JP4524155B2 - Colored curable composition, color filter and method for producing the same - Google Patents

Description

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

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

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

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

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

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

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

On the other hand, it is known that a mixture of a violet dye and a cyan dye is used for a blue filter array of a color filter (see, for example, Patent Document 12). However, the dyes used have insufficient heat resistance and light resistance, and further improvements are desired.
Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 Japanese Patent Laid-Open No. 2002-14222

  As described above, although a curable composition containing a dye is useful in applications such as a solid-state imaging device that requires high definition and uniform color, the color density and hue of a dye such as amber can be stably maintained. In particular, improvement of fastness such as heat resistance and light resistance of cyan dye and violet dye has been an issue. In addition, since the dye has low solubility, improvement of dye precipitation due to low stability over time when it is in the state of a liquid preparation or a coated film is also an issue. .

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

  In the present invention, various dye compound derivatives having a good hue and high fastness to light and heat have been examined in detail. The dye having a specific structure particularly has fastness such as heat resistance and light resistance. Based on this knowledge, a colored curable composition, a color filter, and a method for producing the same were provided, and the above object was achieved.

Specific means for achieving the above object are as follows.
<1> to at least one azomethine dye represented by the following formula (III), characterized in that it contains at least one tetraazaporphyrin dye represented by the following general formula (A) It is a colored curable composition.

In the general formula (III) , R ¹ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group , and R ² , R ^3, and R ⁴ each independently represent a hydrogen atom or a substituent, R ⁶ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ² and R ^3, R ³ and R ^6, R ⁶ and R ^9, and R ⁴ and R ¹⁴ are each independently, may form a five- to seven-membered ring bonded to each other.

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

< 2 > The colored curable composition according to <1 >, wherein the tetraazaporphyrin-based dye represented by the general formula (A) is a phthalocyanine dye represented by the following general formula (B).

In the general formula (B), M ¹ represents a metal, and R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent.

<3> The colored curable composition according to <1> or <2>, further including a polymerizable monomer, a photopolymerizable initiator, and an alkali-soluble binder and configured in a negative type.
<4> and at least one azomethine color element represented by the following formula (III), phthalocyanine represented by the following general formula (A) tetraazaporphyrin represented by dyes and the following general formula (B) It is a color filter characterized by containing at least 1 sort (s) of pigment | dye.

In the general formula (III) , as described above, R ¹ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group , R ^2, R ^3, and R ⁴ each independently represent a hydrogen atom or a substituent, R ⁶ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ² and R ³ , R ³ and R ⁶ , R ⁶ and R ⁹ , and R ⁴ and R ¹⁴ may be independently bonded to each other to form a 5-membered to 7-membered ring.

As described above, in the general formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently composed of an atom selected from a carbon atom and a nitrogen atom. In addition, in general formula (B), M ¹ represents a metal, and R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent.

  <5> A step of coating the colored curable composition according to any one of <1> to <3> on a support, exposing through a mask, and developing to form a pattern image. It is a manufacturing method of the color filter characterized.

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

Hereinafter, the colored curable composition of the present invention, the color filter, and the production method thereof will be described in detail.
[Colored curable composition]
The colored curable composition of the present invention includes, as a colorant (dye), an azomethine dye represented by the following general formula (III) among the azomethine dyes represented by the following general formula (I) : And a tetraazaporphyrin-based dye represented by the general formula (A) shown below (hereinafter also referred to as “the dye according to the present invention” as a whole), and preferably contains a binder, a radiation-sensitive compound, and a polymerizable monomer. Comprising. 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 coloring matter according to the present invention, and can also achieve high sensitivity, high resolution, and high transmittance characteristics.

-Azomethine dye represented by formula (I)-
The azomethine color element represented by the following following general formula (I), the exhibit high good magenta hue transmittance characteristics over time precipitation without stability when the state of the liquid preparation or coated coating film It has excellent resistance to heat and light.
Hereinafter, the azomethine dye represented by the general formula (I) will be described focusing on the description of each group.

In the general formula (I), R ¹ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a straight chain or branched chain having 1 to 48 carbon atoms, more preferably 1 to 18 carbon atoms, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl , 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18. For example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group having a number of 6 to 48, more preferably 6 to 12. For example, phenyl, naphthyl ), A heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2 -Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 12. For example, trimethylsilyl, triethylsilyl, tributyl Silyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group,

An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms. For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy Group (for example, cyclopentyloxy, cyclohexyloxy)), aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 12. For example, phenoxy, 1-naphthoxy), heterocyclic oxy group (Preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy group (preferably 1 carbon atom). ~ 32, more preferably 1-12 silyloxy groups. Methylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetoxy, pivaloyloxy, benzoyloxy, dodeca Noyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group ( Eg cyclohexyloxycarbonyloxy)),

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

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

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

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

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

If R ¹ described above is capable of substitution, yet the substituent represented by R ^1, may have a substituent represented by R ^1, has two or more substituents In some cases, the plurality of substituents may be the same or different.

In the general formula ^{(I), R 2, R} 3, R 4, and R ⁵ each independently represent a hydrogen atom or a substituent. The substituent represented by R ^{2 to} R ⁵ has the same meaning as the substituent represented by R ¹ , and the preferred embodiment is also the same. When R ^{2 to} R ⁵ are substitutable groups, each group represented by R ^{2 to} R ⁵ may further have a substituent represented by R ¹ , and has two or more substituents. The plurality of substituents may be the same or different.

In formula (I), each independently R ⁶ and R ⁷ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The alkyl group, alkenyl group, aryl group and heterocyclic group represented by R ⁶ or R ⁷ are the same as the alkyl group, alkenyl group, aryl group and heterocyclic group listed in the substituent represented by R ^1. It is synonymous and a preferable aspect is also the same.
Further, when R ⁶ and R ⁷ are substitutable groups, each group represented by R ⁶ or R ⁷ may be further substituted with a substituent represented by R ¹ , and two or more groups When it is substituted with, a plurality of groups may be the same or different.

In the above, R ² and R ³ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁵ and R ⁷ , and R ⁶ and R ⁷ are each independently bonded to each other to form a 5-member, 6-member, or A 7-membered ring may be formed. As the 5-membered, 6-membered or 7-membered ring, cyclopentene, cyclohexene, cycloheptene, dihydropyrrole, tetrahydropyridine and the like are preferable, and the ring may be substituted with the substituent represented by R ^1. . Moreover, when substituted with two or more substituents, the plurality of substituents may be the same or different.

In the general formula (I), Za and Zb each independently represent —N═ or —C (R ⁸ ) ═, and R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Alkyl group represented by R ^8, aryl group or heterocyclic group, the alkyl groups of the listed substituent represented by R ^1, are each synonymous with an aryl group or a heterocyclic group, preferred embodiments Is the same.
Further, when the group represented by R ⁸ is a substituted group, each group represented by R ⁸ may be further substituted with a substituent represented by R ^1, at least two groups When substituted, the plurality of groups may be the same or different.

Of the azomethine dyes represented by the general formula (I), azomethine dyes (dyes) represented by the following general formula (II) are preferable.

In the general formula (II), R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. In the general formula ^{(II), R 1, R} 2, R 3, R 4, and R ⁶ are each synonymous with R ¹ to R ⁴ and R ⁶ in Formula (I), these preferred Each aspect is also the same. Za and Zb in the general formula (II) have the same meanings as Za and Zb in the general formula (I), respectively, and preferred embodiments thereof are also the same.

The substituents represented by R ⁹ to R ¹⁴ are the same as the substituents represented by R ¹ of formula (I), preferable embodiments thereof are also the same. Moreover, when the substituent represented by R ^{9 to} R ¹⁴ is a substitutable group, each group represented by R ^{9 to} R ¹⁴ may be further substituted with a substituent represented by R ^1. When substituted with two or more groups, the plurality of groups may be the same or different.

R ² and R ³ , R ³ and R ⁶ , R ⁶ and R ⁹ , R ⁴ and R ¹⁴ may be independently bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Good. As the 5-membered, 6-membered or 7-membered ring, cyclopentene, cyclohexene, cycloheptene, dihydropyrrole, tetrahydropyridine and the like are preferable.

In the case where the substituent represented by R ¹ , R ² , R ³ , or R ⁴ in the general formula (II) is a substitutable group, each group represented by R ^{1 to} R ⁴ is represented by the above general formula ( It may be further substituted with a substituent represented by R ¹ in I), and when it is substituted with two or more groups, the plurality of groups may be the same or different.

The colored curable composition of the present invention, among the azomethine dye represented by the general formula (II), contains at least one azomethine dye represented by the following general formula (III).

In the general formula (III), R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, in the general formula (III), R ¹ ~R ⁴ and R ⁶ and R ⁹ to R ¹⁴ is, R ¹ to R ⁴ and R ⁶ and R ⁹ in the general formula (I) or (II) to R Each of them is synonymous with ^14, and these preferred embodiments are also the same.

The alkyl group, aryl group, and heterocyclic group represented by R ¹⁵ have the same meanings as the alkyl group, aryl group, and heterocyclic group listed in the substituent represented by R ¹ in the general formula (I), respectively. These preferred embodiments are also the same.
Each group represented by R ¹⁵ may be further substituted with a substituent represented by R ¹ in the general formula (I), and when it is substituted with two or more substituents, a plurality of substituents May be the same as or different from each other.

Preferred ranges of the azomethine dyes represented by the general formula (III) are as follows.
In the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group. Carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl sulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group or a phosphinoylamino group, as preferred R ^2, R ^3, and R ^4, each independently, a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, alkoxy Group, aryloxy group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, A heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, or a phosphinoylamino group, and R ⁶ is preferably an alkyl group or an alkenyl group; , An aryl group, or a heterocyclic group, and R ⁸ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and each of R ^{9 to} R ¹⁴ is preferably independently a hydrogen atom, halogen, Atom, alkyl group, or alkoxy It is a group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, imide group, alkylthio group, arylthio group. Group, heterocyclic thio group, alkylsulfonyl group, or arylsulfonyl group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group. , An alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, or an arylthio group, and R ⁶ is preferably an alkyl group, an alkenyl group, an aryl group, or hetero a Hajime Tamaki, preferably an R ⁸ is Hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, is preferably an R ⁹ to R ^14, are each independently a hydrogen atom or an alkyl group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, alkylthio group, arylthio group, alkylsulfonyl group. Or an arylsulfonyl group, and R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, carbonamide Group, ureido group, alkoxycarbonylamino group, sulfonamido group, alkylthio group or arylthio group, R ⁶ is preferably an alkyl group or an aryl group, and R ⁸ is preferably a hydrogen atom, an alkyl group or an aryl group. or a heterocyclic group, R ⁹ ~ Preferably a ¹⁴ are each independently a hydrogen atom or an alkyl group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, An alkyl group or an alkoxy group, R ⁶ is preferably an alkyl group, R ⁸ is preferably an alkyl group, an aryl group, or a heterocyclic group, and R ^{9 to} R ¹⁴ are preferably each independently It is a hydrogen atom or an alkyl group.

Most preferably, in the dye represented by formula (III), R ¹ is a tertiary alkyl group (preferably a tertiary alkyl group having 4 to 16 carbon atoms, more preferably 4 to 8 carbon atoms. For example, t- Butyl, t-amyl, t-octyl, 1-adamantyl), and R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) Preferably a fluorine atom or a chlorine atom), an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8. For example, methyl, ethyl, propyl, isopropyl, t -Butyl, cyclohexyl, 2-ethylhexyl) or an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms such as methoxy, Ethoxy, isopropyloxy, octyloxy, 2-ethylhexyloxy), and R ⁶ is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12. For example, methyl, ethyl, propyl, Isopropyl, octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl), and R ⁸ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms. , Ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, hexadecyl), an aryl group (preferably an aryl group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, for example, phenyl or naphthyl), or Heterocyclic group (preferably a heterocycle having 1 to 12 carbon atoms, more preferably 2 to 12 carbon atoms For example, 2-thienyl, 4-pyridyl, 2-pyridyl, 2-imidazolyl, 3-pyrazolyl), and R ⁹ and R ¹⁰ are alkyl groups (preferably having 1 to 8 carbon atoms, more preferably 1). a to 4 alkyl groups. for example, methyl, ethyl, propyl (most preferably methyl)), a hydrogen atom independently R ¹¹ to R ¹³ are each, R ¹⁴ is an alkyl group (preferably having a carbon number of 1 -8, more preferably 1-4, such as methyl, ethyl, propyl (most preferably methyl)).

  Specific examples (exemplary compounds M-1 to M-84) of the azomethine dyes represented by the general formula (I) are shown below. However, the present invention is not limited to these.

-Synthesis example-
Next, a synthesis example of the azomethine dye represented by the general formula (I) will be described in detail with reference to the following schemes A and B by taking as an example the synthesis of the dye M-1, which is the exemplified compound.

(1) Synthesis of Compound B First, as shown in Scheme A, 94.7 g (0.5 mol) of Compound A (manufactured by Sigma-Aldrich), 37.5 g (0.25 mol) of sodium iodide, and hydrogen carbonate To a mixture of 126 g (1.5 mol) of sodium, 300 ml of dimethylimidazolidinone was added and heated to 95 ° C. and stirred. To this solution, 90.3 g (0.65 mol) of 3-bromopropanol was dropped, and after completion of the dropping, the reaction was completed by heating and stirring at 95 to 100 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 600 ml of water and 500 ml of ethyl acetate. The ethyl acetate phase was washed with water and dried using anhydrous magnesium sulfate. The ethyl acetate phase was concentrated under reduced pressure and then purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 10/1) to obtain 90.5 g of compound B (yield 73.2%). .

(2) Synthesis of Compound C To 90 g (0.364 mol) of Compound B obtained above, 270 ml of methanol was added, cooled to 5 ° C., and stirred. To this solution, 93.7 ml (1.09 mol) of concentrated hydrochloric acid was added dropwise, and further, 27.6 g (0.4 mol) of sodium nitrite was dissolved in 75 ml of water, and the solution was kept at 5 to 10 ° C. It was dripped. After completion of the dropwise addition, the reaction was completed by stirring at 5 to 10 ° C. for 2 hours. After completion of the reaction, 500 ml of ethyl acetate and 1000 ml of water were added, and 84 g of sodium bicarbonate was added little by little to neutralize, and then the aqueous phase was removed. The ethyl acetate phase was washed with water and dried over anhydrous magnesium sulfate, and then the ethyl acetate phase was concentrated under reduced pressure to precipitate crystals. To this crystal, 200 ml of n-hexane and 200 ml of ethyl acetate were added and stirred to disperse the crystal. The crystals were filtered and dried to obtain 78 g of Compound C (yield 77.6%).

(3) Synthesis of Compound E Here, Compound E was synthesized by the method shown in Scheme B below.

-Synthesis of Intermediate (M)-
To 112 g (0.9 mol) of 4-methoxyphenol, 600 ml of dimethylacetamide was added and stirred at room temperature. To the resulting solution was added 196 ml of 28% methanol solution of sodium methoxide. To the solution after completion of the addition, 190 g (0.97 mol) of 2-bromobutanoic acid ethyl ester was added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 3 hours to complete the reaction. To this reaction solution, 1000 ml of water and 1000 ml of ethyl acetate were added and extracted with ethyl acetate. The ethyl acetate phase was washed with brine, and then 250 ml of methanol was added to the residue obtained by distilling off ethyl acetate under reduced pressure, followed by stirring at room temperature. Subsequently, an aqueous solution in which 144 g of sodium hydroxide was dissolved in 1000 ml of water was added to this solution. Subsequently, this solution was heated to 50 to 55 ° C. and stirred for 2 hours. After completion of the reaction, 340 ml of concentrated hydrochloric acid was further added dropwise to the reaction solution to make it acidic. Subsequently, 1000 ml of ethyl acetate was added for extraction, and the ethyl acetate phase was washed with brine and then dried over anhydrous sodium sulfate. The ethyl acetate phase was concentrated under reduced pressure to obtain intermediate (M) quantitatively.

-Synthesis of Intermediate (N)-
400 ml of toluene was added to 93.1 g (0.433 mol) of the intermediate (M) obtained as described above, and the mixture was heated to 85 to 90 ° C. and stirred. To this solution, 50 ml of thionyl chloride was added dropwise and stirred with heating for 3 hours. After completion of the reaction, toluene and excess thionyl chloride were distilled off under reduced pressure. Then, after cooling to room temperature, 100 ml of ethyl acetate was added to obtain a solution of intermediate (N) in ethyl acetate.

-Synthesis of Compound E-
According to the method described in JP-A-2-201443, 5-amino-3-methylpyrazole as a raw material is converted into 5-amino-3-tert-butylpyrazole (synthesized by the method described in Japanese Patent No. 2670943). The intermediate (L) was obtained by modification. To 189 g (0.538 mol) of this intermediate (L), 570 ml of 2-propanol was added and heated and stirred. To this solution, 33.6 g (0.673 mol) of hydrazine monohydrate was added dropwise, and the mixture was heated and stirred for 2 hours. After completion of the reaction, about 400 ml of 2-propanol was distilled off under reduced pressure. Then, 420 g of sodium hydrogen carbonate, 1500 ml of water, and 1200 ml of ethyl acetate were added to this residue, and the mixture was stirred at room temperature.
Subsequently, the ethyl acetate solution of the said intermediate (N) was dripped at this solution, it stirred at room temperature for 2 hours after completion | finish of dripping, and the water phase was removed continuously. When the ethyl acetate phase was washed with water, crystals were precipitated. After adding 1200 ml of n-hexane to this dispersion and stirring for 1 hour, the crystals were filtered, washed with water and dried to obtain 159 g of compound E (yield 86.9%).

(4) Synthesis of Exemplified Compound M-1 Next, according to Scheme A, 50 ml of methanol, 100 ml of ethyl acetate, and 100 ml of water were added to 7.35 g (0.0266 mol) of Compound C obtained above to 40 ° C. Heated and stirred. To this solution, 25 g of hydrosulfite soda was added little by little, and after completion of the addition, reaction was carried out at 40 ° C. for 1 hour to obtain Compound D. After completion of the reaction, the mixture was cooled to room temperature, 100 ml of ethyl acetate and 200 m of water were added, the aqueous phase was removed to obtain an ethyl acetate phase containing Compound D, and this ethyl acetate phase was used below.

Subsequently, 100 g of methanol and 200 ml of water were added to 10.0 g (0.0242 mol) of the compound E obtained above and 21 g of sodium hydrogen carbonate, and the mixture was stirred at room temperature, and the total amount of the ethyl acetate phase was added thereto. After that, an aqueous solution in which 12 g of ammonium persulfate was dissolved in 100 ml of water was added dropwise. After completion of the dropping, the reaction was performed at room temperature for 1 hour. After completion of the reaction, the aqueous phase was removed, then the ethyl acetate phase was washed with water, and the ethyl acetate phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1) to obtain an amorphous dye M-1.
When the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max 556 nm, It was ε5,5000.

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

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

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

In the general formula (A), M ¹ represents a metal, and examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. etc., as well as _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl metal chlorides such as _2, TiO, metal oxides such as VO, is and Si (OH) ₂ or the like of the metal hydroxide .

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

Of the tetraazaporphyrin dyes represented by the general formula (A), phthalocyanine dyes represented by the following general formula (B) are particularly preferable.

In the general formula (B), M ¹ has the same meaning as M ¹ in formula (A), is the same a preferred embodiment thereof.
In the general formula (B), R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is R ^{1 in} the general formula (I) described above. And the preferred embodiments thereof are also the same. When the substituents represented by R ^{101 to} R ¹¹⁶ are substitutable groups, the substituents represented by R ^{101 to} R ¹¹⁶ are further represented by R ¹ in the general formula (I) described above. And when having two or more substituents, the plurality of substituents may be the same or different.

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

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

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

More preferably, in the general formula (B), as the α-substituted product (mono-substituted product), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ Or at least one of R ¹¹⁶ ), or a β-substituted product (mono-substituted product) as (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ^111). ), and a compound having at least one substituent of (R ¹¹⁴ or R ^115).
Preferred substituents in this case include halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy Group, carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide Group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphino Arylamino group and the like, the ^{M 1, Zn, Pd, Cu} , Ni, Co, TiO, VO , and the like.

More preferably, the formula (B), as the α substituents, the (R ¹⁰¹ or R ^104), (R ¹⁰⁵ or R ^108), (R ¹⁰⁹ or R ^112), and (R ¹¹³ or R ¹¹⁶⁾ At least three of them have substituents or β-substituents are (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) It is a compound which has a substituent in at least 3 of these.
Preferred substituents in this case include a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxy group Carbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a sulfo group, a ^{M 1, Zn, Pd, Cu} , Ni, Co, VO , and the like.

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

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

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

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

-Synthesis example-
Next, a synthesis example of the dye represented by the general formula (A) or (B) will be described in detail with reference to the following scheme C by taking as an example the synthesis of the dye C-4 which is the exemplified compound.

(1) Synthesis of Intermediate 100 ml of dimethyl sulfoxide was added to 25.0 g (0.144 mol) of 3-nitrophthalonitrile and 34.7 g (0.159 mol) of mercaptopropionic acid-2-ethylhexyl ester, and the mixture was stirred at room temperature. . To this was further added 17.0 g of sodium carbonate little by little, and after completion of the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The resulting reaction solution was poured into 500 ml of water and extracted with 300 ml of ethyl acetate. Then, the ethyl acetate phase was washed with water and dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain oily intermediate A quantitatively.

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

(2) Synthesis of Dye C-4 To 7.53 g (0.02 mol) of Intermediate B obtained as described above and 3.85 g of ammonium carbonate, 40 ml of butanol was added and heated and stirred at 50 ° C. Next, 0.67 g (0.005 mol) of cupric chloride was added thereto, and the mixture was heated to 100 to 110 ° C. and stirred for 6 hours. After completion of the reaction, butanol was distilled off, the residue was dissolved in chloroform, separated and purified by column chromatography (eluent: chloroform / methanol = 10/1), and amorphous dye C-4 was added to 3. 3 g was obtained (yield 42.0%).

When in ethyl acetate in the resulting dye was measured by spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation) of the maximum absorption wavelength (lambda _max) and molar extinction coefficient (epsilon), the maximum absorption wavelength lambda _max 623. It was 4 nm and ε47,000.

  In addition, other exemplary compounds other than the above-mentioned dye C-4 can also be synthesized by the same method as described above.

In the colored curable composition of the present invention, one or more of the dyes represented by the general formula (I) to the general formula (III) described above and the general formula (A) to the general formula ( B) is used in combination with one or more of the dyes represented by B), and a known xanthene dye or triarylmethane dye may be used in combination as required.
Preferably, one or more azomethine dyes represented by the general formula (III) described above are used in combination with one or more phthalocyanine dyes represented by the general formula (B). It is an aspect.

  The total concentration of the coloring matter according to the present invention in the colored curable composition varies depending on the molecular weight and the molar extinction coefficient, but is preferably 0.5 to 80% by mass with respect to the total solid components of the composition. -60 mass% is more preferable, and 0.5-50 mass% is especially preferable.

  In addition, an azomethine dye represented by general formula (I) to general formula (III) and a tetraazaporphyrin dye represented by general formula (A) (including a phthalocyanine dye represented by general formula (B)) ) And the content ratio [asomethine dye / tetraazaphorphyrin dye (including phthalocyanine dye)] depending on each molecular weight and molar extinction coefficient, but preferably 1/9 to 9/1 in terms of mass ratio. 1/4 to 4/1 is more preferable, and 1/4 to 2/1 is particularly preferable.

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

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

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

  In addition to the above, as a monomer having a hydrophilic group, a tetrahydrofurfuryl group, a phosphoric acid site, a phosphoric acid 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) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.) and Cyclomer P series (Daicel Chemical Industries, Ltd.) are preferred.

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. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde. Each of the phenols and aldehydes can be used in combination of two or more, in addition to being used alone.

  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 as 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 a crosslinking agent. This is useful from the viewpoint of achieving high resolution of the colored curable composition of the present invention.

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

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

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound according to (b) (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound). There is.

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

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

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

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

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

The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of), intermixing with the 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 then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52- Examples include polyester acrylates described in each publication of No. 30490, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. Furthermore, the Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

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

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

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

~ Photoinitiator etc. ~
First, the photopolymerization initiator used when the colored curable composition of the present invention is configured as a negative type will be described. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, but is preferably selected in view of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. In addition, you may further contain in the positive type | system | group containing a naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

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

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

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

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

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

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

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

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B, etc.), Irgacure series (for example, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184) manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocure series (eg Darocure 1173 etc.),

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

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

  The content of the photopolymerization initiator 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, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. It is done.

  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 .; aromatic hydrocarbons such as toluene, xylene, etc. Preferably mentioned .

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

-Various additives-
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended.

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

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

  The 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. Most preferably, a radiation composition layer is formed, the layer is exposed through a predetermined mask pattern, and developed with a developer to form a negative or positive colored pattern (resist pattern). It can be produced (image forming step). At this time, if necessary, a curing step for curing the formed colored pattern by heating and / or exposure can be provided. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used. In addition, when the colored curable composition is configured as a positive type, a step of post-baking the colored pattern after the image forming step can be provided.

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

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

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

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

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

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

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

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

3) Preparation of dye resist solution (colored curable composition [negative type]) 9.4 g of resist solution obtained in the above 1) and the exemplified compound M-1 described above which is a pigment according to the present invention An azomethine dye represented by the formula (I); hereinafter referred to as dye M-1. ] 0.36 g and exemplary compound C-1 [tetraazaporphyrin-based dye represented by the general formula (A); hereinafter referred to as dye C-1. 0.9 g was mixed and dissolved to prepare a dye resist solution (colored curable composition [negative type] solution).

4) Exposure and development of dye resist solution (image formation)
The dye resist solution obtained in 3) above was applied on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1.0 μm. Pre-baked for 120 seconds.
Then, using an exposure apparatus, the coating film was irradiated with an exposure amount of 500 mJ / cm ² through a 5 mm square mask (island pattern) at a wavelength of 365 nm. After irradiation, development was performed using a developer CD-2000 (manufactured by Fuji Film Arch Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.
As described above, a blue pattern suitable as the blue color constituting the color filter was obtained.

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

-Heat resistance-
The glass substrate coated with the dye resist solution is placed on a hot plate at 180 ° C. so as to be in contact with the substrate surface, heated for 1 hour, and then heated by a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The color difference (ΔEab value) was measured as an index for evaluating heat resistance and evaluated according to the following criteria. The ΔEab value indicates that the smaller the value, the better the heat resistance.
[Criteria]
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

-Light resistance-
A glass substrate coated with a dye resist solution is irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and then the color difference (ΔEab value) before and after irradiation is measured to increase the light resistance. As an index to be evaluated, evaluation was performed according to the following criteria. The ΔEab value indicates that the smaller the value, the better the light resistance.
[Criteria]
○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

(Examples 2 to 22)
In Example 1, “3) Preparation of dye resist solution”, a blue pattern was formed in the same manner as in Example 1 except that the coloring matter according to the present invention was changed as shown in Table 1 below (but equimolar). Further, the same evaluation was performed. VB-2620 manufactured by Orient Chemical Co., Ltd. was used. The evaluation results are shown in Table 1 below.

(Example 23)
In “3) Preparation of Dye Resist Solution” in Example 1, Dye C-1 was replaced with VB-2620 in 1/2 mol amount of Dye C-1 and Exemplified Compound C-17 in 1/2 mol amount. In addition, a blue pattern was formed in the same manner as in Example 1 except that the dye M-1 was replaced with the exemplified compound M-76 having a ½ molar amount of the dye M-1, and the same evaluation was performed. It was. VB-2620 manufactured by Orient Chemical Co., Ltd. was used. The evaluation results are shown in Table 1 below.

(Example 24)
In “3) Preparation of dye resist solution” in Example 1, the dye C-1 was changed to 1/2 mole amount of the exemplified compound C-3 and 1/2 mole amount of the exemplified compound C-17 of the dye C-1. In the same manner as in Example 1, except that the dye M-1 was replaced with a ¼ molar amount of the dye M-1 and a 3/4 molar amount of the exemplified compound M-69. A blue pattern was formed and the same evaluation was performed. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-3)
In “1) Preparation of dye resist solution” in Example 1, the dyes according to the present invention (Dye 1 and Dye 2 in Table 1) were changed as shown in Table 1 below (so that the total amount of dye is equimolar). A comparative blue pattern was formed in the same manner as in Example 1 except that the adjustment was made, and the same evaluation was performed. The evaluation results are shown in Table 1 below together with the results of the examples.

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

(Example 25)
1) Preparation of colored curable composition [positive type] The following compositions were mixed and dissolved to prepare a solution-like colored curable composition [positive type].
・ Ethyl lactate (EL): 30 parts ・ Resin P-1: 3.0 parts ・ Naphthoquinonediazide compound N-1: 1.8 parts ・ Hexamethoxymethylolated melamine (crosslinking agent) 0.6 parts TAZ-107 (manufactured by Midori Chemical Co .; photoacid generator) ... 1.2 parts F-475 ... 0.0005 parts (fluorine-based surfactant; Dainippon Ink and Chemicals, Inc.) Industrial)
Exemplified compound M-1 of the dye according to the present invention 0.38 part (Azomethine dye represented by the general formula (I))
-Illustrative compound C-17 of the dye according to the present invention 1.12 parts (tetraazaporphyrin dye represented by the general formula (A))

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

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

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

  Subsequently, the storage stability of the colored curable composition prepared above and the heat resistance and light resistance of the coating film coated on the glass substrate using the colored curable composition were the same as in Example 1. As a result of the evaluation, the storage stability, light resistance and heat resistance were all good as in the case of the negative type.

(Examples 26 to 49)
Except that the glass substrate of Examples 1 to 24 was replaced with a silicon wafer substrate, the same operation as in Examples 1 to 24 was performed to apply a coating film on the silicon wafer substrate to obtain a silicon wafer coated substrate. It was. Next, a 2 μm square pattern is exposed at an exposure amount of 500 mj / cm ² using an i-line reduction projection exposure apparatus, and a developer obtained by diluting CD-2000 (manufactured by Fuji Film Arch) to 60% is used. Developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As described above, a pattern suitable as a CCD color filter having a substantially square cross section and a good profile could be obtained.

Claims (5)

A coloring curable composition comprising at least one azomethine dye represented by the following general formula (III) and at least one tetraazaporphyrin dye represented by the following general formula (A): Composition.

[In General Formula (III) , R ¹ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group , and R ² , R ^3, and R ⁴ each independently represent a hydrogen atom or a substituent, R ⁶ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ² and R ³ , R ³ and R ⁶ , R ⁶ and R ⁹ , and R ⁴ and R ¹⁴ may be independently bonded to each other to form a 5-membered to 7-membered ring. ]

In [Formula (A), M ¹ represents a metal ^{such, Z 1, Z 2, Z} 3, and Z ⁴ are each independently a 6-membered ring comprised of atoms selected from carbon atoms and nitrogen atom Represents the atomic group to be formed. ] The colored curable composition according to claim 1 , wherein the tetraazaporphyrin-based dye represented by the general formula (A) is a phthalocyanine dye represented by the following general formula (B).

[In General Formula (B), M ¹ represents a metal, and R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent. ] Furthermore, the coloring curable composition of Claim 1 or Claim 2 containing the polymerizable monomer, the photopolymerization initiator, and the alkali-soluble binder, and was comprised by the negative type. A color filter comprising at least one azomethine dye represented by the following general formula (III) and at least one tetraazaporphyrin dye represented by the following general formula (A).

[In General Formula (III) , R ¹ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group , and R ² , R ^3, and R ⁴ each independently represent a hydrogen atom or a substituent, R ⁶ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ² and R ³ , R ³ and R ⁶ , R ⁶ and R ⁹ , and R ⁴ and R ¹⁴ may be independently bonded to each other to form a 5-membered to 7-membered ring. ]

In [Formula (A), M ¹ represents a metal ^{such, Z 1, Z 2, Z} 3, and Z ⁴ are each independently a 6-membered ring comprised of atoms selected from carbon atoms and nitrogen atom Represents the atomic group to be formed. ]   A color filter comprising: a step of applying a colored curable composition according to any one of claims 1 to 3 on a support, exposing through a mask, and developing to form a pattern image. Production method.