JP2006058787A - Colored curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition having a good hue, high light and heat fastness and excellent temporal stability. <P>SOLUTION: The colored curable composition contains a compound represented by a general formula (C1) and a compound represented by a general formula Q, wherein Rc<SB>1</SB>represents halogen, an aliphatic group, aryl, a heterocyclic group, cyano, carboxyl, carbamoyl or the like; Zc<SB>1</SB>represents a group of nonmetallic atoms required to form a 6-membered ring; M represents two H atoms, a divalent metal atom, a divalent metal oxide or the like; cm represents 0 or 2; cn represents 0 or 1-5; cr1-cr4 each represent 0-1 (cr1+cr2+cr3+cr4≥1); and R<SP>301</SP>-R<SP>306</SP>each represents H or a substituent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  As a color filter formed on a device for colorizing a solid-state imaging device or a liquid crystal display device, a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to each other on the same plane of the substrate Known color filters include color filters, red filter layers, green filter layers, and blue filter layers. A band-like pattern or a mosaic pattern is formed by these filter layers.

  Various methods have been proposed so far for producing the color filter as described above. In particular, a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeatedly perform a patterning process a required number of times has been widely put into practical use.

  The color resist method is a method for producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which pigments are dispersed in various photosensitive compositions. This method uses pigments. It is stable to light, heat, and the like, and has a sufficient positional accuracy because it is patterned by a photolithography method, and is a suitable method for manufacturing a color filter for a large screen and a high-definition color display.

  When a color filter is produced by a pigment dispersion method in which a pigment is dispersed as described above, a coating film is formed by applying a radiation sensitive composition on a glass substrate using a spin coater or a roll coater. A colored pixel is obtained by pattern exposure and development, and a color filter is obtained by performing this operation in accordance with a desired number of hues. As a pigment dispersion method, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator in an alkali-soluble resin is known. (For example, see Patent Documents 1 to 8 and 12.)

  However, in recent years, further enhancement in definition has been desired for color filters for solid-state imaging devices. However, the conventional pigment dispersion system as described above does not improve the resolution, and also has problems such as color unevenness due to coarse pigment particles. Was not suitable for applications that required

Conventionally, the use of dyes has been proposed for such problems (see, for example, Patent Documents 9 to 10). There are also positive photosensitive compositions (see, for example, Patent Documents 11 to 12). However, the dye-containing curable composition has the following problems, and further improvement has been demanded. That is,
(1) Dyes are generally inferior in heat resistance, light resistance, etc. compared to pigments, and have insufficient fastness.
(2) When the molar absorption coefficient of the dye is low, a large amount of dye must be added. In this case, other compounds such as a polymerizable compound, a binder, and a photopolymerization initiator in the curable composition are added. The components must be relatively reduced, and the curability at the time of curing the composition, the heat resistance of the cured portion that has been cured, the developability of the non-cured portion, and the like are reduced.
(3) Dyes often interact with other components in the curable composition, and it is difficult to adjust the developability (solubility) of the cured part and the non-cured part.
As described above, the dyes conventionally used in the photosensitive composition are not particularly satisfactory in fastness, and further have low solubility in the photosensitive composition, so that they are in the liquid or coated. Dye may precipitate in the state of the film, and it is difficult to contain the dye at a high concentration.

  On the other hand, it is known that a yellow dye or a cyan dye is used for the green filter array of the color filter (see, for example, Patent Document 10). However, the combined use of the copper phthalocyanine dye and the pyridone azo dye used is insufficient in heat resistance and light resistance, and the copper phthalocyanine dye alone is insufficient in heat resistance and dye solubility. In any case, further improvement is desired. Further, phthalocyanine dyes containing specific amine substituents are also known (see, for example, Patent Document 14), but these dyes are also insufficient in heat resistance and light resistance, and further improvements are desired. ing.

Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 JP 2002-14223 A Japanese Patent Laid-Open No. 2002-14220 JP 7-286110 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, the color density and hue of a dye such as amber can be stably maintained. In particular, improvement of fastness such as heat resistance and light resistance of cyan dye and yellow dye has been an issue. In addition, since the dye has low solubility, improvement of dye precipitation due to low stability over time when it is in the state of a liquid preparation or a coated film is also an issue. .

  The present invention has been made in view of the above, and an object of the present invention is to provide a colored curable composition excellent in hue, heat fastness and light fastness, and excellent in stability over time. It is an object of the present invention to provide a color filter having good transmittance characteristics and excellent heat fastness and light fastness, and a method for producing a color filter that enables production of the color filter with high productivity. It is an object of the present invention to achieve.

  In the present invention, various dye compound derivatives having a good hue and high fastness to light and heat have been examined in detail. As a result, specific tetraazaporphyrin-based dyes (dyes) have particularly high heat resistance and light resistance. It is useful for improving fastness, and the combined use of this and a specific yellow dye has the knowledge that it is useful for improving the fastness and obtaining a good hue. A colored curable composition, a color filter, and a method for producing the same are provided, and the object is achieved.

Specific means for achieving the above object are as follows.
<1> A colored curable composition comprising at least one compound represented by the following general formula (C1) and at least one compound represented by the following general formula Q.

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, acylamino 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 heterocyclic 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 Q, R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , and R ³⁰⁶ each independently represent a hydrogen atom or a substituent, and when R ³⁰¹ to R ³⁰⁶ are adjacent to each other, , May be bonded to each other to form a 5-membered or 6-membered ring, and the ring may further have a substituent.

  <2> A color filter comprising at least one compound represented by the following general formula (C1) and at least one compound represented by the following general formula Q.

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, acylamino 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 heterocyclic 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 Q, R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , and R ³⁰⁶ each independently represent a hydrogen atom or a substituent, and when R ³⁰¹ to R ³⁰⁶ are adjacent to each other, , May be bonded to each other to form a 5-membered or 6-membered ring, and the ring may further have a substituent.

  <3> A method for producing a color filter, comprising: applying the colored curable composition according to the above <1> onto a support, exposing through a mask, and developing to form a pattern image. is there.

According to the present invention, a colored curable composition having a good hue, high heat fastness and light fastness, and excellent stability over time can be provided. Also,
According to the present invention, there are provided a color filter having good hue and transmittance characteristics and excellent heat fastness and light fastness, and a method for producing a color filter capable of producing the color filter with high productivity. Can do.

Hereinafter, the colored curable composition of the present invention, the color filter, and the production method thereof will be described in detail.
[Colored curable composition]
The colored curable composition of the present invention is also referred to as a compound represented by the following general formula (C1) and a compound represented by the general formula Q (hereinafter collectively referred to as “dyes according to the present invention”) as pigments. ), Preferably a binder, a radiation sensitive compound, and a polymerizable monomer. Moreover, it can generally comprise using a solvent, and it can comprise using other components, such as a crosslinking agent, as needed.
The colored curable composition of the present invention is particularly excellent in fastness by using the dye according to the present invention, and can also achieve high sensitivity, high resolution, and high transmittance characteristics.

  Regarding the general formula shown below, in the present specification, the term “aliphatic” means that the aliphatic moiety may be linear, branched, or cyclic, and may be saturated or unsaturated. It includes an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group, which may be unsubstituted or substituted with a substituent. Further, “aryl” in the present specification may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent. In the present specification, “heterocycle” means that the heterocycle moiety has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and is either a saturated ring or an unsaturated ring. Either a single ring or a condensed ring may be used, which may be unsubstituted or substituted with a substituent.

  In the present specification, the “substituent” may be any group that can be substituted, and examples thereof include aliphatic groups, aryl groups, heterocyclic groups, acyl groups, imide groups, azo groups, acyloxy groups, carbamoyloxy groups. Group, acylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic ring 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, heterocyclic amino group, aliphatic oxycarbonyl group Group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, nitro 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, diaryloxyphos Examples thereof include a finyl group.

-Compound represented by the general formula (C1)-
The colored curable composition of the present invention contains at least one compound represented by the following general formula (C1) (hereinafter also referred to as “phthalocyanine dye according to the present invention”). This dye exhibits a good cyan hue with high transmittance characteristics, has no stability over time when it is in the form of a liquid preparation or a coated film, and is particularly resistant to heat and light. Have
Hereinafter, the compound represented by formula (C1) will be described focusing on the description of each group.

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, acylamino 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 heterocyclic 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 from 3 to 15 carbon atoms A heterocyclic group having 3 to 10 carbon atoms is more preferable. 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 may be unsubstituted or substituted, and is preferably an aryloxycarbonyl group having 7 to 17 carbon atoms, and an aryloxycarbonyl group having 7 to 15 carbon atoms. A carbonyl group is more preferred. For example, a phenoxycarbonyl group etc. are mentioned.

The acyl group represented by Rc ₁ may be an aliphatic carbonyl group or an arylcarbonyl group, and when it represents an aliphatic carbonyl group, it may further have a substituent. 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. The aliphatic oxycarbonyloxy group is preferably an aliphatic oxycarbonyloxy group having 2 to 16 carbon atoms, preferably an aliphatic oxycarbonyloxy group having 2 to 12 carbon atoms, and an aliphatic group having 2 to 10 carbon atoms. An oxycarbonyloxy group is more preferred. Examples thereof include a methoxycarbonyloxy group and (t) butoxycarbonyloxy group.

The acylamino group represented by Rc ₁ may be unsubstituted or substituted, preferably an acylamino group having 2 to 15 carbon atoms, more preferably an acylamino group having 2 to 12 carbon atoms, An N-alkylacylamino group having 3 to 12 carbon atoms in total is particularly preferable. 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 in total, and a sulfamoylamino group having 0 to 12 carbon atoms in total. A famoylamino group is more preferred. Examples thereof include N, N-dimethylsulfamoylamino group and N, N-diethylsulfamoyl 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, an aliphatic thio group having 1 to 12 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 more preferable. 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 compounds represented by the general formula (C1), a compound represented by the following general formula (C1-1) (the dye according to the present invention) is preferable from the viewpoint of more effectively achieving the effects of the present invention. .

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, an aliphatic group, aryl group, heterocyclic group, acylamino 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, A hydroxy group, a cyano group, a sulfo group, a carboxyl group, a carbamoylamino group, a sulfamoylamino group, and a halogen atom, more preferably an aliphatic group, an N-alkylacylamino group, an aliphatic oxy group, and an aliphatic oxy Carbonyl group, aliphatic sulfonyl group, fat Thio, 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. Also, Rc _1, M, cm, cn and cr1, cr2, cr3, and cr4 in formula (C1-1) has the same meaning as the general formula (C1) definitive, preferable embodiments thereof are also the same.

  Among the compounds represented by the general formula (C1-1), the compound represented by the following general formula (C1-2) (the dye according to the present invention) from the viewpoint of more effectively achieving the effects of the present invention. Is more preferable.

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 formulas (C1) to (C1-2), from the viewpoint of more effectively achieving the effect of the present invention, the Rc ₁ is a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxy Carbonyl group, aryloxycarbonyl group, hydroxy group, aliphatic oxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, fat A preferable embodiment is an 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. An aliphatic group, a carbamoyl group, an aliphatic group Group oxycarbonyl group, aryloxycarbonyl group, aliphatic oxy Group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, imide And a carbamoyl group, aliphatic oxycarbonyl group, aliphatic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, aliphatic oxycarbonylamino group, arylsulfonyl group, imide group Or an aliphatic 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 in which the cp and cq are 0 is preferable in that the effects 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 that is Cu is most preferred,
Moreover, the aspect whose cm is 0 is preferable, the aspect whose cn is 1 or 2 is preferable, and the aspect whose cn is 1 is more preferable.

From the viewpoint of further effectively achieving the effect of the present invention, the Rc ₁ is a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, an aliphatic oxy group, Carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio A group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an imide group, or a sulfo group, the M is VO, Co, Cu, or Zn, the cq is 0, and the cm is 0. An embodiment in which the cn is 1 is preferable, and the Rc ₁ is an aliphatic group, Carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, aliphatic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, aryl A sulfonylamino 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 cp or cq is 0, More preferably, 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 compounds (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 compound (dye) represented by the general formula (C1) will be described in detail with reference to the following scheme, taking as an example 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.

-Compound represented by general formula Q-
The colored curable composition of the present invention includes at least one compound represented by the following general formula Q (hereinafter also referred to as “quinophthalone dye according to the present invention”) together with the compound represented by the general formula (C1). Containing.
Hereinafter, the compound represented by the general formula Q will be described in detail focusing on the description of each group.

In the general formula Q, R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , and R ³⁰⁶ each independently represent a hydrogen atom or a substituent. The substituent represented by R ^{301 to} R ³⁰⁶ may be any group that can be substituted, and includes the groups listed in the above-mentioned “Substituent” section, preferably each independently a halogen atom. Aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, Carbamoyloxy group, heterocyclic oxy group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, acylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino Group, aliphatic sulfonamido group, arylsulfonamido group, nitro group, aliphatic thio group, Thio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group.

When R ³⁰¹ to R ³⁰⁶ are adjacent to each other, that is, when a plurality of groups of R ³⁰¹ to R ³⁰⁶ have a positional relationship such as being bonded to adjacent carbon atoms, for example, A member or 6-membered ring may be formed, and the ring may further have a substituent. Examples of the 5-membered or 6-membered ring include a benzene ring, a naphthalene ring, a cyclohexane ring, a furan ring, and the like, which may further have a substituent. As long as they are substitutable groups.

Next, preferred substituents for R ^{301 to} R ³⁰⁶ will be described in more detail.
Examples of the halogen atom represented by R ^{301 to} R ³⁰⁶ include a fluorine atom, a chlorine atom, or a bromine atom.

The aliphatic group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. And the like, for example, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The total number of carbon atoms of the aliphatic group is preferably 1 to 30, more preferably 1 to 16, for example, methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl Group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4-sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.

The aryl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or may have a substituent. The total number of carbon atoms of the aryl group is preferably 6 to 30, and preferably 6 to 16. More preferably, specific examples include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group.

The heterocyclic group represented by R ^{301 to} R ³⁰⁶ may be saturated or unsaturated, and may be unsubstituted or have a substituent. The total number of carbon atoms of the heterocyclic group is preferably 1-30, more preferably 1-15, and specific examples include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2- Examples thereof include a benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.

The carbamoyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the carbamoyl group is preferably 1 to 30, preferably 1 to 16. More preferably, specific examples include a methylcarbamoyl group, a dimethylcarbamoyl group, a phenylcarbamoyl group, and an N-methyl-N-phenylcarbamoyl group.

The aliphatic oxycarbonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic oxycarbonyl group is preferably 2 to 30, more preferably 2 to 16, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group. Etc.

The aryloxycarbonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxycarbonyl group is preferably 7 to 30, It is preferably 7 to 16, and specific examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

The acyl group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonyl group, an arylcarbonyl group, or a heterocyclic carbonyl group. The total number of carbon atoms in the acyl group is preferably 1 to 30, more preferably 1 to 16, and specific examples include an acetyl group, a methoxyacetyl group, a thienoyl group, and a benzoyl group.

The aliphatic oxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic oxy group is preferably 1-30, more preferably 1-15, and specific examples include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy. Group, 3-carboxypropoxy group and the like.

The aryloxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxy group is preferably 6 to 30, It is more preferable that it is -16, and a phenoxy group, p-methoxyphenoxy group, o-methoxyphenoxy group, etc. are mentioned as a specific example.

The acyloxy group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonyloxy group, an arylcarbonyloxy group, or a heterocyclic carbonyloxy group, and the total number of carbon atoms of the acyloxy group is as follows: It is preferably 1 to 30, more preferably 1 to 16, and specific examples include an acetoxy group, a nicotinoyl group, and a benzoyloxy group.

The carbamoyloxy group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the carbamoyloxy group is preferably 1 to 30. It is more preferably ˜16, and specific examples include N-methylcarbamoyloxy group, dimethylcarbamoyloxy group, phenylcarbamoyloxy group and the like.

As the heterocyclic oxy group represented by R ^{301 to} R ³⁰⁶ , the heterocyclic moiety may be either saturated or unsaturated, and may be unsubstituted or have a substituent. The total number of carbon atoms of the heterocyclic oxy group is preferably 1-30, more preferably 1-15, and specific examples include 2-pyridyloxy group, 2-thienyloxy group, 2-thiazolyloxy. Group, 2-benzothiazolyloxy group, 2-benzoxazolyloxy group, 2-furyloxy group and the like.

The aliphatic amino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or may further have a substituent, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic amino group is preferably 1 to 30, more preferably 1 to 16, and specific examples include a methylamino group, a diethylamino group, a bis-2-ethoxyethylamino group, and N-methyl-N-2-methoxyethylamino group etc. are mentioned.

The arylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylamino group is preferably 6 to 30, It is more preferable that it is -16, and an anilino group, 4-methoxyphenylamino group, etc. are mentioned as a specific example.

The heterocyclic amino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or may further have a substituent, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms in the heterocyclic amino group is preferably 1-30, more preferably 1-16, and specific examples include 2-pyridylamino group, 2-thienylamino group, 2-thiazolylamino group, And 2-benzothiazolyloxy group and the like.

The acylamino group represented by R ^{301 to} R ³⁰⁶ may be an aliphatic carbonylamino group, an arylcarbonylamino group, or a heterocyclic carbonylamino group, and the total number of carbon atoms of the acylamino group is as follows: It is preferably 2 to 30, more preferably 2 to 16, and specific examples include acetylamino group, propionylamino group, benzoylamino group, N-phenylacetylamino group, and 3,5-disulfobenzoylamino. Groups and the like.

The carbamoylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the carbamoylamino group is preferably 1 to 30, It is more preferable that it is 1-16, and a dimethylcarbamoylamino group, a phenylcarbamoylamino group, etc. are mentioned as a specific example.

The sulfamoylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the sulfamoylamino group is 0 to 30. It is preferably 0 to 30, and specific examples include a sulfamoylamino group and an N, N-dipropylsulfamoylamino group.

The aliphatic oxycarbonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic oxycarbonylamino group is preferably 1-30, more preferably 1-16, and specific examples include a methoxycarbonylamino group and a methoxyethoxycarbonylamino group. .

The aryloxycarbonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the aryloxycarbonylamino group is 7 to 30. It is preferably 7 to 18, and specific examples include a phenoxycarbonylamino group and a 3-chlorophenoxycarbonylamino group.

The aliphatic sulfonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic sulfonylamino group is preferably 1-30, more preferably 1-16, and specific examples include methanesulfonylamino group, N-phenylmethanesulfonylamino group, benzenesulfonyl. An amino group, 3-carboxybenzene sulfonylamino group, etc. are mentioned.

The arylsulfonylamino group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylsulfonylamino group is 6 to 30. Preferably, it is 6-18, and a benzenesulfonylamino group, a toluene sulfoneamino group, etc. are mentioned as a specific example.

The aliphatic thio group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic thio group is preferably 1 to 30, more preferably 1 to 16, and specific examples include methylthio group, (t) butylthio group, and ethoxyethylthio group. Can be mentioned.

The arylthio group represented by R ^{301 to} R ³⁰⁶ may have a substituent, and the total number of carbon atoms of the arylthio group is preferably 6 to 30, and preferably 6 to 18. It is more preferable that specific examples include phenylthio group and 4-methylphenylthio group.

As the heterocyclic thio group represented by R ^{301 to} R ³⁰⁶ , the heterocyclic moiety may be either saturated or unsaturated, and may be unsubstituted or have a substituent. The total number of carbon atoms of the heterocyclic thio group is preferably 1-30, more preferably 1-15, and specific examples include 2-pyridylthio group, 2-thienylthio group, 2-thiazolylthio group, Examples include 2-benzothiazolylthio group, 2-benzoxazolylthio group, and 2-furylthio group.

The aliphatic sulfonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. The total number of carbon atoms of the aliphatic sulfonyl group is preferably 1 to 30, more preferably 1 to 16, and specific examples include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group. Can be mentioned.

The arylsulfonyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the arylsulfonyl group is preferably 6 to 30, It is more preferable that it is 6-18, and a benzenesulfonyl group, a toluenesulfonyl group, etc. are mentioned as a specific example.

The sulfamoyl group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and the total number of carbon atoms of the sulfamoyl group is preferably 0 to 30, 16 is more preferable, and specific examples include a sulfamoyl group, a dimethylsulfamoyl group, and a di- (2-hydroxyethyl) sulfamoyl group.

The imide group represented by R ^{301 to} R ³⁰⁶ may be unsubstituted or substituted, and is preferably a 5- to 6-membered imide group, and the total number of carbon atoms is preferably 4 to 30. More preferably, it is 4-20. Specific examples include a succinimide group and a phthalimide group.

Among the above, R ³⁰¹ and R ³⁰² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryl, in that the effects of the present invention can be effectively achieved. An embodiment that is an oxycarbonyl group or a carbamoyl group is preferable, and an embodiment in which a 6-membered ring is formed together with carbon atoms that are bonded to each other and bonded to R ³⁰¹ or R ³⁰² is more preferable.
Similarly, R ³⁰³ is a hydrogen atom, a halogen atom, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, an aliphatic sulfonamido group, or an arylsulfonamido group in that the effect of the present invention can be effectively obtained. A preferred embodiment is a hydrogen atom, a halogen atom, an acylamino group, an aliphatic sulfonamido group, or an arylsulfonamido group, and a most preferred embodiment is a hydrogen atom.
Similarly, from the viewpoint that the effects of the present invention can be effectively achieved, the embodiment in which R ³⁰⁴ is a hydroxy group or an aliphatic oxy group is more preferable, and the embodiment in which it is a hydroxy group is most preferable.
Similarly, R ³⁰⁵ and R ³⁰⁶ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryl, in that the effects of the present invention can be effectively achieved. An embodiment that is an oxycarbonyl group or a carbamoyl group is preferable, and an embodiment in which a 6-membered ring is formed together with carbon atoms that are bonded to each other and bonded to R ³⁰⁵ or R ³⁰⁶ is more preferable.

  Among the compounds represented by the general formula Q, a compound (dye) represented by the following general formula (Q1) is preferable from the viewpoint of more effectively achieving the effects of the present invention.

In the general formula (Q1), R ³⁰⁷ and R ³⁰⁸ each independently represent a substituent, and m and n each independently represent an integer of 0 to 4. R ³⁰³ and R ³⁰⁴ in general formula (Q1) have the same meanings as R ³⁰³ and R ³⁰⁴ in general formula Q described above, respectively.

The substituent represented by R ³⁰⁷ or R ³⁰⁸ may be any substituent as long as it is a substitutable group, and examples thereof include the groups listed in the above-mentioned “Substituent” section. It includes the same groups as the preferred substituents as R ³⁰¹ to R ³⁰⁶ in the general formula Q predicates.

In the general formula (Q1), R ³⁰³ is preferably a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group. Alternatively, an embodiment that is a halogen atom is more preferable, and as R ³⁰⁴ , an embodiment that is a hydrogen atom, a hydroxy group, or an aliphatic oxy group is preferable, and an embodiment that is a hydroxy group is more preferable.

In the general formula (Q1), R ³⁰⁷ is a halogen atom, an aliphatic group, an aliphatic oxy group, an aryloxy group, an aliphatic oxycarbonyl group, an aryloxy group in that the effect of the present invention can be effectively achieved. A preferred embodiment is a carbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, an aliphatic thio group, an arylthio group, an imide group, an aliphatic carbonylamino group, an acylamino group, or an aliphatic sulfonamide group, A more preferable embodiment is a halogen atom, aliphatic group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, sulfamoyl group, aliphatic thio group, imide group, aliphatic carbonylamino group, or aliphatic sulfonamido group. . Similarly, in terms of the effect of the present invention, in the general formula (Q1), R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl. Group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic thio group, arylthio group, or acylamino group is preferred, and halogen atom, aliphatic group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl The aspect which is group, an aliphatic thio group, or an arylthio group is still more preferable.
Similarly, in the general formula (Q1), m is preferably 0 or 1, and n is preferably 1 or 2 from the viewpoint of the effect of the present invention.

In the general formula (Q1), the R ³⁰³ is a hydrogen atom or a halogen atom, and the R ³⁰⁴ is a hydrogen atom, a hydroxy group, or an aliphatic oxy group in that it is particularly effective for the effect of the present invention. R ³⁰⁷ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, fatty acid An aromatic thio group or an arylthio group, wherein R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, An arylsulfonyl group, a sulfamoyl group, an aliphatic thio group, an arylthio group, or an acylamino group, The embodiment in which m is 0 or 1 and n is 1 or 2 is preferable.

Furthermore, in terms of the effects of the present invention, R ³⁰³ is a hydrogen atom or a halogen atom, R ³⁰⁴ is a hydroxy group, and R ³⁰⁷ is a halogen atom, an aliphatic group, an aliphatic oxycarbonyl group. Carbamoyl group, aliphatic sulfonyl group, sulfamoyl group, or aliphatic thio group, wherein R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aryloxy group, aliphatic oxycarbonyl group, aryloxycarbonyl Preferred is an embodiment in which m is 0 or 1, and n is 1 or 2, which is a group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic thio group, arylthio group, or acylamino group. .

Still further, in terms of the effects of the present invention, R ³⁰³ is a hydrogen atom, R ³⁰⁴ is a hydroxy group, and R ³⁰⁷ is a halogen atom, an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group. Group, aliphatic sulfonyl group, sulfamoyl group, or aliphatic thio group, wherein R ³⁰⁸ is a halogen atom, aliphatic group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, sulfamoyl group A preferred embodiment is a group, an aliphatic thio group, or an arylthio group, wherein the m is 0 or 1, and the n is 1 or 2.

  Hereinafter, specific examples of the compound represented by the general formula Q or the general formula (Q1) [Exemplary compounds ya-1 to ya-9, yb-1 to yb-9, yc-1 to yc-9, yd-1 ~ Yd-9, ye-1 to ye-9, yf-1 to yf-2, and yg-1 to yg-4]. However, the present invention is not limited to these examples.

  Examples of the synthesis of the quinophthalone dye represented by the general formula Q or the general formula (Q1) include a synthesis method described in JP-A-6-9891, but are not limited thereto. It is not a thing.

  The total concentration of the dye according to the present invention in the colored curable composition varies depending on the molecular weight and molar extinction coefficient, but is preferably 0.5 to 80% by mass relative to the total solid components of the composition. 5 to 60% by mass is more preferable, and 0.5 to 50% by mass is particularly preferable.

  The phthalocyanine dye and quinophthalone dye according to the present invention described above are used for solid-state image pickup devices such as CCDs and CMOSs, color filters for recording and reproducing color images used for displays such as LCDs and PDPs, and the like. It can utilize suitably for the curable composition for producing.

  The color filter of the present invention uses the dye according to the present invention, that is, two or more pigments including at least one compound represented by the general formula (C1) and at least one compound represented by the general formula Q. Can be produced by any method, for example, a colored curable composition containing the pigment according to the present invention is prepared, and the prepared colored curable composition is applied onto a support. Equal, expose through a mask, develop, and in the case of negative type, for example, a process of forming a pattern image by removing an uncured portion (unexposed portion) (if necessary, a color filter so as to obtain a desired hue The color filter of the present invention can be suitably produced by repeating the process for a desired number of hues constituting the above. Details will be described later.

-Binder-
The colored curable composition of the present invention can contain at least one binder. The 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 morpholinylethyl group Monomers containing are also useful.

From the viewpoint of improving the crosslinking efficiency, a polymer group having a polymerizable group in the side chain and a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain are also useful. Examples of the polymer having a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
From the viewpoint of increasing the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Of the various binders described above, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of control of developability. An acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable. Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS resist-106 (Osaka Organic Chemical Industry). And Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).

Moreover, an alkali-soluble phenol resin can also be used as a binder in the present invention. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is configured as a positive type, and examples thereof include novolak resins and vinyl polymers.
Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Phenols can be used alone or in combination of two or more. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.

  Specific examples of the novolak resin include a condensation product of metacresol, paracresol, or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution using means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder preferably has a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and more preferably 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.

  As content in the colored curable composition of this invention of a binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% Is particularly preferred.

-Crosslinking agent-
While the present invention uses the dye according to the present invention described above, the curing reaction of the film proceeds to a higher degree than before, and a film having good curability can be obtained. It is also possible to obtain a more highly cured film using a crosslinking agent. This is useful from the viewpoint of achieving high resolution of the colored curable composition of the present invention.

  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 is crosslinkable. For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol di Divalent glycidyl group-containing low molecular weight compounds such as glycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, as well as trimethylolpropane triglycidyl ether , Trivalent glycidyl group-containing low molecular weight compounds typified by trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, Tetravalent glycidyl group-containing low molecular weight compounds typified by ruether, tetramethylol bisphenol A tetraglycidyl ether and the like, as well as polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether Glycidyl group-containing polymer compounds represented by polyglycidyl (meth) acrylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and the like, Etc.

  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 (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, 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 trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol A, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl 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 it contains a crosslinking agent in the present invention, the total content of the crosslinking agents (a) to (c) in the colored curable composition varies depending on the material, but relative to 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.

-Polymerizable monomer-
The colored curable composition of the present invention can be suitably constituted by containing at least one polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is configured as a negative type. In addition, it can further contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more.
This polymerizable monomer is useful in that it can achieve high sensitivity and high resolution of the colored curable composition of the present invention by using it together with a photopolymerization initiator described later. Hereinafter, the polymerizable monomer will be described.

  As the polymerizable monomer, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52- Examples include polyester acrylates described in each publication of No. 30490, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, 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.

  The content of the polymerizable monomer in the colored curable composition is preferably 0.1 to 90 mass%, more preferably 1.0 to 80 mass% with respect to the solid content of the composition, and 2.0 -70 mass% is especially preferable.

-Radiosensitive compounds-
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as radical generation, acid generation, base generation, etc., against radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film is alkali-developed by insolubilizing the above-mentioned alkali-soluble resin by reactions such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of making it insoluble in liquid.
This radiation sensitive compound is useful from the viewpoint of achieving high sensitivity and high resolution of the colored curable composition of the present invention.

  When the colored curable composition is configured as a negative type, it contains a photopolymerization initiator, and when it is configured as a positive type, it contains a naphthoquinone diazide compound as an essential component.

~ Photoinitiator etc. ~
First, a photopolymerization initiator used in the case of forming a negative type will be described. The photopolymerization initiator is not particularly limited as long as it can cause the polymerization monomer (a monomer having a polymerizable group) to undergo a polymerization reaction, but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. It is preferable. In addition, you may further contain in the positive type | system | group containing a naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

  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 369, Irgacure 784, Irgacure 651, Irgacure 184) manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocure series (eg Darocure 1173 etc.),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4- Morpholinobyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4 , 5-Diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer , 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, etc. are also useful.

  Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the colored 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 A carbonyl compound, an acyloin ether described in US Pat. No. 2,448,828, an aryl acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, Polynuclear quinone compounds described in Japanese Patent Nos. 3,046,127 and 2,951,758, 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 in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content (mass) of the polymerizable monomer. 1-20 mass% is especially preferable. When the content is less than 0.01% by mass, the polymerization may be difficult to proceed. When the content exceeds 50% by mass, the polymerization rate is increased, but the molecular weight is decreased and the film strength may be decreased.

A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, etc., Tinuvin 1130, 400, etc. Is mentioned.

  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-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

~ Naphthoquinonediazide compound ~
Next, the naphthoquinone diazide compound used in the case of constituting the positive type will be described. The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group, such as o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4-sulfone. Acid ester, o-naphthoquinonediazide-4-sulfonic acid amide, and the like. These esters and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  In addition, when the colored curable composition is constituted as a positive type, the binder and the crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, of the total solid content added to the solvent. It is preferable to dissolve at a ratio of In addition, the contents of the naphthoquinone diazide compound and the dye are preferably about 2 to 30% by mass and about 2 to 50% by mass, respectively, with respect to the mass of the solution in which the binder and the crosslinking agent are dissolved. .

-Solvent-
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent is not particularly limited as long as the solubility of each component and the coating property of the colored curable composition are satisfied, but it is particularly preferable to select the solvent in consideration of the solubility, coating property, and safety of the binder.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, 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 methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aryl compounds such as toluene and xylene are preferred. Be

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

-Various additives-
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. 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 colored curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid 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; aryl monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid Aryl polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenyl And other carboxylic acids such as acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid .

  The colored 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, and an inkjet ink. And can be suitably used as a production application for paints and the like.

<< 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 colored curable composition of the present invention is used. The color filter of the present invention uses the above-described colored curable composition of the present invention, and this colored curable composition is applied to a support by a coating method such as spin coating, cast coating, roll coating, etc. It can be most suitably produced by forming a radiation composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer to form a negative or positive colored pattern ( 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. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used. In addition, when the colored curable composition is configured as a positive type, a step of post-baking the colored pattern after the image forming step can be provided.

  In the production of a color filter, in the case of a negative type, the image forming step (and a curing step if necessary) is repeated according to a desired number of hues. In the case of a positive type, the image forming step and post-baking are performed. By repeating according to the desired number of hues, a color filter configured with a desired number of hues can be produced.

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.

  As the developer used in the method for producing the color filter of the present invention, the portion of the colored curable composition of the present invention to be developed and removed (for example, the uncured portion in the case of a negative type) is dissolved while the filter is cured. Any part can be used as long as it has a composition that does not dissolve. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used for preparation of the colored curable composition of this invention can be mentioned.

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

  The color filter of the present invention can be used for a solid-state 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. Unless otherwise specified, “part” is based on mass.

Example 1
1) Preparation of resist solution (negative type)
Propylene glycol monomethyl ether acetate 5.20 parts (PGMEA)
-Ethyl lactate (EL)-52.6 parts-Binder-30.5 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (copolymerization ratio [molar ratio] = 60) / 20/20) 41% EL solution]
Dipentaerythritol hexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant 0.80 parts (F-475, Dainippon Ink Chemical Industry Co., Ltd.)
-TAZ-107 (manufactured by Midori Chemical Co., Ltd .; photopolymerization initiator): 0.58 parts were mixed and dissolved to prepare a resist solution.

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C./20 minutes). Next, the resist solution obtained in 1) above was applied onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to form a cured film (undercoat layer). .

3) Preparation of dye resist solution (colored curable composition [negative type]) 9.4 g of resist solution obtained in the above 1) and the exemplified compound C-1 described above which is a dye according to the present invention [the above general Compound represented by formula (C1)] 0.75 g and exemplified compound ya-1 [compound represented by general formula Q] 0.35 g are mixed and dissolved to prepare a dye resist solution (colored curable composition). [Negative type solution] was prepared.

4) Exposure and development of dye resist solution (image formation)
The dye resist solution obtained in 3) above was applied on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1.0 μm. Pre-baked for 120 seconds.
Then, using an exposure apparatus, the coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 20 μm with an exposure amount of 500 mJ / cm ² . After irradiation, development was performed using a developer CD-2000 (manufactured by Fuji Film Arch Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.
As described above, a green pattern suitable as the green color constituting the color filter was obtained.

5) Evaluation The storage stability of the dye resist solution prepared above over time, and the heat resistance and light resistance of the coating film coated on the glass substrate using the dye resist solution were evaluated as follows. The evaluation results are shown in Table 1 below.
-Storage stability over time-
After the dye resist solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters in the solution was visually evaluated according to the following criteria.
[Criteria]
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

-Heat resistance-
The glass substrate coated with the dye resist solution is placed on a 200 ° C. hot plate so as to be in contact with the substrate surface, heated for 1 hour, and then heated by a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The color difference (ΔEab value) was measured as an index for evaluating heat resistance and evaluated according to the following criteria. The ΔEab value indicates that the smaller the value, the better the heat resistance.
[Criteria]
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

-Light resistance-
A glass substrate coated with a dye resist solution is irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and then the color difference (ΔEab value) before and after irradiation is measured to increase the light resistance. As an index to be evaluated, evaluation was performed according to the following criteria. The ΔEab value indicates that the smaller the value, the better the light resistance.
[Criteria]
○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
×: ΔEab value> 10

(Examples 2 to 10)
A green pattern was formed in the same manner as in Example 1 except that the dye according to the present invention was changed as shown in Table 1 below (but equimolar) in “3) Preparation of dye resist solution” in Example 1. Further, the same evaluation was performed. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-2)
In “3) Preparation of dye resist solution” in Example 1, a comparative green pattern was prepared in the same manner as in Example 1 except that the dye according to the present invention was changed as shown in Table 1 below (but equimolar). And the same evaluation was performed. The evaluation results are shown in Table 1 below together with the results of the examples.

  As shown in Table 1 above, in the examples using the dyes according to the present invention, the dye resist solution (colored curable composition) prepared in a solution state was compared to the comparative examples using other dyes. All were excellent in storage stability over time, and the green pattern formed using this dye resist solution exhibited good heat resistance and light resistance.

(Example 11)
1) Preparation of colored curable composition [positive type] The following composition was mixed and dissolved to prepare a colored curable composition [positive type] in the form of a solution.
・ Ethyl lactate (EL): 30 parts ・ Resin P-1: 3.0 parts ・ Naphthoquinonediazide compound N-1: 1.8 parts ・ Hexamethoxymethylolated melamine (crosslinking agent) 0.6 parts TAZ-107 (manufactured by Midori Chemical Co .; photoacid generator) ... 1.2 parts F-475 ... 0.0005 parts (fluorine-based surfactant; Dainippon Ink and Chemicals, Inc.) Industrial)
-Illustrative compound C-6 of the dye according to the present invention 1.5 parts (compound represented by formula (C1))
-Illustrative compound ya-4 of the dye according to the present invention 0.7 part (compound represented by general formula Q)

-Synthesis of Resin P-1-
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl, and 600 g of 2-methoxypropanol, and attached with a stirrer, a reflux condenser, and a thermometer under a nitrogen stream. A polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L (liter) of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When this molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

-Synthesis of naphthoquinonediazide compound N-1-
Trisp-PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask, and 24.44 g of triethylamine was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water with stirring. Precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive naphthoquinone diazide compound N-1.

2) Exposure and development of colored curable composition (image formation)
A glass substrate with an undercoat layer was prepared in the same manner as in Example 1, and the colored curable composition prepared as described above was applied onto the glass substrate with an undercoat layer, prebaked, irradiated, Development, rinsing, and spray drying were performed to obtain a green pattern, and then this pattern was heated at 180 ° C. for 5 minutes (post-bake). The formed green pattern showed a good rectangular profile.

  Subsequently, when the storage stability of the dye resist solution prepared above and the heat resistance and light resistance of the coating film coated on the glass substrate using the dye resist solution were evaluated in the same manner as in Example 1, As in the case of the negative type, storage stability, light resistance, and heat resistance were all good.

(Examples 12 to 21)
Except having replaced the glass substrate of Examples 1-10 with the silicon wafer substrate, operation similar to Example 1-10 was performed and the coating film was coated on the silicon wafer substrate. Next, a 2 μm square pattern is exposed at an exposure amount of 500 mj / cm ² using an i-line reduction projection exposure apparatus, and a developer obtained by diluting CD-2000 (manufactured by Fuji Film Arch) to 60% is used. Developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As described above, a pattern suitable as a CCD color filter having a substantially square cross section and a good profile could be obtained.

Claims (3)

A colored curable composition comprising at least one compound represented by the following general formula (C1) and at least one compound represented by the following general formula Q.

[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, acylamino 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 heterocyclic 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 Q, each of R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , and R ³⁰⁶ independently represents a hydrogen atom or a substituent, and when R ³⁰¹ to R ³⁰⁶ are in adjacent positions, , May be bonded to each other to form a 5-membered or 6-membered ring, and the ring may further have a substituent. ] A color filter comprising at least one compound represented by the following general formula (C1) and at least one compound represented by the following general formula Q.

[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, acylamino 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 heterocyclic 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 Q, each of R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , and R ³⁰⁶ independently represents a hydrogen atom or a substituent, and when R ³⁰¹ to R ³⁰⁶ are in adjacent positions, , May be bonded to each other to form a 5-membered or 6-membered ring, and the ring may further have a substituent. ]   A method for producing a color filter, comprising: applying a colored curable composition according to claim 1 onto a support, exposing the film through a mask, and developing to form a pattern image.