JP2006071822A - Colored hardenability composition, color filter, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored hardenability composition, having high sensitivity, high resolution and high transmission characteristics, superior hue, high optical solidity and high heat solidity, and to provide a color filter that uses it and its manufacturing method. <P>SOLUTION: In the colored hardenability composition, the color filter and its manufacturing method, at least one from among colorings denoted by general formula (C1), and at least one selected from among colorings denoted by general formula (P) are included. However, substituents in the above general formulae (C1) and (P) have specific definition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a color filter suitable for a liquid crystal display element and a solid-state image sensor, a method for producing the same, and a colored curable composition suitable for forming the color filter.

  Conventionally, 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 on a substrate There are known color filters composed of the above, and a color filter composed of a red filter layer, a green filter layer, and a blue filter layer. Each of these filter layers is formed with a band-like pattern or a mosaic pattern. Various methods have been proposed for producing color filters. In particular, a so-called color resist method is widely used in which a photosensitive resin composition containing a dye is exposed and developed to repeat a patterning process a required number of times.

  The color resist method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments, and has sufficient positional accuracy for patterning by photolithography, and is suitable for producing color filters for large screens and high-definition color displays. Is the method.

  According to the pigment dispersion method, a radiation-sensitive composition is applied onto a glass substrate using a spin coater, a roll coater, or the like, and after forming a coating film, the coating film is subjected to pattern exposure and developed. By forming this pixel and performing this operation for each color, a color filter is obtained. As said pigment dispersion method, the negative photosensitive composition using a photopolymerizable monomer and a photoinitiator for alkali-soluble resin is disclosed (for example, refer patent documents 1-9).

  On the other hand, in recent years, for use in a solid-state imaging device, further enhancement of the color filter has been desired. However, the conventional pigment dispersion system has a problem that the resolution is not improved and color unevenness occurs due to coarse particles of the pigment, so that a fine pattern like a solid-state image sensor is required. Not suitable for use. In order to solve these problems, the use of a dye instead of a pigment has been conventionally proposed (for example, see Patent Documents 10 and 11). As such a photosensitive composition, a positive photosensitive composition has also been proposed (see, for example, Patent Documents 9 and 12 below).

However, the curable composition containing a dye has the following problems, and further improvements are required.
(I) Dyes are generally inferior in heat resistance, light resistance and the like as compared with pigments, and further improvement in fastness is required.
(Ii) If the molar absorption coefficient of the dye is low, a large amount of dye must be added, and for this purpose other components such as polymerizable compounds, binders and photopolymerization initiators in the curable composition Therefore, there is a problem that the curability of the composition, the heat resistance after curing, the developability of the non-cured portion, and the like are lowered, and an improvement thereof is desired.
(Iii) Dyes often exhibit interaction 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. It has been demanded.

  Thus, the dyes conventionally used in photosensitive compositions are not particularly satisfactory in terms of fastness. Furthermore, the solubility in the photosensitive composition is low, and it is difficult to contain a dye at a high concentration, and these improvements have been demanded.

  On the other hand, it is known that a yellow dye is used for the green and red filter portions of the color filter (see, for example, Patent Document 13). However, the combined use of a copper phthalocyanine dye and a pyridone azo dye has insufficient heat resistance and light resistance, and further improvement is desired. Further, copper phthalocyanine dyes have low heat resistance even when used alone, and further have low solubility in solvents, so that improvement is desired. Furthermore, phthalocyanine dyes containing specific amine substituents are also known, but these are also insufficient in heat resistance and light resistance, and further improvements are desired (for example, see Patent Document 14). .)

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 2002-14223 A JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 Japanese Patent Laid-Open No. 2002-14220 JP 7-286110 A

  As described above, in applications such as solid-state imaging devices that require high definition and color uniformity, a curable composition containing a dye is useful, but the discoloration, the color density of the dye, and the hue are adjusted. It has not yet been able to be held stably, and 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 these dyes have low solubility, improvement of dye precipitation due to low stability over time when a liquid preparation or a coating film is formed by coating is also an issue.

  The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a colored curable composition having a good hue, high light fastness and heat fastness and excellent stability over time. . The present invention also provides a color filter having high resolution and high transmittance characteristics, high light fastness and high heat fastness, and a method for producing a color filter capable of producing the color filter with high productivity. It is an object of the present invention to provide the object and to achieve the object.

  The present inventors have examined in detail various dye compound derivatives having a good hue and high fastness to light and heat. As a result, certain tetraazaporphyrin-based dyes (dyes) are particularly resistant to heat and Based on this finding, the inventors have obtained a colored curable composition, a color filter, and a method for producing the same that are useful for improving fastness such as light resistance. Specific means for achieving the above object are as follows.

  <1> A colored curable composition comprising at least one dye represented by the following general formula (C1) and at least one selected from the dye represented by the following general formula (P). It is a composition.

〔一般式（Ｃ１）中、Ｒｃ₁は、ハロゲン原子、脂肪族基、アリール基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、脂肪族オキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、脂肪族オキシ基、アリールオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、脂肪族オキシカルボニルオキシ基、アシルアミノ基、カルバモイルアミノ基、スルファモイルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族スルホニルアミノ基、アリールスルホニルアミノ基、脂肪族チオ基、アリールチオ基、脂肪族スルホニル基、アリールスルホニル基、スルファモイル基、スルホ基、イミド基またはヘテロ環チオ基を表す。Ｚｃ₁は該炭素原子と共に６員環を形成するに必要な非金属原子群を表し、４つのＺｃ１は同一であっても異なっていてもよい。Ｍは２個の水素原子、２価の金属原子、２価の金属酸化物、２価の金属水酸化物、または２価の金属塩化物を表す。ｃｍは０、１または２を表し、ｃｎは０または１〜５の整数を表す。４つのｃｎは同一でも異なってもよい。但し、ｃｎの１つは１〜５の整数を表し、分子中の複数のＲｃ₁は同一でも異なっていてもよい。ｃｒ１、ｃｒ２、ｃｒ３およびｃｒ４は０または１を表し、ｃｒ１＋ｃｒ２＋ｃｒ３＋ｃｒ４≧１を満たす。〕

[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, An aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a non-metallic atomic group necessary for forming a 6-membered ring together with the carbon atom, four Zc1 may or may not be the same. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, and cn represents 0 or an integer of 1 to 5. The 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. ]

〔一般式（Ｐ）中、Ｒ³⁰¹およびＲ³⁰²は、各々独立して、水素原子または置換基を表す。Ｒ³⁰³は、水素原子、脂肪族基、アリール基、ヘテロ環基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基、アリールスルホニル基またはスルファモイル基を表す。これらは更に置換基によって置換されていてもよい。Ｑはジアゾ成分残基を表す。一般式（Ｐ）で表される色素は、任意の位置で２量体以上の多量体を形成してもよい。〕

[In General Formula (P), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or a substituent. R ³⁰³ represents a hydrogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. These may be further substituted with a substituent. Q represents a diazo component residue. The dye represented by formula (P) may form a dimer or higher multimer at an arbitrary position. ]

〔一般式（Ｃ１）中、Ｒｃ₁は、ハロゲン原子、脂肪族基、アリール基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、脂肪族オキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、脂肪族オキシ基、アリールオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、脂肪族オキシカルボニルオキシ基、アシルアミノ基、カルバモイルアミノ基、スルファモイルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族スルホニルアミノ基、アリールスルホニルアミノ基、脂肪族チオ基、アリールチオ基、脂肪族スルホニル基、アリールスルホニル基、スルファモイル基、スルホ基、イミド基またはヘテロ環チオ基を表す。Ｚｃ₁は該炭素原子と共に６員環を形成するに必要な非金属原子群を表し、４つのＺｃ１は同一であっても異なっていてもよい。Ｍは２個の水素原子、２価の金属原子、２価の金属酸化物、２価の金属水酸化物、または２価の金属塩化物を表す。ｃｍは０、１または２を表し、ｃｎは０または１〜５の整数を表す。４つのｃｎは同一でも異なってもよい。但し、ｃｎの１つは１〜５の整数を表し、分子中の複数のＲｃ₁は同一でも異なっていてもよい。ｃｒ１、ｃｒ２、ｃｒ３およびｃｒ４は０または１を表し、ｃｒ１＋ｃｒ２＋ｃｒ３＋ｃｒ４≧１を満たす。〕 <2> A color filter comprising at least one dye represented by the following general formula (C1) and at least one selected from dyes represented by the following general formula (P). .

[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, An aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a non-metallic atomic group necessary for forming a 6-membered ring together with the carbon atom, four Zc1 may or may not be the same. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, and cn represents 0 or an integer of 1 to 5. The 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. ]

〔一般式（Ｐ）中、Ｒ³⁰¹およびＲ³⁰²は、各々独立して、水素原子または置換基を表す。Ｒ³⁰³は、水素原子、脂肪族基、アリール基、ヘテロ環基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基、アリールスルホニル基またはスルファモイル基を表す。これらは更に置換基によって置換されていてもよい。Ｑはジアゾ成分残基を表す。一般式（Ｐ）で表される色素は、任意の位置で２量体以上の多量体を形成してもよい。〕

[In General Formula (P), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or a substituent. R ³⁰³ represents a hydrogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. These may be further substituted with a substituent. Q represents a diazo component residue. The dye represented by formula (P) may form a dimer or higher multimer at an arbitrary position. ]

  The color filter according to <2> is preferably formed using the colored curable composition according to <1>.

<3> A method for producing a color filter, comprising: applying the colored curable composition according to <1> above onto a support, and then exposing through a mask to form a development pattern image.
In the method for producing a filter, when producing a color filter having a desired hue, the above steps are repeated according to the desired total number of colors. Moreover, the aspect which has the process of hardening | curing the said pattern image by heating and / or exposure as needed is also suitable.

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.
Further, according to the present invention, a color filter having high resolution and high transmittance characteristics, high heat fastness and high light fastness, and a color filter capable of producing the color filter with high productivity. A method can be provided.

  The colored curable composition of the present invention, the color filter, and the production method thereof will be described in detail below.

<Colored curable composition>
The colored curable composition of the present invention includes, as a pigment, a pigment represented by the following general formula (C1) and a pigment represented by the general formula (P) (hereinafter also collectively referred to as “the dye in the present invention”). .), 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.
Below, the pigment | dye represented by general formula (C1) of this invention is demonstrated in detail.

-Compound represented by the general formula (C1)-
The colored curable composition of the present invention contains at least one dye represented by the following general formula (C1) (hereinafter also referred to as “phthalocyanine dye in 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, is preferably a heterocyclic group having 1 to 15 carbon atoms in total, and a heterocyclic group having 3 to 10 carbon atoms in total. More preferred. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group, 1-piperidyl group and the like can be mentioned. Furthermore, you may have a substituent.

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

The aliphatic oxycarbonyl group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, may be cyclic, and may contain total carbon. A C2-C16 aliphatic oxycarbonyl group is preferable, and a C2-C10 aliphatic oxycarbonyl group is more preferable. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.
The aryloxycarbonyl group represented by Rc ₁ 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 12 carbon atoms in total, and a heterocyclic ring having 3 to 10 carbon atoms in total. An oxy group is more preferable. For example, 3-furyloxy group, 3-pyridyloxy group, N-methyl-2-piperidyloxy group and the like can be mentioned.
The aliphatic oxycarbonyloxy group represented by Rc ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and may be cyclic. As the aliphatic oxycarbonyloxy group, an aliphatic oxycarbonyloxy group having 2 to 16 carbon atoms is preferable, and an aliphatic oxycarbonyloxy group having 2 to 12 carbon atoms is more preferable. 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, Particularly preferred is an N-alkylacylamino group having 3 to 12 carbon atoms in total. 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, and an aliphatic thio group having 1 to 12 carbon atoms is more preferable. Examples thereof include a methylthio group, an ethylthio group, and an ethoxyethylthio group.
Examples of the arylthio group represented by Rc _1, which may be the substituted or unsubstituted, a total arylthio group having 6 to 22 carbon atoms are preferred, the total arylthio group having a carbon number of 6 to 12 is preferable. 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 phenyl 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) 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, Hydroxy group, cyano group, sulfo group, carboxyl group, carbamoylamino group, sulfamoylamino group, halogen atom, more preferably aliphatic group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, aliphatic group Group sulfonyl group, aliphatic thio group, a Ruchio group, a sulfo group, a carboxyl group, a halogen atom.

In said general formula (C1-1), cp represents the integer of 0-4, Preferably it is 0 or 1. However, cp + cr1, cp + cr2, cp + cr3, and cp + cr4 all represent integers of 0 to 4.
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 in the present invention) is used from the viewpoint of more effectively achieving the effects of the present invention. More preferred.

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

In the general 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 acylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an aliphatic thio group, an arylthio group in that the effect of the present invention can be more effectively exhibited. The aspect which is a group, a sulfo group, a carboxyl group, or a halogen atom is preferable, and the aspect which 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 in ethyl acetate 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.

  The other exemplified compounds described above can be synthesized in the same manner as described above by changing to a desired compound according to the target dye.

-Dye Represented by General Formula (P)-
The colored curable composition of the present invention includes at least a compound represented by the following general formula (P) (hereinafter also referred to as “pyridone azo dye in the present invention”) together with the compound represented by the general formula (C1). Contains one kind.
Hereinafter, the compound represented by the general formula (P) will be described in detail focusing on the description of each group.

In general formula (P), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or a substituent. R ³⁰³ represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxy group. A carbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group; Each group may be further substituted.
Q represents a diazo component residue. Moreover, the pigment | dye represented by general formula (P) may form a multimer more than a dimer in arbitrary positions.

The substituent represented by R ³⁰¹ or R ³⁰² may be any group that can be substituted, and examples include 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, fat Group oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, nitro group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide Group or heterocyclic thio group And more preferably an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic oxy group, an aryloxy group, an aliphatic amino group , An arylamino group. Each group may be further substituted.

The diazo component residue represented by Q is a residue of the diazo component “A-NH ₂ ”, and is preferably an aryl group or an aromatic heterocyclic group, for example.

Hereinafter, R ^{301 to} R ³⁰³ of general formula (P) and each substituent of Q will be described in detail.
Examples of the halogen atom represented by R ^{301 to} R ³⁰³ include a fluorine atom, a chlorine atom, and a bromine atom.
The aliphatic group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated, unsaturated, or cyclic. Examples include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups. The total number of carbon atoms in the aliphatic group is preferably 1-30, and more preferably 1-16. Specific examples of the aliphatic group include, 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 ³⁰³ may have a substituent, and an aryl group having 6 to 30 total carbon atoms is preferable, and an aryl group having 6 to 16 carbon atoms is more preferable. For example, phenyl group, 4-tolyl group, 4-methoxyphenyl group, 2-chlorophenyl group, 3- (3-sulfopropylamino) phenyl group, 4-sulfamoyl group, 4-ethoxyethylsulfamoyl and 3-dimethylcarbamoyl Groups and the like.

The heterocyclic group represented by R ^{301 to} R ³⁰³ may be saturated or unsaturated, includes the following aromatic heterocyclic group, and includes a nitrogen atom, a sulfur atom, and an oxygen atom in the ring. And those containing any of the heteroatoms such as, may further have a substituent, preferably a heterocyclic group having 1 to 30 carbon atoms in total, and a heterocyclic group having 1 to 15 carbon atoms. More preferably. For example, 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-furyl group and the like can be mentioned.

  The aromatic heterocyclic group is an aromatic ring containing any of hetero atoms such as a nitrogen atom, a sulfur atom and an oxygen atom in the ring, and a 5- to 6-membered ring is preferable. As a carbon atom number of an aromatic heterocyclic group, 1-25 are preferable and 1-15 are still more preferable. Examples of the aromatic heterocycle include a pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group, 1,2,4 thiadiazole group and the like.

The carbamoyl group represented by R ^{301 to} R ³⁰³ may have a substituent, is preferably a carbamoyl group having 1 to 30 carbon atoms, and is further a carbamoyl group having 1 to 16 carbon atoms. preferable. Examples thereof 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 ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number. An aliphatic oxycarbonyl group having 2 to 30 carbon atoms is preferable, and an aliphatic oxycarbonyl group having 2 to 16 carbon atoms is more preferable. Examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.

The aryloxycarbonyl group represented by R ^{301 to} R ³⁰³ may have a substituent, preferably an aryloxycarbonyl group having 7 to 30 carbon atoms in total, and an aryloxycarbonyl group having 7 to 16 carbon atoms. Groups are more preferred. Examples include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

The acyl group represented by R ^{301 to} R ³⁰³ includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and an embodiment having a total carbon number of 1 to 30 is preferable. Is more preferably 1-16. For example, an acetyl group, a methoxyacetyl group, a thienoyl group, a benzoyl group, etc. are mentioned.

The aliphatic oxy group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number of 1 To 30 are preferred, and embodiments having 1 to 15 total carbon atoms are more preferred. Examples include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, and 3-carboxypropoxy group.

The aryloxy group represented by R ^{301 to} R ³⁰² may have a substituent and is preferably an aryloxy group having 6 to 30 carbon atoms in total, and an aryloxy group having 6 to 16 carbon atoms in total. The aspect which is group is further more preferable. For example, a phenoxy group, p-methoxyphenoxy group, o-methoxyphenoxy group, etc. are mentioned.

The acyloxy group represented by R ^{301 to} R ³⁰³ includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably has 1 to 30 carbon atoms in total. Certain embodiments are more preferred. For example, an acetoxy group, a nicotinoyl group, a benzoyloxy group, etc. are mentioned.

The carbamoyloxy group represented by R ^{301 to} R ³⁰³ may have a substituent, and preferably has 1 to 30 carbon atoms in total, and more preferably has 1 to 16 carbon atoms. Examples thereof include an N-methylcarbamoyloxy group, a dimethylcarbamoyloxy group, and a phenylcarbamoyloxy group.

In the heterocyclic oxy group represented by R ^{301 to} R ³⁰³ , the heterocyclic ring may be saturated or unsaturated. Moreover, you may have a substituent and it is preferable that the total carbon number as a heterocyclic oxy group is 1-30, and it is still more preferable that it is 1-15. For example, 2-pyridyloxy group, 2-thienyloxy group, 2-thiazolyloxy group, 2-benzothiazolyloxy group, 2-benzoxazolyloxy group, 2-furyloxy group and the like can be mentioned.

The aliphatic amino group represented by R ^{301 to} R ³⁰³ may further have a substituent, may be saturated or unsaturated, and may be cyclic. Moreover, the aspect whose total carbon number of an aliphatic amino group is 1-30 is preferable, and the aspect which is 1-16 is still more preferable. Examples thereof include a methylamino group, a diethylamino group, a bis-2-ethoxyethylamino group, and an N-methyl-N-2-methoxyethylamino group.
The arylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having 6 to 30 carbon atoms is preferable, and an embodiment having 6 to 16 carbon atoms is more preferable. Examples include anilino and 4-methoxyphenylamino groups.
The heterocyclic amino group represented by R ^{301 to} R ³⁰³ may further have a substituent, may be saturated or unsaturated, and may be cyclic. Moreover, the aspect whose total carbon number of a heterocyclic amino group is 1-30 is preferable, and the aspect which is 1-16 is still more preferable. For example, 2-pyridylamino group, 2-thienylamino group, 2-thiazolylamino, 2-benzothiazolyloxy group and the like can be mentioned.

The acylamino group represented by R ^{301 to} R ³⁰³ includes an aliphatic carbonylamino group, an arylcarbonylamino group, and a heterocyclic carbonylamino group. The aspect in which the total number of carbon atoms of the acylamino group is 2 to 30 is preferable, and the aspect in which 2 to 16 is more preferable. Examples thereof include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

The carbamoylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having 1 to 30 carbon atoms is preferable, and an embodiment having 1 to 16 carbon atoms is more preferable. Examples thereof include a dimethylcarbamoylamino group and a phenylcarbamoylamino group.

The sulfamoylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having 0 to 30 carbon atoms is preferable, and an embodiment having 0 to 30 carbon atoms is further included. preferable. Examples thereof include sulfamoylamino and N, N-dipropylsulfamoylamino groups.

The aliphatic oxycarbonylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, The aspect which is number 1-30 is preferable, and the aspect which is 1-16 is still more preferable. For example, a methoxycarbonylamino group and a methoxyethoxycarbonylamino group are included.

The aryloxycarbonylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having a total carbon number of 7 to 30 is preferable, and an embodiment having 7 to 18 is more preferable. Examples include phenoxycarbonylamino and 3-chlorophenoxycarbonylamino groups.

The aliphatic sulfonylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number. The aspect which is 1-30 is preferable, and the aspect which is 1-16 total carbons is still more preferable. Examples thereof include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.
The arylsulfonylamino group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having a total carbon number of 6 to 30 is preferable, and an embodiment having 6 to 18 is more preferable. Examples thereof include benzenesulfonylamino and toluenesulfonamino groups.

The aliphatic thio group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number of 1 The aspect which is -30 is preferable, and the aspect which is C1-C16 is further more preferable. Examples thereof include a methylthio group, (t) butylthio group, and ethoxyethylthio group.
The arylthio group represented by R ^{301 to} R ³⁰³ may have a substituent, and preferably has 6 to 30 carbon atoms, and more preferably has 6 to 18 carbon atoms. Examples thereof include phenylthio and 4-methylphenylthio groups.
In the heterocyclic thio group represented by R ^{301 to} R ³⁰³ , the heterocyclic ring may be saturated or unsaturated, and may have a substituent. The total number of carbon atoms as the heterocyclic oxy group is preferably 1-30, and more preferably 1-15. Examples include a 2-pyridylthio group, a 2-thienylthio group, a 2-thiazolylthio group, a 2-benzothiazolylthio group, a 2-benzoxazolylthio group, and a 2-furylthio group.

The aliphatic sulfonyl group represented by R ^{301 to} R ³⁰³ may have a substituent, may be saturated or unsaturated, may be cyclic, and has a total carbon number of 1 The aspect which is -30 is preferable, and the aspect which is C1-C16 is further more preferable. Examples thereof include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.
The arylsulfonyl represented by R ^{301 to} R ³⁰³ may have a substituent, and preferably has 6 to 30 carbon atoms, and more preferably has 6 to 18 carbon atoms. Examples thereof include benzenesulfonyl and toluenesulfonyl groups.

The sulfamoyl group represented by R ^{301 to} R ³⁰³ may have a substituent, and an embodiment having 0 to 30 total carbon atoms is preferable, and an embodiment having 0 to 16 total carbon atoms is more preferable. Examples thereof include a sulfamoyl group, a dimethylsulfamoyl group, and a di- (2-hydroxyethyl) sulfamoyl group.
The imide group represented by R ^{301 to} R ³⁰³ may have a substituent, and is preferably a 5- to 6-membered imide group. Moreover, the aspect whose total carbon number of an imide group is 4-30 is preferable, and the aspect which is 4-20 is still more preferable. Examples include succinimide and phthalimide groups.
From the viewpoint of the effect of the present invention, the dye represented by the general formula (P) is preferably a dye represented by the following general formula (P1).

In the general formula (P1), R ³⁰¹ , R ³⁰² and R ³⁰³ are synonymous with those defined in the general formula (P), and preferred ranges are also the same. R ³⁰⁵ represents a substituent, and n represents an integer of 0 to 5.

The substituent represented by R ³⁰⁵ in the general formula (P1) may be any substitutable group, and examples include the groups listed in the above-mentioned “Substituent” section. Preferably, 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 sulfonylamino group, arylsulfonylamino group, nitro group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group or heterocyclic thio Group, even better Or a halogen atom, aliphatic group, aryl group, cyano group, carbamoyl group, heterocyclic group, aliphatic oxycarbonyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, nitro group, aliphatic thio group. It is a group. Each group may be further substituted.

In the general formulas (P) to (P1), R ³⁰¹ and R ³⁰² are a hydrogen atom, an aryl group, an aliphatic group, a cyano group, an aliphatic oxy group from the viewpoint of more effectively achieving the effects of the present invention. And an aliphatic oxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, an aliphatic amino group, an aliphatic sulfonylamino group, and an aliphatic oxyamino group are preferred. Specifically, an embodiment in which R ³⁰¹ is a hydrogen atom, an aryl group, an aliphatic group, a cyano group, an aliphatic oxy group, an acylamino group, or an aliphatic amino group is more preferable, and a hydrogen atom, an aliphatic group, an aliphatic oxy group is more preferable. The aspect which is a group and an aliphatic amino group is particularly preferable, and the aspect which is an aliphatic group is most preferable. An embodiment in which R ³⁰² is a hydrogen atom, a cyano group, an aliphatic oxycarbonyl group or a carbamoyl group is more preferred, an embodiment in which a cyano group, an aliphatic oxycarbonyl group or a carbamoyl group is particularly preferred, and an embodiment in which a cyano group is most preferred. .

Similarly, from the viewpoint that the effects of the present invention can be effectively achieved, R ³⁰³ is an aliphatic group, an acyl group, a heterocyclic group, an aryl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, or an arylsulfonyl group. Is preferable, and an embodiment in which an aliphatic group is used is more preferable.
Further, an embodiment in which R ³⁰⁵ is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, a sulfamoyl group, or an aliphatic thio group is preferable. More preferably, the embodiment is a group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, or a sulfamoyl group, and the embodiment that is an aliphatic group, cyano group, carbamoyl group, aliphatic oxycarbonyl group, or sulfamoyl group is the most. preferable.

  Similarly, from the viewpoint of effectively achieving the effect of the present invention, an embodiment where n is 0 to 3 is preferable, and an embodiment where 0 to 2 is more preferable. Furthermore, when general formula (P) and (P1) forms a multimer, the aspect which is a dimer is also preferable.

From the viewpoint of further effectively achieving the effect of the present invention, R ³⁰¹ is a hydrogen atom, a halogen atom, an aliphatic group, a cyano group, an aliphatic oxy group, an acylamino group, or an aliphatic amino group, and R ³⁰² Is a hydrogen atom, a cyano group, an aliphatic oxycarbonyl group or a carbamoyl group, and R ³⁰³ is an aliphatic group, an acyl group, an aryl group, an aliphatic carbonyl group, an aliphatic sulfonyl group or an arylsulfonyl group, An embodiment in which R ³⁰⁵ is a halogen atom, an aliphatic group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, a sulfamoyl group, or an aliphatic thio group, and n is 0 to 2, is preferred. the R ³⁰¹ is a hydrogen atom, an aliphatic group, an aliphatic oxy group or an aliphatic amino group, R ³⁰² is a cyano group, an aliphatic oxycarbonyl group or Karubamoi A group, a R ³⁰³ is an aliphatic group, R ³⁰⁵ is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group or a sulfamoyl group, An embodiment in which n is 0 to 2 is more preferable.

Similarly, from the viewpoint of the effect of the present invention, in particular, R ³⁰¹ is an aliphatic group, R ³⁰² is a cyano group, an aliphatic oxycarbonyl group, or a carbamoyl group, and R ³⁰³ is an aliphatic group, An embodiment in which R ³⁰⁵ is a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, or a sulfamoyl group and n is 0 to 2 is more preferable, and R ³⁰¹ is an aliphatic group. R ³⁰² is a cyano group, R ³⁰³ is an aliphatic group, R ³⁰⁵ is a halogen atom, an aliphatic group, a cyano group, a carbamoyl group, an aliphatic oxycarbonyl group, or a sulfamoyl group, An embodiment in which n is 1 to 2 is most preferable.

  Specific examples (exemplary compounds (p-1) to (p-58)) of pyridone azo dyes represented by the general formula (P) and the general formula (P1) are shown below. It is not limited.

Synthesis examples of azo dyes represented by the general formula (P) will be given below. [Synthesis Example 2]: Synthesis of pyridone azo dye (Exemplified Compound (p-1))

<Synthesis of Intermediate (5)>
21.94 g of the compound (2) and 33.93 g of the compound (1) were mixed and stirred at 70 ° C. for 3 hours. Subsequently, it cooled to room temperature, ethanol 90ml methyl acetoacetate 41.80g was added, and it heated up to 45 degreeC. Next, an ethanol solution of potassium hydroxide (KOH 25.25 g, ethanol 150 ml) was added dropwise, and the mixture was stirred at 85 ° C. for 6 hours. The solvent was distilled off, 45 g of hydrochloric acid was added, and the precipitate was filtered. 1300 ml of acetone and 250 ml of ethyl acetate were added to the filtrate, and the precipitate was separated by decantation. The liquid phase was dried over magnesium sulfate, and the solvent was distilled off to obtain the compound (3) (yield 59.07 g, yield 95%).

  78.22 g of the compound (3), 58.06 g of the compound (4), 33.67 g of potassium hydroxide and 320 ml of ethanol were mixed and stirred at 85 ° C. for 6 hours. The solvent was distilled off from the reaction mixture, 60 g of hydrochloric acid was added, and the precipitate was filtered. 1750 ml of acetone and 350 ml of ethyl acetate were added to the filtrate, and the precipitate was separated by decantation. The liquid phase was dried over magnesium sulfate, and the solvent was distilled off to obtain an intermediate (5).

<Synthesis of Intermediate (8)>
Separately, 33.24 g of the compound (7), 75 ml of orthodichlorobenzene, 7.5 ml of distilled water and 20.55 g of the compound (6) were mixed and heated to 45 ° C. After heating, an aqueous solution of 7.95 g of sodium carbonate was further added dropwise and stirred for 30 minutes. The mixture was further stirred at 70 ° C. for 1 hour, and then cooled to room temperature. The reaction mixture was filtered and washed with water to obtain the intermediate (8) (yield 44.81 g, yield 95%).

<Synthesis of Intermediate (9)>
Next, 27.3 g of reduced iron, 19.5 g of acetic acid, and 58.5 g of water were mixed and stirred at 80 ° C. for 1 hour, and 20 g of the intermediate (8) obtained above was gradually added thereto. Further, 93.6 ml of ethanol was added dropwise and stirred at 80 ° C. for 1 hour. Next, the mixture was cooled to room temperature, and an aqueous solution of 23.79 g of sodium carbonate was added to the reaction mixture. Subsequently, the mixture was filtered through Celite and washed with acetone, and then the solvent in the liquid phase was distilled off. Furthermore, it melt | dissolved in 600 ml of acetone, the insoluble matter was removed, it dried and concentrated with sodium sulfate, and the intermediate body (9) was obtained (yield about 14.3 g, yield about 79%).

<Azo dye (synthesis of exemplary compound (p-1)>
Next, 3.41 g of the intermediate (9), 12.5 ml of 36% hydrochloric acid, and 57 ml of distilled water were mixed and cooled to 0 ° C. A sodium nitrite aqueous solution (NaNO ₂ : 0.84 g, water: 10 g) was added dropwise thereto while maintaining the internal temperature at 5 ° C. or lower. After the dropping, the internal temperature was maintained at 5 to 10 ° C. and stirred for 3 hours (preparation of diazo solution).

  A solution containing the intermediate (5) separately prepared (2.62 g of the compound (5) and 20 g of water were mixed, and a 2N aqueous sodium hydroxide solution was added to set the pH to 8). The solution was added dropwise at 0 ° C. or less over 1 hour. Next, a 10% aqueous sodium carbonate solution was added dropwise to adjust the pH to 6 to 7, followed by filtration. Furthermore, it melt | dissolved in 500 ml of acetone, activated carbon and sodium sulfate were added, and it filtered by Celite. Subsequently, the solvent was distilled off, and the solid was vacuum-dried to obtain 3.05 g of the exemplified compound (p-1), which is the target pyridone azo compound of the present invention (yield 51%).

  Other exemplary compounds in general formula (P) can also be synthesized by the same synthesis method as described above. In addition, the colored curable composition, the color filter, and the method for producing the same of the present invention may be used in combination with other known dyes as necessary as long as the effects of the present invention are not impaired.

The concentration of the dye used in the present invention varies depending on the molecular weight and molar extinction coefficient, but is preferably 0.5 to 80% by mass, and preferably 0.5 to 60% by mass, based on the total solid components of the colored curable composition. Is more preferable, and 0.5 to 50% by mass is particularly preferable.
Individually, the dye represented by the general formula (C1) is preferably contained in the composition of the present invention in an amount of 10 to 90% by mass based on the total solid content from the viewpoint of the spectral characteristics. More preferably, it is contained in an amount of 20 to 80% by mass. Moreover, it is preferable that 10-80 mass% is contained with respect to the total solid in the composition of this invention, and, as for the pyridone azo dye in this invention, it is still more preferable that 10-70 mass% is contained.

  Among these, the content ratio (mass basis) of the dye represented by the general formula (C1) and the pyridone azo dye in the present invention is preferably 10/90 to 90/10 from the viewpoint of the spectral characteristics. More preferred is / 85 to 85/10. Moreover, when using the pigment | dye other than the pigment | dye represented by general formula (C1) and a pyridone azo dye as said colorant, 40 mass% or more is preferable, and, as for content which occupies in these all colorants, 60 mass% or more Is more preferable.

  The composition of the present invention may contain a radiation-sensitive compound such as a binder, a crosslinking agent, a polymerizable monomer, and a photopolymerization initiator, a solvent, and other additives in addition to the colorant. Hereinafter, these will be described.

-Binder-
The colored curable composition of the present invention can contain at least one binder. The binder in the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder 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) Those obtained by copolymerization using acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, etc. It is.

  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, etc. 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 a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, 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-
The present invention uses the dye according to the present invention described above, and 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 an 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 compounds, guanamine compounds, glycoluril compounds, or urea compounds 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 in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

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

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
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 top-coated 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 (meth) acrylate after addition of 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 in the present invention is a compound that can cause a chemical reaction such as generation of a radical, generation of an acid, generation of a base, etc. with respect to radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film can be made into an alkaline developer by insolubilizing the alkali-soluble resin by a reaction 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 insolubilizing.
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, 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. wear.

  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 JP-B 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 the above, 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 those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, 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 of 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 the negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of hues, and in the case of the 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.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following description, “part” means “part by mass” unless otherwise specified.

[Example 1]
1) Adjustment of contained photosensitive coloring composition (negative type)
(I) Preparation of resist solution The following composition was mixed and dissolved to prepare a resist solution.
〔composition〕
Propylene glycol monomethyl ether acetate 5.20 parts (PGMEA)
-Ethyl lactate (EL) 52.6 parts-Binder 30.5 parts ((benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) copolymer, molar ratio = 60: 20: 20, 41% EL solution) )
・ Dipentaerythritol hexaacrylate 10.2 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.006 parts ・ Fluorosurfactant 0.80 parts (trade name: F-475, Dainippon Ink & Chemicals, Inc.) Made)
-Photopolymerization initiator (trade name: TAZ-107, manufactured by Midori Chemical Co., Ltd.) 0.58 parts

2) Production of glass substrate with undercoat layer Glass substrate (trade name: Corning 1737, manufactured by Corning) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). .
Next, a glass substrate with an undercoat layer is formed by applying the resist solution of 1) above onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and drying by heating at 220 ° C. for 1 hour to form a cured film. Got.

3) Preparation of dye-containing resist solution (colored curable composition (negative type))
9.4 g of the resist solution obtained in the above 1), 0.75 g of the dye represented by the general formula (C1) in the present invention (the exemplified compound (C-1)) and the pyridone azo dye (general formula (P ): 0.35 g of the exemplified compound (p-1)) was mixed and dissolved to prepare a dye-containing resist solution (colored curable composition (negative type)).

4) Exposure and development of resist (image formation)
The colorant-containing resist solution obtained in 3) above was applied on the undercoat layer of the glass substrate with the undercoat layer obtained in 2) so as to have a film thickness of 1.0 μm using a spin coater, Prebaked at 100 ° C. for 120 seconds.
Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using a developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.) under conditions of 25 ° C. and 40 seconds. Then, it rinsed with running water for 30 second, and the pattern suitable for a green color filter was obtained by spray-drying.
When the temporal stability of the dye-containing resist solution, the heat resistance and the light resistance of the resist solution coated on a glass substrate were measured, excellent performance was shown in each. The results are shown in Table 1 below.

  In this example, the temporal stability, heat resistance and light resistance were measured by the following measuring methods.

-Stability of resist solution over time-
“Stability over time” was evaluated according to the following criteria by observing the degree of occurrence of precipitates in the dye-containing resist solution by visual observation of foreign matter after the dye-containing resist solution was stored at room temperature for 1 month (about 720 hours). .
Judgment criteria (circle): Generation | occurrence | production of the deposit was not recognized at all.
Δ: Slight occurrence of precipitates was observed. ×: Precipitation was significantly observed.

−Pattern heat resistance−
“Heat resistance” refers to heating a glass substrate coated with a dye-containing resist solution at 200 ° C. for 1 hour with a hot plate and heating with a chromaticity meter (trade name: MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.). The ΔEab value of the color difference before and after was measured and evaluated according to the following criteria. A smaller ΔEab value indicates better heat resistance.
<Criteria>
○: ΔEab value was less than 5.
Δ: ΔEab value was 5 or more and 10 or less.
X: The ΔEab value exceeded 10.

-Light resistance of patterns-
“Light resistance” means that a glass substrate coated with a resist solution is irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and a chromaticity meter (trade name: MCPD-1000, Otsuka Electronics ( Manufactured by Co., Ltd.), the ΔEab value of the color difference before and after irradiation was measured and evaluated according to the following criteria. A smaller ΔEab value indicates better light resistance.
<Criteria>
A: ΔEab value was less than 3.
Δ: ΔEab value was 3 or more and 10 or less.
X: The ΔEab value exceeded 10.

[Examples 2 to 10]
Example 1 3) Preparation of the dye-containing resist solution was performed in the same manner as Example 1 except that each dye was changed to the dye shown in Table 1 below (equal moles (1/2 mole in the case of bis)). The same evaluation was performed. The results are shown in Table 1.

[Comparative Examples 1-2]
In Example 1 3) Preparation of the dye-containing resist solution, the same evaluation was performed in the same manner as Example 1 except that each dye was changed to the dye (equal mole) shown in Table 1 below. The results are shown in Table 1.

  From the results in Table 1, it can be seen that the colored curable composition of the present invention is excellent in stability over time. Moreover, it turns out that the color filter using the curable composition containing the dye in this invention is excellent in heat resistance and light resistance.

[Example 11]
1) Preparation of colorant curable composition (positive type)
The following composition was mixed and dissolved to prepare a positive colorant-containing curable composition.
〔composition〕
• 30 parts of ethyl lactate (EL) • 3.0 parts of resin (P-1) (below) • 1.8 parts of naphthoquinonediazide compound (N-1) (below) • Hexamethoxymethylolated melamine (crosslinking agent) 6 parts Photoacid generator 1.2 parts (trade name: TAZ-107 (manufactured by Midori Chemical Co., Ltd.)
・ Fluorosurfactant 0.0005 parts (trade name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-1.5 parts of pigment | dye represented by the said general formula (C1) (The said exemplary compound (C-6))
-Dye represented by the general formula (P) (Exemplary Compound (p-1)) 0.7 part

  When the temporal stability, heat resistance and light resistance of the positive colorant-containing curable composition using the dye in the present invention were examined in the same manner as in Example 1, the temporal stability and light resistance were excellent, and the heat resistance. Was found to be good.

  Below, the synthesis | combining method of the said resin (P-1) and the said naphthoquinone diazide compound (N-1) is demonstrated.

(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 a stirrer, a reflux condenser, and a thermometer A polymerization initiator (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 was added at 65 ° C. under an attached nitrogen stream, and the mixture was stirred for 10 hours. The obtained resin solution was added dropwise to 20 L 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 the 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 (manufactured by 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 over 1 hour at room temperature. did. 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 while stirring. The naphthoquinone diazide sulfonic acid ester precipitated in the reaction solution was collected by suction filtration, and this was vacuum-dried at 40 ° C. for 24 hours to obtain a photosensitive compound (N-1).

[Examples 12 to 21]
Except having changed the glass substrate of Examples 1-10 into the silicon wafer substrate, all the same operations as Example 1 were performed, and the coated substrate of the silicon wafer was obtained.
Next, using a i-line reduction projection exposure apparatus, a 2 μm square pattern was exposed at an exposure amount of 500 mJ / cm ² , and a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Arch Co., Ltd.) And developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds and spray drying, a pattern suitable as a color filter for CCD having a square cross section was obtained.

Claims (3)

A colored curable composition comprising at least one pigment represented by the following general formula (C1) and at least one pigment selected from the pigment represented by the following general formula (P).

[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, An aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a non-metallic atomic group necessary for forming a 6-membered ring together with the carbon atom, four Zc1 may or may not be the same. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, and cn represents 0 or an integer of 1 to 5. The 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 (P), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or a substituent. R ³⁰³ represents a hydrogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. These may be further substituted with a substituent. Q represents a diazo component residue. The dye represented by formula (P) may form a dimer or higher multimer at an arbitrary position. ] A color filter comprising at least one dye represented by the following general formula (C1) and at least one selected from dyes represented by the following general formula (P).

[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, An aryloxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, an imide group, or a heterocyclic thio group. Zc ₁ represents a non-metallic atomic group necessary for forming a 6-membered ring together with the carbon atom, four Zc1 may or may not be the same. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. cm represents 0, 1 or 2, and cn represents 0 or an integer of 1 to 5. The 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 (P), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or a substituent. R ³⁰³ represents a hydrogen atom, aliphatic group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. These may be further substituted with a substituent. Q represents a diazo component residue. The dye represented by formula (P) may form a dimer or higher multimer at an arbitrary position. ]   A method for producing a color filter, comprising: applying a colored curable composition according to claim 1 onto a support, and then exposing through a mask to form a development pattern image.