside the tetraazaporphyrin skeleton, and each benzene ring has a portion (carbon atom) into which four substituents can enter. Formula (C1-2) is one in which hydrogen atoms are bonded to two positions (β position) far from the tetraazaporphyrin skeleton of each benzene ring.

In the general formula (C1-2), Rc ₁ is a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryl, from the viewpoint of more effectively achieving the effects of the present invention. Oxycarbonyl group, hydroxy group, aliphatic oxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group An arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group is preferred, and an aliphatic group, a carbamoyl group, an aliphatic oxycarbonyl group , Aryloxycarbonyl group, aliphatic oxy group, fat Oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, imide group, or sulfo A more preferred embodiment is a carbamoyl group, aliphatic oxycarbonyl group, aliphatic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, aliphatic oxycarbonylamino group, arylsulfonyl group, imide group, or aliphatic group. The embodiment that is a sulfonyl group is most preferred.

Similarly, Rc ₂ is an aliphatic group, an N-alkylacylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an aliphatic group, in that the effects of the present invention can be more effectively exhibited. An embodiment that is a thio group, an arylthio group, a sulfo group, a carboxyl group, or a halogen atom is preferable, and an embodiment that is an aliphatic group or a halogen atom is more preferable. Similarly, the aspect that cq is 0 is preferable in that the effect of the present invention can be further achieved. Similarly, in the point that the effects of the present invention can be further exerted, the M is preferably VO, Mn, Co, Ni, Cu, Zn or Mg, more preferably VO, Co, Cu or Zn. The embodiment in which Cu is the most preferable, the embodiment in which cm is 0 is preferable, the embodiment in which cn is 1 or 2 is preferable, and the embodiment in which cn is 1 is more preferable.

From the viewpoint of further effectively achieving the effects of the present invention, in the general formula (C1-2), Rc ₁ is a halogen atom, aliphatic group, cyano group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl. Group, hydroxy group, aliphatic oxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, aryl A sulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group, wherein the M is VO, Co, Cu, or Zn, and the cq Is preferably 0, the cm is 0, and the cn is 1. Ku, also, the Rc ₁ is an aliphatic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbonyl group, carbamoylamino group, sulfamoylamino group, aliphatic An oxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group, and the M is VO, Co, Cu, or Zn. More preferably, the cq is 0, the cm is 0, and the cn is 1.

In particular, similarly, from the viewpoint of the effect of the present invention, the Rc ₁ is carbamoyl group, aliphatic oxycarbonyl group, aliphatic oxy group, carbamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonyl group, arylsulfonyl group. Or an imide group, wherein M is Cu, cq is 0, cm is 0, and cn is 1.

  Hereinafter, specific examples (Exemplary Compounds C-1 to C-59) of the pigments (dyes) represented by the general formulas (C1) to (C1-2) are shown. However, the present invention is not limited to these.

-Synthesis example-
Next, a synthesis example of the coloring matter (dye) represented by the general formula (C1) will be described in detail with reference to the following scheme by way of an example of the synthesis of the dye C-1 as the exemplified compound.

<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 further cooled and stirred at 5 ° C., and further 9 ml of 30% hydrogen peroxide solution was kept at an internal temperature of 25 ° C. While dripping. The reaction solution after dropping was further stirred at 25 ° C. for 30 minutes, cooled again to 5 ° C., 15 ml of concentrated hydrochloric acid was added dropwise with stirring, 200 ml of water was further added, and the mixture was stirred at 25 ° C. for 1 hour. The precipitated crystals were filtered, washed thoroughly with water, and dried to obtain 24.7 g of intermediate product B as white crystals (yield 99.5%).

<Synthesis of Intermediate Products C, D, and E>
Subsequently, 100 ml of toluene and 0.25 ml of dimethylacetamide were added to 17.5 g (0.114 mol) of the intermediate product B obtained above, and further 25 ml of thionyl chloride was added dropwise over 10 minutes under reflux. This was further heated under reflux for 1 hour and then concentrated under reduced pressure to obtain a viscous liquid. On the other hand, while adding 10 ml of dimethylacetamide and 100 ml of acetonitrile to 38.0 g (0.235 mol) of diethoxyethylamine and stirring at 10 ° C., the viscous liquid was kept at 15 ° C. over 15 minutes. It was dripped. After further stirring for 30 minutes, this 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 distilled off under reduced pressure to obtain an intermediate product C which was 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 a solution obtained by diluting 10 ml of sulfuric acid in 40 ml of water was added dropwise over 20 minutes under reflux with heating. The mixture was further heated and stirred for 30 minutes and then cooled, and insoluble matters were separated by filtration. To the resulting solution were added 50 ml of saturated brine and 100 ml of ethyl acetate, and the mixture was separated, and the ethyl acetate phase was washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to obtain an intermediate product D which was a pale yellow viscous liquid.

  Next, 70 ml of dimethylacetamide and 15 g (0.108 mol) of potassium carbonate were added to this intermediate product D under stirring in a nitrogen atmosphere, and 19.7 g (0. 113 mol) was gradually added while maintaining the temperature below 25 ° C. This was further stirred for 30 minutes, and then poured into 300 ml of water with stirring. The obtained crystals were filtered, and the crystals were thoroughly washed with water. The obtained crystals were recrystallized with 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 as white crystals (yield 72.6%).

<Synthesis of Dye C-1>
Next, 150 ml of butanol, 6.7 g (0.070 mol) of ammonium carbonate, and 4.7 g (0.035 mol) of copper chloride are added to 34.4 g (0.081 mol) of the intermediate product E, and the mixture is heated and stirred. For 7 hours. Thereafter, butanol was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 25 g of a dye C-1 powder (yield 72.7%). When the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max 706. It was 8 nm and ε55,600.

  In addition, it can synthesize | combine similarly to the above also about another above-mentioned exemplary compound by changing into a desired compound according to the target dye.

-Quinophthalone dye represented by the general formula (1)-
The dye-containing negative curable composition of the present invention includes a dye represented by the general formula (C1) and a quinophthalone dye represented by the following general formula (1) (hereinafter referred to as “quinophthalone system according to the present invention”). At least one kind of dye. Hereinafter, the quinophthalone dye according to the present invention will be described focusing on details of each group of the general formula (1).

  The quinophthalone colorant represented by the following general formula (1) is a compound that satisfies both high light resistance and high heat resistance, which are not conventionally used, and can be freely dissolved in water or a solvent when necessary. is there.

In the general 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 . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ¹ , R ² , R ³ , and R ⁴ represents —S—R ⁵ .

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

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

Examples of the alkyl group represented by R ⁵ include 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 3-ethoxypropyl group, 2- Ethoxy-1-methylpropyl group, 3-propoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 4-methoxybutyl group, 4-propoxybutyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 2,3-dimethoxypropyl group, 2,3-diethoxypropyl group, 2,3-dipropoxypropyl group, 2,3-diisopropoxypropyl group, 2,3-dibutoxypropyl group, 2,3-dicyclohexyl Propyl group,

2,3-di (2-ethoxyethoxy) propyl group, 2,3-di (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxy) -3- (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxyethoxy) -3- (2-propoxyethoxyethoxy) propyl group, 2,3-di (1,3-dioxolan-2-yl-ethoxy) propyl group, (2,2-dimethyl- 1,3-dioxolan-4-yl) methyl group, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl group, (2,2-diethyl-1,3-dioxolane-4- Yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2,2-dipropyl-1,3-dioxolan-4-yl) methyl group, (2-propyl-1, - dioxolan-4-yl) methyl group, (2-pentyl-1,3-dioxolan-4-yl) methyl group,

2- (tetrahydrofurfuryloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) propyl group, 2- (tetrahydropyran-2-methyloxy) ethyl group, 2- (1,3-dioxan-2-ylethyloxy) ethyl group, 2 -(1,3-dioxan-2-ylethyloxy) propyl group, hydroxyethoxyethyl group, hydroxyethoxyethoxyethyl group, 2- (hydroxyethoxy) propyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy -3-Ethoxypropyl group, 2-hydroxy-3-butoxypropyl group, 2-hydroxy-3- (ethoxyethoxy) Propyl group, and the like.

When R ^{1 to} R ⁴ represent —S—R ⁶ , R ⁶ is preferably an alkyl group having 1 to 4 hydroxy groups and 2 to 12 carbon atoms in total, from the viewpoint of the optical density of the dye. An alkyl group having 2 to 8 carbon atoms and containing 1 to 3 hydroxy groups is particularly preferred.

Examples of the alkyl group represented by R ⁶ include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-1-methylpropyl group, 4-hydroxybutyl group, 2,3,4-trihydroxybutyl group, 2,3,4,5-tetrahydroxypentyl group, 6-hydroxyhexyl group, 11-hydroxyundecanyl group, 12-hydroxydodecanyl group , Etc.

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

  The quinophthalone dye [the following compound (1)] according to the present invention includes tautomers having structures such as the following compounds (1 ′) and (1 ″). Sexual bodies are also included in the scope of the present invention.

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

-Synthetic method-
Next, a method for synthesizing the quinophthalone dye (quinophthalone dye) represented by the general formula (1) will be described in detail. An outline of typical synthesis methods (first and second synthesis methods) is as follows.

<First synthesis method>
In a first synthetic method, the organic solvent first, with respect to 1 molar amount of the following compound (A), with 1 to 16 molar amount of the alkali compound, HS-R ⁵ [compound (B); R ⁵ is And has the same meaning as R ⁵ in formula (1). It is reacted at 20 to 200 ° C. for 1 to 8 hours together with 1 to 8 moles.

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

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

<Second synthesis method>
In the second synthesis method, an organic solvent first, with respect to the compound (A) 1 molar amount, with 1 to 16 molar amount of the alkali compound, HS-R ⁶ [compound (C); R ⁶ is It is synonymous with R < ⁶ > in the said General formula (1). The reaction is carried out at 20 to 200 ° C. for 1 to 24 hours.

  Next, the solution is discharged into water, neutralized with dilute hydrochloric acid or acetic acid, collected by filtration and washed with water to obtain the following compound (D). In this case, as the organic solvent and alkali compound used in the reaction, the same ones as used in the first synthesis method can be used.

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

Then, the compound (D) is used in an organic solvent at 1 to 24 mol at 20 to 200 ° C. together with 1 to 24 mol of Z-R ⁹ [compound (E)] using 1 to 24 mol of an alkali compound. By reacting for a time, the quinophthalone dye represented by the general formula (1) is obtained. About the said organic solvent and the said alkali compound, the thing similar to what was mentioned by said 1st synthesis method can be used.

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

  Further, even when the compound (D) and the compound (E) are reacted in an organic solvent in a two-phase system using a phase transfer catalyst and an alkaline aqueous solution, the compound (D) and the compound (E) are similarly represented by the general formula (1). A quinophthalone dye can be synthesized. As the organic solvent used in this reaction, the same organic solvent as used in the first synthesis method can be used.

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

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

  In addition to the above-described dye according to the present invention, other dyes conventionally known as color filter applications can be used in combination as necessary. For example, a known xanthene dye or triarylmethane dye can be used in combination.

  The content of the coloring matter according to the present invention (and other coloring matter if necessary) in the dye-containing negative curable composition varies depending on the molecular weight, molar extinction coefficient, or dye type, but the total solid content of the composition 0.5-80 mass% is preferable with respect to a component, and 10-60 mass% is more preferable.

  In addition, toning by mixing two or more dyes, that is, the coloring matter represented by the general formula (C1) and the quinophthalone coloring matter represented by the general formula (1) and other coloring matters as necessary In addition, the addition amount of the dye to be added in the smallest amount among the added dyes is preferably at least 10% or more of the addition amount of all the dyes, and more preferably 10 to 80%.

  The coloring matter according to the present invention represented by the above general formula is a color filter for recording / reproducing a color image used for a solid-state imaging device such as a CCD or CMOS, a display such as an LCD or PDP, or these colors. It is suitable for a curable composition for producing a filter. When producing a color filter, the pigment | dye which concerns on this invention, ie, 2 or more types of pigment | dyes containing the pigment | dye represented by general formula (C1) as described above, and the quinophthalone type pigment | dye represented by General formula (1) is used. Can be produced by any method as long as it is configured, for example, as described later, for example, a curable composition containing the dye according to the present invention is prepared, and the prepared composition is applied, It can be suitably produced by providing a process of forming a pattern through exposure, development, and the like.

(C) Photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one photopolymerization initiator. This photopolymerization initiator is contained together with the radically polymerizable monomer described later when the dye-containing negative curable composition is constituted as a negative type. The photopolymerization initiator is not particularly limited as long as it can cause the radical polymerizable monomer described below to undergo a polymerization reaction, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

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

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

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

  Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1) Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho 2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4 7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine,

2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophen Le] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloro) Ethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B, etc.), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000) manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocur series (eg Darocur 1173, etc.),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, Also useful are 4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like.

  Among the above initiator types, oxime compounds are preferable, and 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime)- 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is most preferred.

  Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the dye-containing negative curable composition of the present invention. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned.

  The content of the photopolymerization initiator (including the other known photopolymerization initiators) in the dye-containing negative curable composition is based on the solid content (mass) of the (D) radical polymerizable monomer described later. 0.01 to 50% by mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable. When the content is in the above range, sufficient polymerization and curing can be performed, and polymerization does not proceed easily, and the polymerization rate increases but the molecular weight does not decrease and the film strength does not decrease. When the oxime compound and a photopolymerization initiator other than the oxime compound are used in combination, the amount of the oxime compound in the total amount of the photopolymerization initiator is preferably 30% by mass or more, more preferably 50% by mass or more. Further preferred.

Moreover, a sensitizer and a light stabilizer can be used in combination with the above photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. It is done.

(D) Radical polymerizable monomer The dye-containing negative curable composition of the present invention contains at least one radical polymerizable monomer. As the radically polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group is preferable. By containing the radical polymerizable monomer together with the (C) photopolymerization initiator, a negative curable composition can be formed.

  As the ethylenically unsaturated group, a (meth) acryloyl group is particularly preferable. The (meth) acryloyl group represents acryloyl or methacryloyl. Similarly, in the following, (meth) acrylate represents acrylate or methacrylate.

Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates described in JP-A-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, epoxy resin and (meth) acrylic Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids; and mixtures thereof. Furthermore, the Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.
Among the above, a polyfunctional (meth) acryl compound having two or more (meth) acryloyl groups is preferable from the viewpoint of improving the curing degree, and a polyfunctional (meth) acrylate is particularly preferable.

  The content of the radical polymerizable monomer in the dye-containing negative curable composition is preferably 1 to 60% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the composition. When the content is within the above range, a sufficient degree of curing and elution of the unexposed area can be maintained, and the degree of cure of the exposed area is not insufficient and the elution of the unexposed area is not significantly reduced.

(E) Organic solvent In preparing the dye-containing negative curable composition of the present invention, generally at least one organic solvent can be used. The organic solvent is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but especially considering the solubility, coating property, and safety of the alkali-soluble binder. In the present invention, a cyclic ketone solvent is preferably used.

  In preparing the dye-containing negative curable composition of the present invention, an embodiment using a mixed solvent containing at least two kinds of organic solvents is preferable, and other organic solvents other than the cyclic ketone solvent and the cyclic ketone solvent; An embodiment using a mixed solvent in combination with is more preferable. An embodiment in which a cyclic ketone solvent is used alone is also suitable.

  Examples of the cyclic ketone solvent include cyclopentanone, cyclohexanone, cycloheptanone, and the like, and cyclohexanone is particularly preferable.

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

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

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Preferable examples include ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like; aromatic hydrocarbons such as toluene and xylene.

  Of the above, other organic solvents used in combination with the cyclic ketone solvent are preferably ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and ethyl lactate. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

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

  In this invention, about the usage-amount of an organic solvent, the quantity from which a total solid content concentration of the dye-containing negative curable composition of this invention becomes 5-80 mass% is preferable from a coating property viewpoint, 5-60 mass% The amount which becomes is more preferable, and the amount which becomes 10 to 50% by mass is particularly preferable.

(H) Other component-crosslinking agent-
In the present invention, it is also possible to obtain a film that is further cured by using a cross-linking agent. In this case, it can comprise using at least 1 type of the crosslinking agent shown below.

  The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one group selected from melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one group selected from: (c) methylol group, alkoxymethyl group, and acyloxymethyl group Phenolic compounds, naphthol compounds, or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are particularly preferred.

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

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

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

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

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

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

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

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

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

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

  Examples of the skeletal compound in the crosslinking agent (c) include a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, trimethylol-3- Compound obtained by methoxymethylating one or two methylol groups of cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol Compounds obtained by methoxymethylating 1 to 3 methylol groups of bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishi Roxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound in which 1 to 5 methylol groups are methoxymethylated are naphthol compounds as bishydroxyl And methyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

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

  When the crosslinking agent (a) to (c) is contained, the total content of the crosslinking agent in the dye-containing negative curable composition varies depending on the material, but the solid content (mass) of the composition 1 to 70% by mass is preferable, 5 to 50% by mass is more preferable, and 7 to 30% by mass is particularly preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

-Various additives-
The dye-containing negative curable composition of the present invention includes various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, agglomerates. An inhibitor or the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

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

  The dye-containing negative curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display (LCD), a solid-state imaging device (for example, CCD, CMOS, etc.), a printing ink, It can be suitably used as a production application for ink-jet inks and paints.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used. The color filter of the present invention can be most preferably produced using the above-described dye-containing negative curable composition of the present invention. Specifically, the dye-containing negative curable composition is used as a support. By applying a coating composition such as spin coating, cast coating, roll coating and the like to form a radiation sensitive composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer, A negative colored pattern can be formed (image forming step). At this time, if necessary, a curing step for curing the formed colored pattern by heating and / or exposure can be provided.
In the present invention, the exposure is preferably performed by the stepper exposure described above.

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

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

  The developer used in the method for producing the color filter of the present invention is a developer that dissolves the uncured part of the dye-containing negative curable composition of the present invention, but has a composition that does not dissolve the cured part forming the filter. Anything can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the organic solvents described above used for preparing the dye-containing negative curable composition of the present invention.

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

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

(Examples 1-9 and Comparative Example 1)
1) Preparation of dye-containing negative curable composition The compounds having the compositions shown in Table 1 below are mixed and dissolved, and the dye-containing negative curable compositions (1) to (9) of the present invention and a comparative dye-containing composition are prepared. A negative curable composition (10) was prepared.

Details of the compositions (A) to (D) in Table 1 are as follows.
* Alkali-soluble binder / resin A: ACA250 (manufactured by Daicel Chemical Industries, Ltd.)
(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
-Resin B: ACA300 (manufactured by Daicel Chemical Industries, Ltd.)
(Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
Resin C: benzyl methacrylate / methacrylic acid copolymer (60/40 [= molar ratio])
* Radically polymerizable monomer / monomer A: Nippon Kayaku Co., Ltd., DPHA (main component: dipentaerythritol hexaacrylate)
* Organic Solvent-Soluble Dye The symbol of the exemplary compound described in the column of the organic solvent-soluble dye in the examples is the exemplary compound described above for the pigment represented by the general formula (C1), and the specific example number is the general formula (1 The quinophthalone dye represented by the above-described example compounds.
* Photopolymerization initiator TAZ-107: manufactured by Midori Chemical Co., Ltd. Oxime A: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione [Ciba Specialty・ Chemicals Co., Ltd.]
Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone [manufactured by Ciba Specialty Chemicals Co., Ltd.]

2) Preparation of glass substrate with undercoat layer A resist CT-2000L solution (manufactured by Fuji Film Arch Co., Ltd.) was applied on a silicon wafer substrate using a spin coater so as to have a film thickness of 2 μm, and was heated at 220 ° C. for 1 hour. A cured film (undercoat layer) was formed by heating and drying.

3) Exposure and development of dye-containing negative curable composition (image formation)
Using each of the dye-containing negative curable compositions obtained in 1) above in turn, a spin coater so that the film thickness becomes 1 μm on the undercoat layer of the glass substrate with the undercoat layer obtained in 2). It was applied and prebaked at 100 ° C. for 120 seconds.
Next, using an i-line reduction projection exposure apparatus, the coating film was irradiated with a wavelength of 365 nm through a mask having a line width of 2 μm while changing the exposure amount. After irradiation, the film was developed using a 60% CD-2000 (Fuji Film Arch Co., Ltd.) developer at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image (color filter). The formation of the image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

4) Evaluation The following evaluation was performed on each pattern image obtained using the dye-containing negative curable compositions (1) to (10). The evaluation results are shown in Table 2 below.
(1) Sensitivity In a 2 μm width pattern, the exposure amount at which the dot-space width is 1: 1 was defined as the appropriate exposure amount, and the exposure amount was defined as the sensitivity. Smaller values indicate higher sensitivity, indicating better sensitivity.

(2) Profile Using the SEM image at the appropriate exposure amount of (1) above, the cross-sectional shape of the pattern image is visually observed. A portion having a round shape was designated as “Δ”, and a round top shape was clearly designated as “X”.

(3) Non-exposed portion residue The pattern image was visually observed with the SEM image at the appropriate exposure amount described in (1), and no residue was found in the non-exposed portion. Although some inspections were recognized, those that were practically acceptable were marked with “Δ”, and those that clearly showed a residue in the non-exposed area were marked with “x”.

(4) Heat resistance Each of the dye-containing negative curable compositions is applied to a separately prepared glass substrate at a film thickness of 1 μm, and each coating film is brought into contact with the glass substrate side on a 200 ° C. hot plate. Placed and left for 1 hour. Then, the spectral change was measured using a spectrophotometer MS-1500 (manufactured by Shimadzu Corporation), and ΔE ^* ab was calculated using a color analysis program. The calculated value was used as an index for evaluating heat resistance. A smaller value indicates better heat resistance.

(5) Light resistance Each of the dye-containing negative curable compositions is coated on a separately prepared glass substrate at a film thickness of 1 μm, and each coated film is applied to a xenon irradiation weather meter SX75 (manufactured by Suga Test Instruments Co., Ltd.). For 20 hours (200,000 lux · h). Thereafter, the spectral change was measured using a spectrophotometer MS-1500 (manufactured by Shimadzu Corporation), ΔE ^* ab was calculated with a color analysis program, and the calculated value was used as an index for evaluating light resistance. . A smaller value indicates better light resistance.

  As shown in Table 2, in the examples using the phthalocyanine dye and the quinophthalone dye according to the present invention together, high sensitivity was obtained, and a pattern profile having a good rectangular cross section was formed in the exposed area, and no exposure There was no development residue in the part, and the formed pattern image showed excellent heat resistance and light resistance. On the other hand, in the comparative example in which the dye according to the present invention was not used in combination, the sensitivity was inferior to that of the example, and the cross-sectional shape of the formed pattern image was rounded to form a favorable rectangular shape. No development residue was formed in the non-exposed area. In addition, the formed pattern image is greatly inferior in terms of heat resistance and light resistance.

Claims (6)

A dye-containing negative curable composition containing at least (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, and (D) a radical polymerizable monomer, The organic solvent-soluble dye (B) includes at least one dye represented by the following general formula (C1) and at least one quinophthalone dye represented by the following general formula (1). A dye-containing negative curable composition.

[In the general formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, hydroxy Group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxy Carbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, or heterocyclic ring Represents a thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a 6-membered ring together with carbon atoms, and the four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents 0 or an integer of 1 to 5, and four cns may be the same or different. However, one of the cn represents an integer of 1 to 5, a plurality of Rc ₁ in the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1. ]

[In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ , or —S—R ⁶ , and R ¹ , R ^At least one of ² , R ³ , and 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. ]   The dye-containing negative curable composition according to claim 1, wherein the (C) photopolymerization initiator is an oxime compound.   The dye-containing negative curable 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.   The dye-containing negative curable composition according to any one of claims 1 to 3, further comprising an organic solvent, wherein the organic solvent contains a cyclic ketone solvent. A color filter comprising at least one dye represented by the following general formula (C1) and at least one quinophthalone dye represented by the following general formula (1).

[In the general formula (C1), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, hydroxy Group, aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxy Carbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, or heterocyclic ring Represents a thio group. Zc ₁ represents a nonmetallic atom group necessary for forming a 6-membered ring together with carbon atoms, and the four Zc ₁ may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, cn represents 0 or an integer of 1 to 5, and four cns may be the same or different. However, one of the cn represents an integer of 1 to 5, a plurality of Rc ₁ in the molecule may be the same or different. cr1, cr2, cr3 and cr4 represent 0 or 1, and satisfy cr1 + cr2 + cr3 + cr4 ≧ 1. ]

[In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ , or —S—R ⁶ , and R ¹ , R ^At least one of ² , R ³ , and 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 further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. ]   It has the process of applying through a mask after developing the dye-containing negative curable composition of any one of Claims 1-4 on a support body, and developing, and forming a pattern image. A method for producing a color filter.