JP2007094187A - Colored curable composition, and color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition having high storage stability and excellent in heat and light stabilty of a formed pattern image, and a color filter using the composition and a method for producing the color filter. <P>SOLUTION: The colored curable composition contains a dye represented by formula (I), wherein R<SP>1</SP>-R<SP>6</SP>each independently represent hydrogen atom or a substituent; R<SP>7</SP>and R<SP>8</SP>each independently represent hydrogen atom, alkyl, alkenyl, aryl or a heterocyclic group; Za and Zb each independently represent -N= or -C(R<SP>9</SP>)=, R<SP>9</SP>represents hydrogen atom or a substituent, and R<SP>3</SP>and R<SP>4</SP>, R<SP>4</SP>and R<SP>8</SP>, R<SP>5</SP>and R<SP>6</SP>, R<SP>6</SP>and R<SP>7</SP>, and/or R<SP>7</SP>and R<SP>8</SP>can bond to each other to form a 5-, 6- or 7-membered ring. The color filter using the composition and the method for producing the color filter are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored curable composition suitable for forming a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), a color filter using the same, and a production thereof. Regarding the method.

  A color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to the same plane on a substrate as a color filter formed on the element for colorizing a solid-state image sensor or a liquid crystal display element A color filter including a filter, a red filter layer, a green filter layer, and a blue filter layer is known. In each of these filter layers, a belt-like pattern or a mosaic pattern is formed. Various methods have been proposed as a method for producing a color filter. Among them, there is a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeat a patterning process a required number of times. Widely used.

  The color resist method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions (hereinafter also referred to as “pigment dispersion method”). . The pigment dispersion method uses a pigment, so it is stable to light and heat, etc., and has sufficient positional accuracy for patterning by photolithography, making it possible to produce color filters for large screens and high-definition color displays. This is the preferred method.

  In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied on a glass substrate using a spin coater, a roll coater or the like, a coating film is formed, and the coating film is subjected to pattern exposure. Colored pixels are obtained by developing, and this operation is performed for each color to obtain a color filter. As said pigment dispersion method, the negative photosensitive composition using a photopolymerizable monomer and a photoinitiator for alkali-soluble resin is disclosed (for example, refer patent document 1-patent document 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 does not improve resolution, and has problems such as color unevenness due to coarse pigment particles, so that a fine pattern such as a solid-state image sensor is required. It was not suitable for use. In order to solve this problem, the use of dyes has been proposed in the past, and positive photosensitive compositions using dyes have been disclosed (for example, see Patent Documents 9 to 12).

However, dye-containing colored curable compositions have the following problems, and further improvements are required.
i) Dyes are generally inferior in heat resistance, light resistance and the like compared to pigments and require further improvement in fastness.
ii) If the molar absorption coefficient of the dye is low, a large amount of dye must be added. For this reason, other components such as a polymerizable compound, a binder, and a photopolymerization initiator in the colored curable composition must be reduced, and the curability of the composition, the heat resistance after curing, and the developability of the non-cured portion. It is desirable to improve the problems such as lowering.
iii) Dyes often interact with other components in the curable composition, making it difficult to adjust the developability (solubility) of the cured and non-cured areas, resulting in decreased sensitivity and degraded resolution. Arise. Further improvements are also required in terms of sensitivity and resolution.
As described above, the fastness of the dyes conventionally used in the photosensitive composition is not sufficiently satisfactory. Furthermore, it is difficult to contain a dye at a high concentration because of its low solubility in the photosensitive composition, and an improvement has been demanded.

On the other hand, blue or cyan dyes are used for the blue filter array and the green filter array of the color filter (see, for example, the above-mentioned Patent Documents 10 to 11). Triarylmethane dyes used as cyan dyes are desired to be improved in terms of fastness, and phthalocyanine dyes are excellent in fastness but have improved solubility and color value.
Furthermore, phthalocyanine dyes have the problem of deteriorating the light fastness of other dyes to be mixed. On the other hand, regarding the pyrrolotriazole-based azomethine dyes, details of the colored curable composition, the color filter, and the production method thereof are not disclosed (for example, Patent Document 13).
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 Japanese Patent Laid-Open No. 2002-14222 JP 2002-14221 A Japanese Patent Publication No.7-111485 JP 2003-96327 A

  An object of the present invention is to provide a colored curable composition having high storage stability and excellent heat fastness and light fastness of a pattern image to be formed, a color filter using the same, and a method for producing the same. is there.

  In the present invention, various dye compounds having a good hue and high fastness to light and heat are examined in detail. A dye having a specific structure is particularly effective in improving fastness such as heat resistance and light resistance. Obtained knowledge that it is useful, and based on this knowledge, a colored curable composition having the following constitution having high sensitivity, high resolution and high transmittance characteristics, a color filter, and a method for producing the same are provided, and the object is achieved. It has been done. Specific means for achieving the above object are as follows.

  <1> A colored curable composition containing a dye represented by the following general formula (I).

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、およびＲ⁶は、各々独立に、水素原子または置換基を表す。Ｒ⁷およびＲ⁸は、各々独立に、水素原子、アルキル基、アルケニル基、アリール基、またはヘテロ環基を表す。ＺａおよびＺｂは、各々独立に、−Ｎ＝または−Ｃ（Ｒ⁹）＝を表す。Ｒ⁹は水素原子または置換基を表す。Ｒ³とＲ⁴、Ｒ⁴とＲ⁸、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、および／またはＲ⁷とＲ⁸とが互いに結合して５員、６員、または７員の環を形成してもよい。〕

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Za and Zb each independently represent —N═ or —C (R ⁹ ) ═. R ⁹ represents a hydrogen atom or a substituent. R ³ and R ⁴ , R ⁴ and R ⁸ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and / or R ⁷ and R ⁸ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed. ]

  <2> The colored curable composition according to <1>, wherein the coloring matter is represented by the following general formula (II).

〔式中、Ｒ¹〜Ｒ⁸は、前記一般式（Ｉ）におけるＲ¹〜Ｒ⁸と同義である。Ｒ¹⁰は、水素原子または置換基を表す。〕

Wherein, R ¹ to R ⁸ have the same meanings as R ¹ to R ⁸ in the general formula (I). R ¹⁰ represents a hydrogen atom or a substituent. ]

<3> at least one dye represented by formula (I);
At least one of a triarylmethane dye having an absorption maximum at 550 nm to 650 nm and / or a xanthene dye having an absorption maximum at 500 nm to 600 nm;
The colored curable composition as described in <1> or <2> above, which contains

  <4> The above <1> to <<>, characterized by containing at least one dye represented by the general formula (I) and at least one dye represented by the following general formula (III): 3> a colored curable composition.

〔式中、Ｒ¹⁰¹〜Ｒ¹⁰⁵は、各々独立に、水素原子または置換基を表す。Ｒ¹⁰⁶〜Ｒ¹⁰⁷は、各々独立に、アルキル基、アルケニル基、アリール基、またはヘテロ環基を表す。ＺｃおよびＺｄは各々独立に−Ｎ＝、または−Ｃ（Ｒ¹⁰⁸）＝を表す。Ｒ¹⁰⁸は水素原子または置換基を表す。Ｒ¹⁰²とＲ¹⁰³、Ｒ¹⁰³とＲ¹⁰⁶、Ｒ¹⁰⁴とＲ¹⁰⁵、Ｒ¹⁰⁵とＲ¹⁰⁷、および／またはＲ¹⁰⁶とＲ¹⁰⁷とが互いに結合して５員、６員、または７員の環を形成してもよい。〕

[Wherein, R ^{101 to} R ¹⁰⁵ each independently represents a hydrogen atom or a substituent. R ^{106 to} R ¹⁰⁷ each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Zc and Zd each independently represent —N═ or —C (R ¹⁰⁸ ) ═. R ¹⁰⁸ represents a hydrogen atom or a substituent. ^R102 and ^R103 , ^R103 and ^R106 , ^R104 and ^R105 , ^R105 and ^R107 , and / or ^R106 and ^R107 are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed. ]

  <5> A color filter comprising the colored curable composition according to <1> to <4>.

  <6> A process for producing a color filter comprising the steps of applying the colored curable composition of <1> to <4> on a support, exposing through a mask, and developing to form a pattern. Is the method.

According to the present invention, a colored curable composition having high storage stability and excellent in heat fastness and light fastness of a pattern image to be formed can be provided.
Further, according to the present invention, the color curable composition is composed of the colored curable composition and has high resolution and high transmittance characteristics, and has high heat fastness and light fastness, and high production of the color filter. It is possible to provide a method of manufacturing a color filter that can be manufactured with the property.

Below, the colored curable composition of this invention, a color filter, and its manufacturing method are demonstrated in detail.
<Colored curable composition>
The colored curable composition of the present invention comprises a dye represented by the following general formula (I), and preferably comprises a binder, a radiation sensitive compound, and a polymerizable monomer. The colored curable composition of the present invention contains a dye represented by the general formula (I), and in combination with this, a triarylmethane dye having an absorption maximum at 550 nm to 650 nm and / or 500 nm to 600 nm. At least one xanthene dye having an absorption maximum or at least one dye represented by formula (III) described later can be used.
Moreover, generally the colored curable composition of this invention can be comprised further using a solvent, and can be comprised using other components, such as a crosslinking agent, as needed.

<Dye>
(Dye represented by general formula (I))
The colored curable composition of the present invention contains at least one dye represented by the following general formula (I). This dye has a good hue, does not precipitate over time when it is in the form of a liquid preparation or a coated film, has excellent storage stability, and particularly has high heat and light fastness.

In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. Examples of the substituent for R ^{1 to} R ⁶ include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 linear, branched or cyclic). For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-norbornyl Adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably 6 to 24 carbon atoms). , More preferably 6-12 aryl groups such as phenyl, naphthyl), heterocyclic groups (preferably Is a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 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 24 carbon atoms, more preferably 3 to 12 carbon atoms such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, n -Hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as methoxy, ethoxy, 1-butoxy, 2-butoxy , Isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example Cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenoxy or 1-naphthoxy), a heterocyclic oxy group (preferably having 1 carbon atom) To 24, more preferably 1 to 12 heterocyclic oxy groups such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy groups (preferably having 1 to 24 carbon atoms, more preferably 1). -12 silyloxy groups, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy groups (preferably 2-24 carbon atoms, more preferably 2-12 acyloxy groups, for example, acetoxy , Pivaloyloxy, benzoyloxy, dodeca Yloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, an ethoxycarbonyloxy, t-butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group, for example, Cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having a carbon number) 1 to 24, more preferably 1 to 12, carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenyl Rubamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy ), An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 12 carbon atoms such as phenylsulfonyloxy), an acyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). An acyl group of, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, Methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonyl), An yl group (preferably a carbamoyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, n-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propyl Carbamoyl, N-phenylcarbamoyl, N-methyl N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably an amino group having 24 or less carbon atoms, more preferably 12 or less, such as amino, methyl Amino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms such as anilino, N -Methylanilino), a heterocyclic amino group (preferably A heterocyclic amino group having a prime number of 1 to 24, more preferably 1 to 12, such as 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, , Acetamide, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), a ureido group (preferably a ureido group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as ureido, N, N-dimethylureido, N-phenyl). Ureido), an imide group (preferably an imide group having 20 or less carbon atoms, more preferably 12 or less, such as N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably having 2 to 24 carbon atoms, more preferably 2-12 alkoxycarbonylamino groups, for example methoxy Carbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms, more preferably 7 to 12 aryloxycarbonylamino group) And a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide) , Cyclohexanesulfonamido), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as N, N-dipropylsulfa Ylamino, N- ethyl -N- dodecyl sulfamoylamino)

An azo group (preferably an azo group having 1 to 24 carbon atoms, more preferably 1 to 24 carbon atoms such as phenylazo, 3-pyrazolylazo), an alkylthio group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms); An alkylthio group, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably an arylthio group having 6 to 24 carbon atoms, more preferably 6-12 carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably A heterocyclic thio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably having a carbon number of 1 to 24, more preferably 1-12 alkylsulfinyl groups, for example dodecanesulfinyl ), An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). Alkylsulfonyl groups of, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 to 24 carbon atoms) More preferably an arylsulfonyl group having 6 to 12, for example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, more preferably 16 or less carbon atoms). Moyl group such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, A phosphonyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably having a carbon number of 1 to 24, more preferably 1-12 phosphinoylamino groups, for example diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

When the substituents of R ^{1 to} R ⁶ are further substitutable groups, they may have the above substituents, and when they have two or more substituents, those substituents The groups may be the same or different.

R ⁷ and R ⁸ in formula (I) each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Preferred ranges of the alkyl group, alkenyl group, aryl group, and heterocyclic group are the same as the alkyl group, alkenyl group, aryl group, and heterocyclic group described in the above R ^{1 to} R ⁶ .
The alkyl group, alkenyl group, aryl group, and heterocyclic group of R ⁷ and R ⁸ may be further substituted with the substituents described in the above R ^{1 to} R ⁶ and substituted with two or more substituents. The substituents may be the same or different.

Za and Zb in formula (I) each independently represent -N =, or -C represents the (R ⁹⁾ =. R ⁹ represents a hydrogen atom or a substituent. The substituent of R < ⁹ > is synonymous with the substituent demonstrated by said R < ¹ > -R < ⁶ >. When the substituent of R ⁹ is a further substitutable group, it may have the substituent described in the above R ^{1 to} R ⁶ , and when it is substituted with two or more substituents These substituents may be the same or different.

R ³ and R ⁴ , R ⁴ and R ⁸ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and / or R ⁷ and R ⁸ in general formula (I) are bonded to each other to form 5-membered, 6-membered, Alternatively, a 7-membered ring may be formed. Such 5-membered, 6-membered, or 7-membered is, for example, a ring composed of an element selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, and a triazole ring. Examples of the 6-membered ring include a pyridine ring, a pyrimidine ring, and a pyrazine ring. A 7-membered ring includes a heptane ring. Moreover, the said 5-membered ring and 6-membered ring may be a saturated ring. Preferably, the 6-membered ring and a saturated ring thereof are used.

  The dye represented by the general formula (I) is preferably represented by the general formula (II).

R ^{1 to} R ⁸ in the general formula (II) are synonymous with those in the general formula (I). When R ^{1 to} R ⁸ in the general formula (II) are further substitutable groups, they may be substituted with the substituents described for R ^{1 to} R ⁶ and substituted with two or more substituents. The substituents may be the same or different.
In the general formula (II), R ³ and R ⁴ , R ⁴ and R ⁸ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and / or R ⁷ and R ⁸ are bonded to each other to form 5 or 6 members. Or a 7-membered ring.

R ¹⁰ in the general formula (II) represents a hydrogen atom or a substituent. Substituents R ¹⁰ has the same meaning as the substituent described in the R ¹ to R ^6. When the substituent of R ¹⁰ is a further substitutable group, it may be substituted with the substituent described in the above R ^{1 to} R ⁶ , and when it is substituted with two or more substituents These substituents may be the same or different.

  The dye represented by the general formula (I) is more preferably a dye represented by the following general formula (IV), and particularly preferably a dye represented by the following general formula (V).

In formula, R < ³ > -R < ⁸ > is synonymous with it in the said general formula (I).
R ¹¹ and R ¹² in the general formula (IV) represent a substituent having a sum of Hammett substituent constants σp selected from the substituents described in R ^{1 to} R ⁶ of 0.7 or more. R ¹³ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

  Hammett's law was established in 1935 by L. P. This is an empirical rule proposed by Hammett and is described in a general book. For example, J. et al. A. Dean, “Lange's and book of ChemistRy”, 12th edition, 1979 (McGRew-Hill) and “Areas of Chemistry” special edition, 122, 96-103, 1979 (Nankodo). However, even if each substituent is limited or specified by Hammett's substituent constant σp value in the present invention, it is not limited to only a substituent having a known value that can be found in the above-mentioned book, Substituents whose values fall within the range when measured based on As for the “Hammett substituent constant σp value” in the present invention, the σp value is used as a scale indicating the electronic effect of a substituent even for a substituent that is not a benzene derivative, regardless of the substitution position.

  Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.3 or more include an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms such as acetyl, pivaloyl, 2 -Ethylhexyl, benzoyl, cyclohexanoyl), acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetoxy, pivaloyloxy), carbamoyl group (preferably having 1 to 24 carbon atoms, More preferably, it is a carbamoyl group of 1 to 18, for example, carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, Nt-butylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl, N , N-diisopropylcarbamoyl, N-ethyl- -Phenylcarbamoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, cyclohexylcarbonyl), aryloxycarbonyl group ( Preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyl, cyano group, nitro group, alkylsulfinyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 18 alkylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, 2-ethylhexylsulfinyl, cyclopentylsulfinyl), arylsulfinyl groups (preferably having 6 to 6 carbon atoms) 24, more preferably an arylsulfinyl group having 6-18, for example, phenylsulfinyl, p-toluenesulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1-24 carbon atoms, more preferably 1-18, , Methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthylsulfonyl), sulfamoyl groups ( A sulfamoyl group having preferably 24 or less carbon atoms, more preferably 18 or less carbon atoms, such as N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-phenylsulfoyl. Moyl, N-cyclohexylsulfamoyl), halogenated alkyl group (preferably a halogenated alkyl group having 1 to 24 carbon atoms, more preferably 1 to 12, for example, trifluoromethyl, pentafluoropropyl), halogenated alkoxy A group (preferably a halogenated alkoxy group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms such as trifluoromethoxy), a halogenated aryloxy group (preferably having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms). A halogenated aryloxy group, for example, pentafluorophenyloxy), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1-12, such as 2-benzoxazoyl, 2-benzothiazolyl 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1 Pyrrolyl), or the like can be mentioned.

R ¹³ in the general formula (IV) represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The alkyl group, alkenyl group, aryl group, or heterocyclic group represented by R ¹³ has the same meaning as the alkyl group, alkenyl group, aryl group, and heterocyclic group described in the above R ^{1 to} R ⁶ .

  The dye represented by the general formula (I) is most preferably represented by the following general formula (V).

In formula, R < ³ > -R < ⁵ > is synonymous with it in the said general formula (I). R ^{11 to} R ¹³ have the same meaning as that of the general formula (IV). R ¹⁴ represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ¹⁵ , R ¹⁶ , and R ¹⁷ each independently represent a hydrogen atom or an alkyl group.

R ³ and R ⁴ , R ⁴ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ⁵ and R ¹⁷ in the general formula (V) are bonded to each other to form 5, 6 or 7 members. The ring may be formed.

R ¹⁴ in the general formula (V) represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and the alkyl group, the alkenyl group, the aryl group, and the heterocyclic group represented by R ¹⁴ are the above R ^1. alkyl group described for to R ^6, an alkenyl group, an aryl group, and the same meanings of the group and heterocyclic group.
When the alkyl group, alkenyl group, aryl group and heterocyclic group of R ¹⁴ are further substitutable groups, they may be substituted with the groups described for the substituents of R ^{1 to} R ^6. When it is substituted with more than one substituent, these substituents may be the same or different.

R ^{15 to} R ¹⁷ in the general formula (V) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ^{15 to} R ¹⁷ preferably has 1 to 12 carbon atoms, and more preferably represents a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The substituent of the substituted alkyl group of R ^{15 to} R ¹⁷ represents a group having the same meaning as the group described for the substituent of R ^{1 to} R ⁶ . When substituted with two or more substituents, these substituents may be the same or different.

A more preferable range of the dye represented by formula (V) will be described.
The dye represented by the general formula (V) is preferably R ³ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkoxy group, an alkoxycarbonylamino group, a ureido group, an alkylthio group, an arylthio group, Or a heterocyclic group, R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹¹ and R ¹² each independently represent a perfluoroalkyl group, an alkoxycarbonyl group, or a carbamoyl group. , A cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a heterocyclic group, R ¹³ is represented by an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ¹⁴ is an alkyl group, alkenyl, R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom or an alkyl group. It is.

More preferably, R ³ represents a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, an alkoxycarbonylamino group, or a ureido group, and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, or represents an alkyl group, R ^11, R ¹² are each independently, perfluoroalkyl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a heterocyclic group,, R ¹³ Is represented by an alkyl group, an aryl group, or a heterocyclic group, R ¹⁴ is represented by an alkyl group, and R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently represented by a hydrogen atom or an alkyl group.

Most preferably, R ³ is a hydrogen atom, alkyl group, acylamino group, or alkoxycarbonyl group, R ⁴ or R ⁵ is a hydrogen atom, and R ¹¹ is a trifluoromethyl group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group. , R ¹² is a perfluoroalkyl group, alkoxycarbonyl group, carbamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, or heterocyclic group, R ¹³ is an alkyl group, aryl group, or heterocyclic group, R ¹⁴ Is an alkyl group, and R ¹⁵ , R ¹⁶ and R ¹⁷ are each represented by a methyl group.

  Specific examples of the dyes represented by formulas (I) to (V) (exemplary dyes CD-1 to CD46) are shown below, but the present invention is not limited thereto.

  Synthesis of the dyes represented by the above general formula (I), general formula (II), general formula (IV), and general formula (V) is disclosed in JP-A-5-177959, JP-A-2003-96326, It can be synthesized by the method described in Kaikai 2003-96327.

(Triarylmethane dyes / xanthene dyes)
The colored curable composition of the present invention has at least one dye represented by formula (I), a triarylmethane dye having an absorption maximum at 550 nm to 650 nm, and / or an absorption maximum at 500 nm to 600 nm. It is preferable to contain at least one xanthene pigment.

-Triarylmethane dye having absorption maximum at 550 nm-650 nm-
As the triarylmethane dye having an absorption maximum at 550 nm to 650 nm (hereinafter sometimes simply referred to as “triarylmethane dye”), a dye represented by the following general formula (VI) is preferable.

In the formula, R ²⁰ and R ²¹ each independently represents a hydrogen atom or an alkyl group, R ²² represents a hydrogen atom or a sulfo group, R ²³ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group, R represents a sulfo group or a carboxyl group, and R ²⁴ represents an alkyl group.

The alkyl groups represented by R ²⁰ , R ²¹ and R ²⁴ in the general formula (VI) represent groups having the same meaning as the alkyl groups described in the above R ^{1 to} R ⁶ , and preferably methyl, ethyl, propyl, butyl, etc. Can be mentioned.
The alkyl group, alkoxy group, aryloxy group, and amino group of R ²³ in the general formula (VI) have the same meaning as the alkyl group, alkoxy group, aryloxy group, and amino group described in the above R ^{1 to} R ⁶ . Represents a group.
The dye represented by the general formula (VI) may form a salt. Examples of the salt include alkali metal salts (for example, sodium, potassium, lithium, calcium, magnesium, strontium), organic amine salts (for example, triethylamine, triethanolamine, diethanolamine, morpholine, piperidine, pyridine, guanidine, diphenylguanidine), etc. Is mentioned.
The salt of the dye represented by the general formula (VI) may be formed of —SO ₃ —, and may be formed of a sulfo group or a carboxyl group of R ²² or R ²³ .

  Examples of the dye represented by the general formula (VI) include C.I. Acid Blue 7 (C.I. Acid Blue 7), C.I. Acid Blue 83 (C.I. Acid Blue 83), and C.I. Acid Blue 90 (C.I. Acid Blue 90), C.I. Solvent Blue 38 (C.I. Solvent Blue 38), C.I. Acid Violet 17 (C.I. Acid Violet 17), C.I. -Acid violet 49 (CI Acid Violet 49), C.I. Acid Green 3 (CI. Acid Green3), etc. are mentioned.

-Xanthene dye having absorption maximum at 500 nm to 600 nm-
Next, a xanthene dye having an absorption maximum at 500 nm to 600 nm (hereinafter sometimes simply referred to as “xanthene dye”) will be described. As the xanthene dye, a dye represented by the following general formula (VII) is preferable.

In the formula, R ^{30 to} R ³³ each independently represents a hydrogen atom or an alkyl group, and R ^{34 to} R ³⁶ each independently represents a sulfo group or a salt thereof, a sulfonamide group, or a sulfamoyl group.

The alkyl group represented by R ^{30 to} R ³³ in the general formula (VII) represents a group having the same meaning as the alkyl group described for R ^{1 to} R ⁶ . The alkyl group of R ^{30 to} R ³³ may further have the substituent described in the above R ^{1 to} R ⁶ , and when it is substituted with two or more substituents, these substituents are They may be the same or different.

The sulfonamide group and sulfamoyl group of R ^{34 to} R ³⁶ in the general formula (VII) represent groups having the same meaning as the sulfonamide group and sulfamoyl group described in the above R ^{1 to} R ⁶ . When the sulfonamide group of R ^{34 to} R ³⁶ and the sulfamoyl group are further substitutable groups, they may be substituted with the substituents described in the above R ^{1 to} R ⁶ , and two or more substituents In the case of being substituted with these, these substituents may be the same or different.

  As a pigment | dye represented by general formula (VII), C.I. Acid Red 289 (CI Acid.Red 289) etc. are mentioned, for example.

(Dye represented by general formula (III))
Next, the dye represented by formula (III) will be described in detail.

In the formula, R ^{101 to} R ¹⁰⁵ each independently represents a hydrogen atom or a substituent. R ^{106 to} R ¹⁰⁷ each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Zc and Zd each independently represent —N═ or —C (R ¹⁰⁸ ) ═. R ¹⁰⁸ represents a hydrogen atom or a substituent. ^R102 and ^R103 , ^R103 and ^R106 , ^R104 and ^R105 , ^R105 and ^R107 , and / or ^R106 and ^R107 are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed.

R ^{101 to} R ¹⁰⁷ , Zc, and Zd in the general formula (III) will be described in detail.
R ^{101 to} R ¹⁰⁵ in the general formula (III) each independently represents a hydrogen atom or a substituent, and the preferred range of the substituent for R ^{101 to} R ¹⁰⁵ is the same as the substituent described for R ^{1 to} R ⁶ above. It is.
When the substituents of R ^{101 to} R ¹⁰⁵ are further substitutable groups, they may be substituted with the substituents described for R ^{1 to} R ⁶ and are substituted with two or more substituents. In some cases, these substituents may be the same or different.

^R102 and ^R103 , ^R103 and ^R106 , ^R106 and ^R107 , ^R107 and ^R105 , ^R104 and ^R105 are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. May be. Examples of the 5-membered, 6-membered, or 7-membered ring include the same rings as those described for R ^{1 to} R ⁶ .

R ¹⁰⁶ and R ¹⁰⁷ in the general formula (III) each independently 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 ¹⁰⁶ and R ¹⁰⁷ have the same meaning as the alkyl group, alkenyl group, aryl group, and heterocyclic group described in the above R ^{1 to} R ⁶ . Represents a group. When the alkyl group, alkenyl group, aryl group, and heterocyclic group of R ¹⁰⁶ and R ¹⁰⁷ are further substitutable groups, they may be substituted with the substituents described above for R ^{1 to} R ⁶ , When substituted with two or more substituents, these substituents may be the same or different.

Zc and Zd in the general formula (III) each independently represent -N = or -C ( ^R108 ) =. R ¹⁰⁸ represents a hydrogen atom or a substituent, and the substituent represented by R ¹⁰⁸ represents a group having the same meaning as the substituent described for R ^{1 to} R ⁶ . The substituent of R ¹⁰⁸ may be further substituted with the substituent described in the above R ^{1 to} R ⁶ . When substituted with two or more substituents, these substituents may be the same or different.

  The dye represented by the general formula (III) is preferably represented by the following general formula (VIII).

In the formula, R ^{101 to} R ¹⁰⁴ have the same meanings as those in the general formula (III). R ²⁰¹ represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ^{202 to} R ²⁰⁴ each independently represent a hydrogen atom or an alkyl group. ^R205 represents a hydrogen atom or a substituent.

In the general formula (VIII), a preferable range of the alkyl group, alkenyl group, aryl group, and heterocyclic group represented by R ^{201 is} the alkyl group, alkenyl group, aryl group, and heterocyclic group described in the above R ^{1 to} R ^6. It is the same.

The alkyl group of R ^{202 to} R ²⁰⁴ in the general formula (VIII) is preferably a linear, branched, cyclic, substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms. For example, methyl, ethyl, propyl, butyl, isopropyl, cyclohexyl and the like. Examples of the substituent of the substituted alkyl group include the substituents described in the above R ^{1 to} R ⁶ . When substituted with two or more substituents, these substituents may be the same or different.

R ²⁰⁵ in the general formula (VIII) represents a hydrogen atom or a substituent, and the substituent of R ²⁰⁵ represents a group having the same meaning as the substituent described in the above R ^{1 to} R ⁶ . When the substituent of R ²⁰⁵ further if a displaceable group, the may be substituted with a substituent described in the R ¹ to R ^6, which are substituted by two or more substituents These substituents may be the same or different.

Next, a preferable range of the dye represented by the general formula (VIII) will be described.
R ¹⁰¹ in the general formula (VIII) is an alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, carbamoyloxy group, acyl group, alkoxycarbonyl Group, carbamoyl group, imide group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ are each independently a hydrogen atom, Halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfonamide Group, sulfamoylamino group, Zo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, carboxyl group, ^R201 is an alkyl group, alkenyl group, aryl group, or heterocyclic group R ^{202 to} R ²⁰⁴ are each independently represented by a hydrogen atom or an alkyl group, and R ²⁰⁵ is represented by an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

More preferably, R ¹⁰¹ in the general formula (VIII) is an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyloxy group, alkoxycarbonyl group, carbamoyl group, imide group, alkylthio group. , arylthio group, represented by a heterocyclic thio group, R ^102, R ^103, and R ¹⁰⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxy Represented by a carbonyl group, a carbamoyl group, an amino group, an anilino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a sulfonamido group, a sulfamoyl group, a sulfo group, a carboxyl group, and ^R201 is an alkyl group, an aryl group, or represented by heterocyclic group, R ²⁰² to R ²⁰⁴ are each independently hydrogen Represented by child or an alkyl group, R ²⁰⁵ represents an alkyl group, represented by an aryl group or a heterocyclic group.

More preferably, R ¹⁰¹ in the general formula (VIII) is represented by an alkyl group, an aryl group, or a heterocyclic group, and R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, Expressed by an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a sulfonamido group, a sulfamoyl group, a sulfo group, or a carboxyl group, ^R201 is an alkyl group, an aryl group Or R ^{202 to} R ²⁰⁴ each independently represents a hydrogen atom or an alkyl group, and R ²⁰⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

Most preferably, R ¹⁰¹ in formula (VIII) is represented by a tertiary alkyl group, and R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, an alkoxycarbonylamino group, a sulfonamido group, a sulfamoyl group, a sulfo group, represented by a carboxyl group, R ²⁰¹ is represented by an alkyl group, R ²⁰² to R ²⁰⁴ are each independently represented by a methyl group, and R ²⁰⁵ is represented by an alkyl group, an aryl group, or a heterocyclic group.

Next, specific examples (illustrated dyes MD-1 to MD50) of the dyes represented by the general formula (III) and the general formula (VIII) are shown below. However, the present invention is not limited to these.

  Next, the synthesis of the dyes represented by the general formula (III) and the general formula (VIII) will be described by way of examples of the synthesis of the above-described exemplary dye MD-1. Illustrative dye MD-1 in this invention is compoundable according to the following reaction scheme A. However, the present invention is not limited to this.

[Synthesis Example 1]
-Synthesis of Exemplified Dye MD-1-

(1) Synthesis of Compound B 300 ml of dimethylimidazolidinone was added to 94.7 g (0.5 mol) of Compound A, 37.5 g (0.25 mol) of sodium iodide and 126 g (1.5 mol) of sodium bicarbonate. Heated to 95 ° C. and stirred. To this solution, 90.3 g (0.65 mol) of 3-bromopropanol was added dropwise. After completion of the dropwise addition, the reaction was completed by heating and stirring at 95 ° C 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 solution was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 10/1). 90.5 g (yield: 73.2%) of compound B was obtained. Compound A was manufactured by Sigma-Aldrich.

(2) Synthesis of Compound C 270 ml of methanol was added to 90 g (0.364 mol) of Compound B obtained by the above method, and the mixture was cooled to 5 ° C. and stirred. To this solution, 93.7 ml (1.09 mol) of concentrated hydrochloric acid was added dropwise. Further, a solution obtained by dissolving 27.6 g (0.4 mol) of sodium nitrite in 75 ml of water was added dropwise while maintaining the temperature at 5 ° C to 10 ° C. After completion of the dropwise addition, the reaction was completed by stirring at 5 ° C. to 10 ° C. for 2 hours. After completion of the reaction, 500 ml of ethyl acetate and 1000 ml of water were added. After neutralizing the solution by adding 84 g of sodium hydrogen carbonate little by little, the aqueous phase was removed. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. When this ethyl acetate solution was concentrated under reduced pressure, crystals were precipitated. To these crystals, 200 ml of n-hexane and 200 ml of ethyl acetate were added and stirred to disperse the crystals. The crystals were filtered and dried. 78 g (yield: 77.6%) of compound C was obtained.

(3) Synthesis of Compound E Compound E was synthesized by the method shown in Reaction 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 this solution was added 196 ml of 28% methanol solution of sodium methoxide. After completion of the addition, 190 g (0.974 mol) of 2-bromobutanoic acid ethyl ester was added dropwise to this solution. After completion of the dropwise 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 solution was washed with brine, and then ethyl acetate was distilled off under reduced pressure. To the residue, 250 ml of methanol was added and stirred at room temperature. An aqueous solution in which 144 g of sodium hydroxide was dissolved in 1000 ml of water was added to this solution. This solution was heated to 50 ° C. to 55 ° C. and stirred for 2 hours. After completion of the reaction, 340 ml of concentrated hydrochloric acid was added dropwise to the reaction solution to make it acidic, and then extracted with 1000 ml of ethyl acetate. The ethyl acetate solution was washed with brine and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure. Intermediate M was obtained quantitatively.

-Synthesis of Intermediate N-
400 ml of toluene was added to 93.1 g (0.433 mol) of intermediate M obtained by the above method, and the mixture was heated to 85 ° C. 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 an ethyl acetate solution of intermediate N, which was used in the next step.

-Synthesis of Compound E-
According to the method described in JP-A-2-201443, the starting material 5-amino-3-methylpyrazole was changed to 5-amino-3-t-butylpyrazole (synthesized by the method described in Japanese Patent No. 2670943). Intermediate L was synthesized.
To 189 g (0.538 mol) of this intermediate L, 570 ml of 2-propanol was added and stirred with heating. 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. To the residue, 420 g of sodium bicarbonate, 1500 ml of water, and 1200 ml of ethyl acetate were added and stirred at room temperature.
To this solution was added dropwise an ethyl acetate solution of intermediate N obtained by the above method. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the aqueous phase was removed. When this ethyl acetate solution 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 Illustrative Dye MD-1 As shown in Scheme 1, 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 by the above method and heated to 40 ° C. And stirred. To this solution, 25 g of hydrosulfite soda was added little by little. After completion of the addition, the reaction was carried out at 40 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate and 200 m of water were added, and the aqueous phase was removed. This ethyl acetate solution was used in the next step.
100 ml of methanol and 200 ml of water were added to 10.0 g (0.0242 mol) of compound E and 21 g of sodium hydrogen carbonate, and the mixture was stirred at room temperature. To this solution was added the total amount of the ethyl acetate solution. An aqueous solution in which 12 g of ammonium persulfate was dissolved in 100 ml of water was added dropwise to this solution. 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, and then the ethyl acetate solution was washed with water. The ethyl acetate solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1). An amorphous exemplified dye MD-1 was obtained. λmax = 556 nm, and the absorption coefficient was 5,5000 (ethyl acetate solution).

As the dye in the colored curable composition of the present invention, a dye represented by the above-described general formula (I) (including the dyes represented by the general formulas (II) to (IV)) may be used alone. Or two or more types can be used in combination.
Moreover, in this invention, although the density | concentration in the coloring curable composition of all the pigments changes with molecular weight and a molar extinction coefficient, 0.5-80 mass% is preferable with respect to all the solid components of this composition, 0 0.5-60 mass% is more preferable, and 0.5-50 mass% is the most preferable.

In order to produce a blue filter array, a dye represented by general formula (I) (including dyes represented by general formulas (II) to (IV)) and the triarylmethane dye (general It is preferable to use a mixture of a triarylmethane dye represented by the formula (VI) and / or a xanthene dye (including a xanthene dye represented by the general formula (VII)).
Moreover, it is also preferable to mix and use the pigment | dye represented by general formula (I), and the pigment | dye represented by general formula (III) (The pigment | dye represented by general formula (VIII) is included).

  A dye represented by the general formula (I) is mixed with another dye such as at least one selected from the triarylmethane dye, the xanthene dye and the dye represented by the general formula (III). When used, the mixing ratio (general formula (I) / other dyes) varies depending on the molar extinction coefficient, the required spectral characteristics, film thickness, etc. It can be used in the range of 1:20, and is preferably used in the range of 10: 1 to 1:10.

  The colored curable composition of the present invention may be any as long as it is cured by light or heat. Preferably, in addition to the dye of the present invention, a binder, a crosslinking agent or a polymerizable monomer, a radiation-sensitive compound. Etc. are preferably included.

<Binder>
The colored curable composition of the present invention preferably contains at least one binder. The binder in the present invention is not particularly limited as long as it is soluble in alkali, 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, etc., and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. There are polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  In addition, the alkali-soluble binder may be a copolymer of a monomer having a hydrophilic group, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and glycerol (meth) acrylate. (Meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, Methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl ( Data) acrylate, and the like.

  Other useful monomers having a hydrophilic group include tetrahydrofurfuryl group, phosphoric acid, phosphoric acid ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, and morpholinoethyl group. It is.

In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful.
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
In order to increase 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.

  Among the various binders, the binder in the present invention is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.), Cyclomer P-series and the like are preferable.

Moreover, an alkali-soluble phenol resin can be used as a binder which can be used for this invention. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin 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 the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, 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.
10-90 mass% is preferable with respect to the total solid in this composition, and, as for the usage-amount of the said binder in the colored curable composition of this invention, 20-80 mass% is still more preferable. 30-70 mass% is especially preferable.

<Crosslinking agent>
In the present invention, by using the dyes represented by the above general formulas (I) to (III), the curing reaction of the film is advanced to a higher degree than before, and a film having good curability can be obtained. However, it is possible to obtain a film that is more highly cured using a cross-linking agent.

  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, the crosslinking agent is selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one substituent selected from (c) at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; Examples thereof include substituted phenol compounds, naphthol compounds, and hydroxyanthracene compounds. A polyfunctional epoxy resin is particularly preferable.

  As the epoxy resin of the component (a), any epoxy resin having an epoxy group and crosslinkability may be used. Examples of these compounds include bisphenol A-glycidyl ether, ethylene glycol. Contains divalent glycidyl groups such as diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester, N, N-diglycidyl aniline Low molecular weight compounds, trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether, trivalent glycidyl group-containing low molecular weight compounds represented by Trisp-PA triglycidyl ether, etc. Tetravalent glycidyl group-containing low molecular weight compounds typified by pentaerythritol tetraglycidyl ether, tetramethylol bisphenol-A-tetraglycidyl ether, and the like, as well as polyvalent compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, etc. Glycidyl group-containing low molecular weight compounds, polyglycidyl (meth) acrylate, glycidyl represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like And group-containing polymer compounds.

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the component (b) is 2 to 6 for melamine compounds, and 2 to 4 for glycoluril compounds, guanamine compounds, and urea compounds. However, it is preferably 5 to 6 in the case of a melamine compound, and 3 to 4 in the case of a glycoluril compound, a guanamine compound or a urea compound.

  These methylol group-containing compounds can be obtained by heating the alkoxymethyl group-containing compound 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 can be obtained by mixing and stirring a methylol group-containing compound with an acyl chloride in the presence of a basic catalyst.

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

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

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds 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. These may be used alone or in combination.
The compounds according to (b) may be used alone or in combination.

  The number of methylol groups, acyloxymethyl groups, or alkoxymethyl groups contained in the component (c) is at least two per molecule. From the viewpoint of thermal crosslinkability and storage stability, 2 of the phenolic compound is required. A compound in which all of the 4th and 4th positions are substituted is 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 3-position or 5-position of the phenolic compound that serves as the skeleton may be unsubstituted or may have a substituent. Also in the naphthol compound serving as the skeleton, the OH group other than the ortho position may be unsubstituted or may have a substituent.

  These methylol group-containing compounds use a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkyl. It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonium hydroxide. The alkoxymethyl group-containing compound can be obtained by heating the methylol group-containing compound 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 can be obtained by reacting the methylol group-containing compound with acyl chloride in the presence of a basic catalyst.

  As the skeletal compound in component (c), the phenolic OH group ortho- or para-position unsubstituted phenol compound, naphthol compound, hydroxyanthracene compound, for example, phenol, cresol isomers, 2,3-xyleno- , 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol-A, 4,4′-bishydroxybiphenyl, Trisp-PA (manufactured by Honshu Chemical Industry Co., Ltd.) ), Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

  Specific examples of the component (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, trimethylol. (Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol bisphenol-A , Tetramethoxymethyl bisphenol-A, compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol-A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bis Hydroxy bifu Cycloalkenyl, hexamethylol of TRISP-PA, hexamethoxymethyl of TRISP-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated in hexamethylol of TRISP-PA, there is bishydroxymethyl 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, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, hexamethylol of Trisp-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxy. It is a phenol compound substituted with both a methyl group and a methylol group and an alkoxymethyl group.
These compounds in (c) may be used alone or in combination.

  The colored curable composition of the present invention does not necessarily contain a crosslinking agent, but when a crosslinking agent is used as necessary, the total content of the components (a) to (c) depends on the material. Although differing, 1-70 mass% is preferable with respect to solid content of this composition, 5-50 mass% is more preferable, and 7-30 mass% is especially 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 of the present invention is configured as a negative type.
The polymerizable monomer can be contained in a positive type system containing a naphthoquinone diazide compound described later together with a photopolymerization initiator described later. In this case, the degree of cure of the formed pattern can be further promoted. Hereinafter, the polymerizable monomer will be described.

As the polymerizable monomer, a compound having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) Polyfunctional alcohols such as sosocyanurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, JP-B-48-41708, JP-B-50-6034, JP-A-51-51 Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with (meth) acrylic acid, and mixtures thereof.
Examples of the polymerizable monomer further include 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% by mass, more preferably 1.0 to 80% by mass, and 2.0 to 70% by mass with respect to the solid content. Particularly preferred.

<Radiation sensitive compounds>
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound in the present invention is a compound that causes a chemical reaction such as generation of a radical, generation of an acid, generation of a base, and the like with respect to radiation such as UV, Deep UV, visible light, infrared light, and electron beam, The coating film is made free of alkali developer by insolubilizing it by reactions such as crosslinking, polymerization, decomposition of acidic groups, polymerizing polymerizable monomers and oligomers coexisting in the coating film, and causing crosslinking reaction of the crosslinking agent. Used for insolubilization.

  In particular, when the colored curable composition is composed of a negative type, it preferably contains a photopolymerization initiator, and when it constitutes a positive type, it preferably contains a naphthoquinonediazide compound.

-Photopolymerization initiator-
The photopolymerization initiator contained when the colored curable composition of the present invention is a negative composition will be described.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
In addition, you may further contain the said photoinitiator in the positive type | system | group containing a naphthoquinone diazide compound. In this case, the degree of pattern hardening to be formed can be further promoted.
Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

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

  As photopolymerization initiators of halomethyl-s-triazine compounds, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428 are disclosed. 1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

Other 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) -naphtho 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-triazi 2- (6-methoxy-naphth-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- [pN- (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) aminopheny ] -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 (chloroethyl) 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- p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2 , 6-di (tri (Loromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -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 (trichloromethyl) -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- ( -Bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di ( And trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ-104) manufactured by Midori Chemical, manufactured by PANCHIM T series (T-OMS, T-BMP, T-R, TB), Irgacure series (Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, manufactured by Ciba Specialty Chemicals, Inc. , Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (Darocur 1173); 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) Fe L] -1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl Dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, etc. Useful used.

In addition to the photopolymerization initiator, other known photopolymerization initiators can be used in combination with the colored curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triaryl imidazole dimer / p-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / Examples include trihalomethyl-s-triazine compounds.

  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, and 1 to 20% by mass with respect to the polymerizable monomer solid content. Is particularly preferred. When the content is within the above range, it is possible to prevent the polymerization from becoming difficult or the polymerization rate to increase, but the molecular strength to be lowered and the film strength to be weakened.

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

  Moreover, it is preferable to add a thermal polymerization inhibitor to the colored curable composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t). -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

~ Naphthoquinonediazide compound ~
Next, the naphthoquinone diazide compound contained when the colored curable composition of the present invention is positive will be described.
The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group. For example, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4- Examples thereof include sulfonic acid esters and o-naphthoquinonediazide-4-sulfonic acid amide. 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. .

  When the colored curable composition of the present invention is constituted in a positive type, the alkali-soluble phenol resin and the above-mentioned crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, in the organic solvent. It is preferable to dissolve at a ratio of The content of the naphthoquinone diazide compound is usually preferably added at a ratio of about 2 to 30% by mass and 2 to 50% by mass with respect to 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 used. The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the colored curable composition, but considers the solubility, applicability, safety, etc. of the binder. Is preferably selected.
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, methyl 3-oxypropionate, 3-oxypropionic acid Alkyl esters of 3-oxypropionic acid such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl lopionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, 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 Ethyl 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 For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene are preferable.

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

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

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

  Further, when the alkali solubility of the non-irradiated part (non-image part) is promoted and the developability of the colored curable composition of the present invention is further improved, an organic carboxylic acid, preferably Addition of a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be performed. Specifically, 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, glutar Aliphatic dicarboxylic acids such as 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 carbaryl acid, aconitic acid, and camphoronic 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, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa 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 element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), printing ink, inkjet ink, and It can be suitably used as a production application for paints and the like.

<< Color filter and manufacturing method thereof >>
The color filter of the present invention will be described in detail through its manufacturing method. The color filter of the present invention is characterized by using a colored curable composition. That is, the color filter of the present invention contains at least the dye represented by the above general formula (I).
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 method for producing a color filter of the present invention includes a step of forming a pattern by applying on a support, exposing through a mask, and developing. That is, the color filter of the present invention forms a radiation-sensitive composition layer by applying the colored curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, etc. A negative or positive colored pattern (resist pattern) can be formed by exposing the radiation-sensitive composition layer through the mask pattern and developing with a developer (image forming step). . At this time, if necessary, a curing step of curing the formed pattern by heating and / or exposure can be provided. In addition, as light or radiation used in this case, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  In the method for producing the color filter, when the coloring composition of the present invention is a negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of colors to obtain a positive type. In this case, by repeating the image forming step and the post-baking step according to the desired number of colors, a color filter having a desired number of hues can be produced.

  As the support, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for imaging elements, for example, A silicon substrate, a complementary metal oxide semiconductor (CMOS), etc. are mentioned. These supports may be formed with black stripes that separate pixels.

  In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the support.

  As a developer used in the method for producing a color filter of the present invention, a non-pixel portion (for example, an uncured portion in the case of a negative type) of the colored curable composition of the present invention is dissolved, while a pixel portion (for example, a negative). In the case of a mold, any material can be used as long as it has a composition that does not dissolve the radiation irradiated portion (cured portion). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used when preparing the colored curable composition of this invention is 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 so dissolved is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

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

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In Examples, unless otherwise specified, “part” means “part by mass”.

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

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737, manufactured by Corning) 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 on a cleaned glass substrate using a spin coater to a film thickness of 2 μm, dried by heating at 220 ° C. for 1 hour to form a cured film, and undercoating A glass substrate with a layer was produced.

3) Preparation of dye resist solution (colored curable composition [negative type]) 9.4 g of the resist solution obtained in the above 1) and the exemplified dye CD-1 (general formula (I ) 1.1 g) was mixed and dissolved to prepare a dye resist solution (colored curable composition [negative type] solution).

4) Exposure and development of resist (image formation)
The dye resist solution obtained in 3) above was applied on the undercoat layer of the glass substrate with the undercoat layer obtained in 2) so as to have a film thickness of 1.0 μm using a spin coater, and 100 ° C. For 120 seconds.
Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using a developer (trade name: CD-2000 (60%), manufactured by Fuji Electronics Materials 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 pattern suitable for a cyan color filter was obtained.

5) Evaluation The storage stability of the dye resist solution prepared above and the heat resistance and light resistance of the coating film formed on the glass substrate using the dye resist solution were evaluated as follows. The evaluation results are shown in Table 1 below.

(1) Storage stability After the dye resist solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation of foreign matters was observed.
(Triangle | delta): Precipitation of the foreign material was recognized slightly.
X: Precipitation of foreign matters was observed.

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

(3) Light resistance After irradiating a glass substrate coated with the dye resist solution with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), the ΔEab value of the color difference before and after the light resistance test was measured. . A smaller ΔEab value indicates better light resistance.
<Criteria>
○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

[Examples 2 to 15]
In the preparation of 3) the dye resist solution in Example 1, all except that the dye was replaced with the equimolar amount of the dyes shown in Table 1 below (Example 15 was used in 1/2 mol with respect to the exemplified dye in Example 1). A pattern was formed in the same manner as in Example 1 and the same evaluation was performed. The results are shown in Table 1.

[Comparative Examples 1-3]
In the preparation of 3) the dye resist solution in Example 1, a pattern was formed in the same manner as in Example 1 except that the dye was changed to the dye shown in Table 1 below, and the same evaluation was performed. The results are shown in Table 1.

  From the result of Table 1, the colored curable composition of the Example using the pigment | dye (dye) in this invention was excellent in the storage stability in the solution form with respect to the comparative example using other dye. . Furthermore, it turns out that the image pattern formed using the colored curable composition of this invention is excellent in both heat resistance and light resistance.

[Example 16]
1) Preparation of colored curable composition [positive type] The following compositions were mixed and dissolved to obtain a colored curable composition [positive type].
-30 parts of ethyl lactate (EL)-3.0 parts of the following resin P-1-1.8 parts of the following naphthoquinonediazide compound N-1-Crosslinking agent: 0.6 parts of hexamethoxymethylolated melamine-Photoacid generator: TAZ -107 (manufactured by Midori Chemical Co., Ltd.) 1.2 parts, 0.005 part of fluorosurfactant (trade name: MegaFuck F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Illustrative dye CD-4 1.2 parts in the present invention

  The resin P-1 and the naphthoquinone diazide compound N-1 were synthesized as follows.

-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. A reflux condenser and a thermometer were attached to the stirrer, and the temperature was 65 ° C. under a nitrogen stream. 1 g of a polymerization initiator (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When the molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

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

2) Exposure and development (image formation) of the colored curable composition
In the same manner as in Example 1, the colored curable composition prepared as described above was applied to a glass substrate with an undercoat layer, prebaked, irradiated, developed and rinsed, and dried to form a magenta image pattern image, and then The pattern image was heated at 180 ° C. for 5 minutes (post-bake). The formed magenta pattern image showed a good rectangular profile.

  The storage stability of the colored curable composition using the coloring matter (dye) in the present invention, and the heat resistance and light resistance of the coated color curable composition of the present invention were evaluated in the same manner as in Example 1. However, it was found that the storage stability was excellent and the heat resistance and light resistance were good.

[Examples 17 to 31]
Except that the glass substrate of Example 1 was changed to a silicon wafer substrate, the same operation as in Example 1 was performed to prepare a coated substrate of a silicon wafer with an undercoat layer. Next, in the same manner as in Examples 1 to 15, a dye resist solution was applied on a silicon wafer with an undercoat layer.
Next, using a i-line reduction projection exposure apparatus, a 2 μm square pattern was exposed at an exposure amount of 500 mJ / cm ² and developed (product name: CD-2000 (60%), manufactured by Fuji Electronics Materials). And developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable as a color filter for CCD having a square cross section was obtained.

[Example 32]
A) Preparation of a blue resist solution (colored curable composition [negative type]) 9.4 g of the resist solution obtained in the above 1) and the exemplified dye CD-1 (described above) which is a dye (dye) in the present invention 0.75 g of the dye represented by the general formula (I)) and 0.25 g of the exemplified dye MD-1 (the dye represented by the general formula (III)) in the present invention are mixed and dissolved to dissolve the blue dye resist solution. (Colored curable composition [negative type] solution) was prepared.
The obtained blue dye resist solution (colored curable composition) was applied onto a glass substrate with an undercoat layer in the same manner as in Example 1, and exposed and developed to form a pattern image. About the obtained pattern image, similarly to Example 1, the storage stability of the colored curable composition and the heat resistance and light resistance of the coating film coated on the glass substrate were evaluated. The results are shown in Table 2 below.

[Examples 33 to 49]
In the preparation of the blue resist solution in Example 32, a pattern image was formed in the same manner as in Example 37, except that each dye was placed in an equimolar amount of the dyes shown in Table 2 below. The results are shown in Table 2.

[Comparative Examples 4 to 6]
In the preparation of the blue resist solution in Example 32, a pattern was formed in the same manner as in Example 32 except that each dye was replaced with a comparative dye in Table 2 below, and the same evaluation was performed. The results are shown in Table 2.

It turned out that the colored curable composition using the pigment | dye (dye) in this invention is excellent in storage stability, and the heat resistance of a coating film and light resistance are favorable.
In particular, in Example 47 (invention) and Comparative Example 4, Example 48 (invention) and Comparative Example 5, and in comparison between Example 49 and Comparative Example 6, a remarkable improvement effect of fastness was observed. It was.

Claims (6)

The coloring curable composition characterized by containing the pigment | dye represented by the following general formula (I).

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Za and Zb each independently represent —N═ or —C (R ⁹ ) ═. R ⁹ represents a hydrogen atom or a substituent. R ³ and R ⁴ , R ⁴ and R ⁸ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and / or R ⁷ and R ⁸ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed. ] The colored curable composition according to claim 1, wherein the dye is represented by the following general formula (II).

Wherein, R ¹ to R ⁸ have the same meanings as R ¹ to R ⁸ in the general formula (I). R ¹⁰ represents a hydrogen atom or a substituent. ] At least one dye represented by the general formula (I);
At least one of a triarylmethane dye having an absorption maximum at 550 nm to 650 nm and / or a xanthene dye having an absorption maximum at 500 nm to 600 nm;
The colored curable composition according to claim 1, comprising: It contains at least 1 sort (s) of the pigment | dye represented by general formula (I), and at least 1 sort (s) of the pigment | dye represented by the following general formula (III), The any one of Claims 1-3 characterized by the above-mentioned. The colored curable composition according to item.

[Wherein, R ^{101 to} R ¹⁰⁵ each independently represents a hydrogen atom or a substituent. R ^{106 to} R ¹⁰⁷ each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Zc and Zd each independently represent —N═ or —C (R ¹⁰⁸ ) ═. R ¹⁰⁸ represents a hydrogen atom or a substituent. ^R102 and ^R103 , ^R103 and ^R106 , ^R104 and ^R105 , ^R105 and ^R107 , and / or ^R106 and ^R107 are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed. ]   A color filter comprising the colored curable composition according to claim 1.   A color filter comprising a step of forming a pattern by applying the colored curable composition according to any one of claims 1 to 4 on a support, exposing through a mask, and developing the pattern. Production method.