JP4359541B2 - Colorant-containing curable composition, color filter using the same, and method for producing the same - Google Patents

Description

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

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

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

  According to the pigment dispersion method, a radiation-sensitive composition is applied onto a glass substrate using a spin coater, a roll coater, or the like, and after forming a coating film, the coating film is pattern-exposed and developed for coloring. By forming this pixel and performing this operation for each color, a color filter is obtained. As said pigment dispersion method, the negative photosensitive composition which uses a photopolymerizable monomer and a photoinitiator for alkali-soluble resin is disclosed (for example, refer patent documents 1-8).

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

However, the curable composition containing a dye has the following problems, and further improvements are required.
(I) Dyes are generally inferior in heat resistance, light resistance and the like as compared with pigments, and further improvement in fastness is required.
(Ii) When the molar absorption light 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 curable composition Therefore, there is a problem that the curability of the composition, the heat resistance after curing, the developability of the non-cured portion, and the like are lowered, and an improvement thereof is desired.
(Iii) Dyes often exhibit an interaction with other components in the curable composition, and it is difficult to adjust the developability (solubility) of the cured part and the non-cured part. It has been demanded.

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

  On the other hand, it is known that a yellow dye is used for the green and red filter layers of the color filter (see, for example, Patent Document 12). However, the pyridone azo coloring matter used as the yellow dye has insufficient heat resistance and light resistance, and further improvement is desired. Similarly, in a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer, further improvement in fastness of the yellow dye used in the yellow filter layer is desired.

  It is also known that a magenta dye is used for the red filter layer of the color filter. However, the magenta dyes known so far have insufficient heat resistance and light resistance, and further improvements are desired. Similarly, in a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer, further improvement in fastness of the magenta dye used in the magenta filter layer is desired.

Japanese Patent Laid-Open No. 1-102469 Japanese Patent Laid-Open No. 1-152499 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP-A-6-75375 JP 2002-14221 A Japanese Patent Publication No.7-111485 JP 2002-14223 A

  An object of the present invention is to provide a curable composition having excellent stability over time, high sensitivity, high resolution, and high transmittance, and a pattern formed using the same having high heat fastness and light fastness. And providing a color filter using the same and a method for producing the same.

〔上記一般式（１）中、Ａは、５員複素環を表す。Ｂ¹及びＢ²は、各々−ＣＲ²⁰¹＝及び−ＣＲ²⁰²＝、或いは、いずれか一方が窒素原子を表し、他方が−ＣＲ²⁰¹＝又は−ＣＲ²⁰²＝を表す。Ｒ²⁰⁵，Ｒ²⁰⁶は、各々独立に、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、又はスルファモイル基を表す。これらは、更に置換基を有していてもよい。Ｇ、Ｒ²⁰¹及びＲ²⁰²は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキル基，芳香族基又は複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、又は、スルホ基を表す。各基は更に置換されていてもよい。また、Ｒ²⁰²とＲ²⁰⁵、及び、Ｒ²⁰⁵とＲ²⁰⁶は、結合して５〜６員環を形成してもよい。］ The present inventors have examined various dye compound derivatives in detail in order to obtain a dye having a good hue and high fastness to light and heat. It was found that it was possible to solve the point.
That is, according to the present invention, a colorant-containing curable composition having the following constitution and a color filter using the same are provided, and the object of the present invention is achieved.
<1> A colorant-containing curable composition comprising a dye represented by the following general formula (1) and a pyridone azo dye.

[In said general formula (1), A represents a 5-membered heterocyclic ring. B ¹ and B ² are —CR ²⁰¹ ═ and —CR ²⁰² ═, respectively, or one of them represents a nitrogen atom and the other represents —CR ²⁰¹ ═ or —CR ²⁰² ═. R ²⁰⁵ and R ²⁰⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aromatic group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic ring Thio group, alkyls Honiru group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or a sulfo group. Each group may be further substituted. R ²⁰² and R ²⁰⁵ , and R ²⁰⁵ and R ²⁰⁶ may combine to form a 5- to 6-membered ring. ]

〔上記一般式（２）中、Ｒ³⁰¹，Ｒ³⁰²、Ｒ³⁰³及びＲ³⁰⁴は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、チオール基、又は、スルホ基を表す。各基は更に置換されていてもよい。Ｑは、芳香族環又は複素環を表し、これらは更に置換されていてもよい。〕 <2> The colorant-containing curable composition according to <1>, wherein the pyridone azo dye is represented by the following general formula (2).

[In the above general formula (2), R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, or a carboxyl group. Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio Group, alkylsulfonyl group, Reel sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. Q represents an aromatic ring or a heterocyclic ring, which may be further substituted. ]

〔上記一般式（３）中、Ｒ³⁰¹，Ｒ³⁰²、Ｒ³⁰³，Ｒ³⁰⁴及びＲ³⁰⁵は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、チオール基、又は、スルホ基を表す。各基は更に置換されていてもよい。ｎは０〜５の整数を表す。〕 <3> The colorant-containing curable composition according to <1>, wherein the pyridone azo dye is represented by the following general formula (3).

[In the above general formula (3), R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ and R ³⁰⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a cyano group. , Carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, Heterocyclic thio group, alkyl sulfo Group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. n represents an integer of 0 to 5. ]

  <4> A color filter comprising the colorant-containing curable composition of the above <1> to <3>.

<5> A color filter comprising a step of coating the colorant-containing curable composition of the above <1> to <3> on a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method.
This manufacturing method may include a step of curing the pattern by heating and / or exposure as necessary, or may repeat these steps a plurality of times. Further, the dye may be changed to form a plurality of types of color filters.

  According to the present invention, a curable composition having excellent temporal stability, high sensitivity, high resolution, and high transmittance, and a pattern formed using the same having high heat fastness and light fastness. And a color filter using the same and a method for producing the same.

Hereinafter, the present invention will be described in detail.
<< Colorant-containing curable composition >>
The colorant-curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) has a dye represented by the following general formula (1) and a pyridone azo dye.
Since the composition of the present invention has a dye represented by the following general formula (1) and a pyridone azo dye, the composition has excellent temporal stability and excellent heat fastness and light fastness of the resulting pattern.

(Coloring agent)
-Dye represented by general formula (1)-
First, the pigment | dye (azo dye) represented by the said General formula (1) in this invention is demonstrated in detail.

〔上記一般式（１）中、Ａは、５員複素環を表す。Ｂ¹及びＢ²は、各々−ＣＲ²⁰¹＝及び−ＣＲ²⁰²＝、或いは、いずれか一方が窒素原子を表し、他方が−ＣＲ²⁰¹＝又は−ＣＲ²⁰²＝を表す。Ｒ²⁰⁵，Ｒ²⁰⁶は、各々独立に、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、又はスルファモイル基を表す。これらは、更に置換基を有していてもよい。Ｇ、Ｒ²⁰¹及びＲ²⁰²は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキル基，芳香族基又は複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、又は、スルホ基を表す。各基は更に置換されていてもよい。また、Ｒ²⁰²とＲ²⁰⁵、及び、Ｒ²⁰⁵とＲ²⁰⁶は、結合して５〜６員環を形成してもよい。］

[In said general formula (1), A represents a 5-membered heterocyclic ring. B ¹ and B ² are each —CR ²⁰¹ ═ and —CR ²⁰² ═, or one of them represents a nitrogen atom and the other represents —CR ²⁰¹ ═ or —CR ²⁰² ═. R ²⁰⁵ and R ²⁰⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aromatic group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic ring Thio group, alkyls Honiru group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or a sulfo group. Each group may be further substituted. R ²⁰² and R ²⁰⁵ , and R ²⁰⁵ and R ²⁰⁶ may combine to form a 5- to 6-membered ring. ]

In general formula (1), A represents a 5-membered heterocyclic ring. The 5-membered heterocyclic ring is a residue of the diazo component “A-NH ₂ ”. Examples of heteroatoms contained in the 5-membered heterocycle include N, O, and S. As the 5-membered heterocyclic ring, a nitrogen-containing 5-membered heterocyclic ring is preferable. The 5-membered heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
Preferable examples of A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. The above A may further have a substituent. As A, the pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring or benzothiazole ring represented by the following (a) to (f) is particularly preferable.

In the above (a) ~ (f), R 209 ~R 222 represents the same substituent G, and R ²⁰¹ and R ²⁰² in formula (1) described later.
Among the above (a) to (f), as A, the pyrazole ring and the isothiazole ring represented by (a), (a ′) and (b) are preferable, and the pyrazole ring represented by (a) is more preferably, it is particularly preferably a monocyclic heterocycle represented by a pyrazole ring and R ²¹¹ is 5 membered (a).

In the general formula (1), B ¹ and B ² represent —CR ²⁰¹ ═ and —CR ²⁰² ═, respectively, or one of them represents a nitrogen atom and the other represents —CR ²⁰¹ ═ or —CR ²⁰² ═, which each represent a -CR ²⁰¹ = and -CR ²⁰² = it is preferable. R ²⁰¹ and R ²⁰² will be described later.
In the general formula (1), R ²⁰⁵ and R ²⁰⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent.

R ²⁰⁵ and R ²⁰⁶ are preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group and an arylsulfonyl group, and a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, An alkylsulfonyl group and an arylsulfonyl group are more preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. However, R ²⁰⁵ and R ²⁰⁶ are not simultaneously hydrogen atoms. Each group may further have a substituent.

In the general formula (1), G, R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, or an alkoxycarbonyl. Group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group; alkyl group, aromatic An amino group substituted with an aromatic group or a heterocyclic group; acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio Group, arylthio group, complex Thio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or represents a sulfo group, each group may be further substituted.

  As G, a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group; an alkyl group, an aromatic group, or a heterocyclic group is substituted. An amino group; an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, and a heterocyclic thio group, preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group Group, alkoxy group, aryloxy group, acyloxy group; amino group substituted with alkyl group, aromatic group or heterocyclic group; or acylamino group is more preferable, and among them, hydrogen atom, arylamino group, and acylamino group are most preferable. . Each group may further have a substituent.

R ²⁰¹ and R ²⁰² are preferably a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group and a cyano group. Each group may further have a substituent.

R ²⁰² and R ²⁰⁵ , and R ²⁰⁵ and R ²⁰⁶ may combine to form a 5- to 6-membered ring. Examples of the 5- to 6-membered ring include a pyridine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and a triazole ring.
In the general formula (1), when each substituent represented by A, R ²⁰¹ , R ²⁰² , R ²⁰⁵ , R ²⁰⁶ and G further has a substituent, the substituent includes the above G, R ²⁰¹ and R ^The substituents exemplified in ²⁰² can be exemplified.

When the coloring matter represented by the general formula (1) is a water-soluble dye, an ionic hydrophilic group is further added as a substituent on any of A, R ²⁰¹ , R ²⁰² , R ²⁰⁵ , R ²⁰⁶ , and G. It is preferable to have. Examples of the ionic hydrophilic group as the substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable. The sulfo group and the carboxyl group may be in a salt state. Examples of counter ions that form the salt include alkali metal ions (for example, sodium ions, potassium ions) and organic cations (for example, tetramethylguanidinium ions).

〔上記一般式（２）中、Ｒ³⁰¹，Ｒ³⁰²、Ｒ³⁰³及びＲ³⁰⁴は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、チオール基、又は、スルホ基を表す。各基は更に置換されていてもよい。Ｑは、芳香族環又は複素環を表し、これらは更に置換されていてもよい。〕 -Pyridone azo dye-
Next, the pyridone azo coloring matter (dye) will be described in detail.
As said pyridone azo pigment | dye, the pigment | dye (dye) represented by following General formula (2) is mentioned, for example.

[In the above general formula (2), R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, or a carboxyl group. Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio Group, alkylsulfonyl group, Reel sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. Q represents an aromatic ring or a heterocyclic ring, which may be further substituted. ]

In the general formula (2), as R ³⁰¹ , a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxy group, A fluoroalkyl group is preferable, an aliphatic group, an aromatic group, and a heterocyclic group are more preferable, and an aliphatic group and an aromatic group are particularly preferable.

R ³⁰² is preferably a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, more preferably a cyano group, a carbamoyl group, an alkoxycarbonyl group or an acyl group, and a cyano group Is particularly preferred.

R ³⁰³ is preferably an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.

As said ^R304 , a hydroxy group, an amino group, an alkoxy group, and a thiol group are preferable, and a hydroxy group is especially preferable.

  Q is preferably a substituted or unsubstituted aromatic group or a substituted or unsubstituted aromatic heterocyclic group, and particularly preferably a substituted or unsubstituted aromatic group.

  As a pigment | dye represented by the said General formula (2), the pigment | dye (dye) represented by following General formula (3) is preferable.

〔上記一般式（３）中、Ｒ³⁰¹，Ｒ³⁰²、Ｒ³⁰³，Ｒ³⁰⁴及びＲ³⁰⁵は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、複素環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、スルファモイル基、チオール基、又は、スルホ基を表す。各基は更に置換されていてもよい。ｎは０〜５の整数を表す。〕

[In the above general formula (3), R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ and R ³⁰⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a cyano group. , Carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, Heterocyclic thio group, alkyl sulfo Group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. n represents an integer of 0 to 5. ]

In the general formula (3), as R ³⁰¹ , R ³⁰² , R ³⁰⁴ , and R ³⁰⁵ , a hydrogen atom, aliphatic group, aromatic group, hydroxy group, cyano group, carbamoyl group, and sulfamoyl group are preferable. The aliphatic group or aromatic group may be substituted or unsubstituted.
Examples of R ³⁰³ include a substituted or unsubstituted aliphatic group.

The substituents defined in this specification will be described in detail below.
Examples of the “halogen atom” include a fluorine atom, a chlorine atom and a bromine atom.

  “Aliphatic group” means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch or may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl moiety of the aralkyl group and the substituted aralkyl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. Examples of the aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4- Examples thereof include a sulfobutyl group, a cyclohexyl group, a benzyl group, a 2-phenethyl group, a vinyl group, and an allyl group.

“Aromatic group” means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The number of carbon atoms in the aromatic group is preferably 6-20, and more preferably 6-16. Examples of the aromatic group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and An m- (3-sulfopropylamino) phenyl group is included.

  The “heterocyclic group” includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. In addition, the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent of the heterocyclic ring include an aliphatic group, a halogen atom, an alkyl and arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group, and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

  The “carbamoyl group” includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent of the carbamoyl group include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The “alkoxycarbonyl group” includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable. Examples of the substituent of the alkoxycarbonyl group include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The “aryloxycarbonyl group” includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. Examples of the substituent for the aryloxycarbonyl group include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The “acyl group” includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent of the acyl group include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

  The “alkoxy group” includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent of the alkoxy group include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The “aryloxy group” includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent of the aryloxy group include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The “acyloxy group” includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent of the acyloxy group include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The “carbamoyloxy group” includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent of the carbamoyloxy group include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The “amino group substituted with an alkyl group, aromatic group or heterocyclic group” may further have a substituent. Further, the “amino group substituted with an alkyl group, aromatic group or heterocyclic group” does not include an unsubstituted amino group. The amino group substituted with an alkyl group (alkylamino group) is preferably an alkylamino group having 1 to 6 carbon atoms. Examples of the substituent of the alkylamino group include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The amino group substituted with an aryl group (arylamino group) includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms. Examples of the substituent of the arylamino group include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.
Examples of the amino group substituted with a heterocyclic group include a 2-pyridinylamino group, a 3-pyrrolylamino group, and a 3-indolylamino group.

  The “acylamino group” includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. Examples of the substituent of the acylamino group include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The “ureido group” includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. Examples of the substituent of the ureido group include an alkyl group and an aromatic group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The “sulfamoylamino group” includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent of the sulfamoylamino group include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

  The “alkoxycarbonylamino group” includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent of the alkoxycarbonylamino group include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The “aryloxycarbonylamino group” includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent of the aryloxycarbonylamino group include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The “alkylsulfonylamino group” and “arylsulfonylamino group” include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. The sulfonylamino group in the alkyl and arylsulfonylamino groups is preferably a sulfonylamino group having 1 to 12 carbon atoms. Examples of substituents for the alkyl and arylsulfonylamino groups include ionic hydrophilic groups. Examples of the alkyl and arylsulfonylamino groups include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.

  The “alkylthio group”, “arylthio group” and “heterocyclic thio group” include substituted alkyl, aryl and heterocyclic thio groups, and unsubstituted alkyl, aryl and heterocyclic thio groups. As the alkyl, aryl and heterocyclic thio groups, those having 1 to 12 carbon atoms are preferred. Examples of the substituent of the alkyl, aryl and heterocyclic thio group include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

Examples of the “alkylsulfonyl group” and “arylsulfonyl group” include a methanesulfonyl group and a phenylsulfonyl group, respectively.
Examples of the “alkylsulfinyl group” and “arylsulfinyl group” include a methanesulfinyl group and a phenylsulfinyl group, respectively.

  The “sulfamoyl group” includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent of the sulfamoyl group include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Examples of the “silyloxy group” include trimethylsilyloxy group, tributylsilyloxy group, triphenylsilyloxy group and the like.
Examples of the “heterocyclic oxy group” include pyridinyloxy group, pyrrolyloxy group, pyrazolyloxy group, imidazolyloxy group, triazolyloxy group and the like.

Examples of the “alkoxycarbonyloxy group” include methoxycarbonyloxy group, butoxycarbonyloxy group, isopropoxycarbonyloxy group, cyclohexylocarbonyloxy group and the like.

Examples of the “aryloxycarbonyloxy group” include phenoxycarbonyloxy group, 4-nitrophenoxycarbonyloxy group, 2-chloro-4-
Examples thereof include a methylphenoxycarbonyloxy group.

  Although the specific example of the pigment | dye represented by the said General formula (1) is shown below, the dye used for this invention is not limited to the following example.

  Specific examples of the pyridone azo dye (the dyes represented by the general formula (2) and the general formula (3)) are shown below, but the dye used in the present invention is not limited to the following examples.

  Next, a synthesis example of the coloring matter (azo dye) represented by the general formula (1) will be described.

[Synthesis Example 1]: Azo Dye <Synthesis of Azo Dye (ma-1) [Exemplary Compound])>

(Synthesis of Intermediate (ma-1c))
70 g (131 mmol) of the dye intermediate (above ma-1a), 21.7 g (157 mmol) of potassium carbonate, 240 mL of dimethyl sulfoxide, and 240 mL of acetonitrile were mixed under a nitrogen stream. While stirring the above mixture at room temperature, 19.4 g (144 mmol) of chloromethylthiadiazole (ma-1b above) was added dropwise over 2 minutes. The reaction was allowed to proceed at room temperature for 10 hours, and then allowed to stand overnight. When water (940 mL) was added thereto, a target crystal was precipitated, and this was filtered to obtain 77.3 g (crude yield: 93.3%) of crude crystals. The crude crystals were dissolved in chloroform (310 mL), acetonitrile (930 mL) was added dropwise, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered and dried to obtain 60.2 g of crystals of the intermediate (above ma-1c) (yield 72.6%).

<Synthesis of azo dye (ma-1)>
52 g (82.2 mmol) of the intermediate (ma-1c) obtained by the above method was dissolved in 210 mL of N, N-dimethylacetamide, and 22.7 g (164 mmol) of potassium carbonate was added and stirred at room temperature. To this was added dropwise 9.66 mL (14.85 g, 107 mmol) of 3-bromopropanol over 3 minutes, and the reaction was carried out at an external temperature of 70 ° C. 1 mL of 3-bromopropanol was additionally added 3 hours and 4 hours after the start of the reaction. After stirring at an external temperature of 70 ° C. for a total of 4 hours, the reaction solution was added to 520 mL of water, and crystals of the target azo dye (ma-1) were precipitated. The crystals were separated by filtration and dried to obtain 56.5 g of crude crystals. The crude crystals were purified by silica gel column chromatography to obtain 38.8 g of azo dye (ma-1) (yield 68.3%). The maximum absorption wavelength of the obtained azo dye (ma-1) was λmax) = 538.3 nm, and the molar extinction coefficient (ε) = 57000.

  In addition, exemplified compounds of the dye represented by the general formula (1) exemplified above can also be synthesized by a method almost the same as the above synthesis example.

The synthesis example of the pigment | dye (pyridone azo pigment | dye) represented by General formula (2) below is given.
[Synthesis Example 2]: Synthesis of pyridone azo dye (ya-1)

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

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

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

<Synthesis of Intermediate (9)>
Next, 27.3 g of reduced iron, 19.5 g of acetic acid, and 58.5 g of water were mixed and stirred at 80 ° C. for 1 hour, and 20 g of the compound (8) obtained above was gradually added thereto. Further, 93.6 ml of ethanol was added dropwise and stirred at 80 ° C. for 1 hour. The reaction mixture was then cooled to room temperature and an aqueous solution of 23.79 g sodium carbonate was added. Thereafter, 175 ml of methanol was added and stirred for 15 minutes. Next, the mixture was filtered through Celite, washed with acetone, and then the solvent in the liquid phase was distilled off. Furthermore, it melt | dissolved in 600 ml of acetone, the insoluble matter was removed, it dried and concentrated with sodium sulfate, and the compound (9) was obtained (yield about 14.3 g, yield about 79%).

<Synthesis of pyridone azo dye (ya-1)>
Next, 3.41 g of compound (9), 12.5 ml of 36% hydrochloric acid and 57 ml of distilled water were mixed and cooled to 0 ° C. A sodium nitrite aqueous solution (NaNO2: 0.84 g, water: 10 g) was added dropwise thereto while maintaining the internal temperature at 5 ° C. or lower, and the mixture was stirred for 3 hours while maintaining 5-10 ° C. (preparation of diazo solution). .

  This diazo solution was added to the above-mentioned aqueous solution containing the compound (5) (2.62 g of the above compound (5) and 20 g of water were mixed and a 2N aqueous sodium hydroxide solution was added to set the pH to 8) at 0 ° C. or lower. The solution was added dropwise over 1 hour. Next, a 10% aqueous sodium carbonate solution was added dropwise, and the pH was adjusted to 6-7, followed by filtration. Furthermore, it melt | dissolved in 500 ml of acetone, activated carbon and sodium sulfate were added, and cerite filtration was carried out. Next, the solvent was distilled off, and the solid was vacuum-dried to obtain 3.05 g of the above pyridone azo dye (ya-1) which is the dye represented by the general formula (2) in the present invention (yield: 51%) ).

  Although the total use concentration of the colorant contained in the composition of the present invention varies depending on the molecular weight and molar extinction coefficient, the total solid content of the composition of the present invention is preferably 0.5 to 80% by mass, 0.5 -60 mass% is more preferable, and 0.5-50 mass% is especially preferable. Individually, the dye represented by the general formula (1) is 0.5 to 0.5% based on the total solid content in the composition of the present invention from the viewpoints of curability, spectral absorption, filter film thickness, and solubility. It is preferable that 40 mass% is contained, and 0.5-30 are still more preferable. Moreover, it is preferable that the pyridone azo pigment | dye in this invention is contained 0.5-40 mass% with respect to the total solid in the composition of this invention, and 0.5-30 are still more preferable.

  Among these, the content ratio (mass) of the dye represented by the general formula (1) and the pyridone azo dye is 1/5 to 5/1 from the viewpoints of curability, spectral absorption, filter film thickness, and solubility. 1/3 to 3/1 is more preferable. Moreover, when using the pigment | dye other than the pigment | dye represented by General formula (1) and a pyridone azo pigment | dye as said colorant, 2 mass% or more is preferable, and, as for content which occupies in these all colorants, 5 mass% or more Is more preferable.

  In addition to the colorant, the composition of the present invention may contain a binder, a crosslinking agent, a monomer, a photopolymerization initiator, a solvent, and other additives as necessary. Hereinafter, these will be described.

(binder)
The binder will be described. The binder that can be used in the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in the specifications of No. 25957, JP-A-59-53836, JP-A-59-71048, etc. There are a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid in the side chain is useful. In addition to this, a polymer having a hydroxyl group with an acid anhydride added, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

  The binder may be a copolymer of a monomer having a hydrophilic group. Examples include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylol acrylamides, secondary and tertiary alkyl acrylamides, and 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 straight Examples include chain butyl (meth) acrylate and phenoxyhydroxypropyl (meth) acrylate.

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 salts, and monomers containing morpholinylethyl group. is there.
Moreover, in order to improve the crosslinking efficiency, the binder may have a polymerizable group in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain is also useful. It is.
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 these various binders, binders that can be used in the present invention include polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, acrylic / acrylamide copolymers from the viewpoint of heat resistance. Resins are preferred. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Industrial Co., Ltd.) and Cyclomer P-series (Daicel Chemical Industries, Ltd.) are preferred.

Moreover, an alkali-soluble phenol resin can be used as the binder. The alkali-soluble phenol resin can be suitably used particularly when the 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 a phenol compound and an aldehyde compound in the presence of an acid catalyst. Examples of the phenol compounds include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. The said phenol compound can be used individually or in combination of 2 or more types.
Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.

  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 by means of fractionation or the like. 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 is preferably a polymer having 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 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.
10-90 mass% is preferable with respect to the total solid in the composition of this invention, and, as for the usage-amount in the composition of this invention of the said binder, 20-80 mass% is still more preferable. 30-70 mass% is especially preferable.

(Crosslinking agent)
Next, the crosslinking agent will be described.
The crosslinking agent that can be used in the present invention is not particularly limited as long as it can cure the film by a crosslinking reaction. For example, it is selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one selected substituent, (c) at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group Examples include substituted phenol compounds, naphthol compounds, and hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are particularly preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and crosslinkability. Examples of these compounds include bisphenol A-glycidyl ether, ethylene glycol diglycidyl. Divalent glycidyl group-containing low molecules such as ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline Compound; Similarly, trivalent propane triglycidyl ether, trimethylol phenol triglycidyl ether, trivalent glycidyl group-containing low molecular weight compound represented by TrisP-PA triglycidyl ether, etc .; Tetravalent glycidyl group-containing low molecular weight compounds represented by erythritol tetraglycidyl ether, tetramethylol bisphenol-A-tetraglycidyl ether, and the like; similarly, polyvalent glycidyl such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, etc. Glycidyl groups represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of group-containing low molecular weight compounds, polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol Containing polymer compounds and the like.

  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 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 a compound in which 1 to 5 methylol groups of melamine are acyloxymethylated, or a mixture thereof.

  Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethyl glycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol glycoluril, or a mixture thereof, or a methylol group of tetramethylol glycoluril. A compound obtained by acylating 1 to 3 or a mixture thereof may be mentioned.

  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.

  In the case of the component (b), the component (c), that is, the phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group In the same manner as described above, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength.

  The number of methylol groups, alkoxymethyl groups or acyloxymethyl groups contained in the component (c) is at least 2 per molecule, and is the second position of the phenolic compound from the viewpoint of thermal crosslinkability and stability over time. , Compounds in which all the 4-positions are substituted are preferred. Further, 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.

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

  Examples of the skeleton compounds include phenol compounds in which the ortho- or para-position of the phenolic OH group is unsubstituted, naphthol, hydroxyanthracene compounds, such as phenol and cresol isomers, 2,3-xylenol, , 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 Tris P-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-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, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, hexamethylol body of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxymethyl. And a phenol compound substituted with both a methylol group and an alkoxymethyl group. These may be used alone or in combination.

  The content of the crosslinking agent in the composition of the present invention varies depending on the material, but is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and particularly preferably 7 to 30% by mass with respect to the total solid content. .

(monomer)
Next, the monomer contained when the composition of the present invention is constituted into a negative composition will be described.
As the monomer, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples of such compounds 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, trimethylol Ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) Polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication Nos. 48-41708, 50-6034, Japanese Patent Publication No. 51 Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof.

Examples of the 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 monomer in the composition of the present invention is preferably 0.1 to 90% by mass, more preferably 1.0 to 80% by mass, and particularly preferably 2.0 to 70% by mass with respect to the total solid content. preferable.

(Photopolymerization initiator)
Next, the photopolymerization initiator contained in the case where the composition of the present invention is constituted into a negative composition will be described. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable monomer, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like.
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 compounds include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, and 2-trichloro. Methyl-5-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-) ) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho- -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-trichloromethyl-s-triazine, 4- [pN, 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 − [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophen L] 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) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloro) Ethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m- Bromo-p N-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-ethoxycarbonyl) Methylaminophenyl) -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-tri Azine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series made by Midori Chemical Co., Ltd., for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ-104; T series manufactured by PANCHIM, for example, T-OMS, T-BMP, TR, TB; Irgacure series, for example, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, manufactured by Ciba Specialty Chemicals , Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261; Darocur series such as Darocur 1173, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4 − Phenylthio) phenyl] -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-methoxy) Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2-mer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin Propyl ether are used also useful.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include, for example, 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- -Methyl styryl ketone, 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. are mentioned.

In addition to the above photopolymerization initiators, other known photopolymerization initiators can be used in the 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. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples include teal-s-triazine compounds.
The amount of the photopolymerization initiator used is preferably 0.01% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 1% by mass to 20% by mass with respect to the monomer solid content. . When the amount of the photopolymerization initiator used is in the range of 0.01 to 50% by mass, the polymerization is easy to proceed and the film strength can be increased.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the 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.

(solvent)
The solvent used in the present invention is basically not particularly limited as long as the solubility and applicability of the composition are satisfied. However, the solvent is preferably selected in consideration of the solubility, applicability and safety of the binder.
Solvents used in preparing the composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid. Ethyl, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxy 3-oxypropionic acid alkyl esters such as methyl propionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2 -Oxypro Methyl onate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion Ethyl acetate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether Acetates and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferable.

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

(Other additives)
In the composition of the present invention, various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like are blended as necessary. be able to.

  Specific examples of these 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.

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

(Positive type composition)
In order to obtain a positive image, that is, when the composition of the present invention is a positive composition, the composition of the present invention preferably contains a naphthoquinone diazide compound.
Examples of the naphthoquinone diazide compound include o-naphthoquinone diazide-5-sulfonic acid ester, o-naphthoquinone diazide-5-sulfonic acid amide, o-naphthoquinone diazide-4-sulfonic acid ester, o-naphthoquinone diazide-4-sulfone. Examples include acid amides. 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 composition of the present invention is a positive composition, the alkali-soluble phenol resin and the crosslinking agent are usually dissolved in an organic solvent at a ratio of about 2 to 50% by mass and 2 to 30% by mass, respectively. Is preferred. The naphthoquinone diazide compound and the organic solvent-soluble use amount are usually added at a ratio of about 2 to 30% by mass and 2 to 50% by mass, respectively, with respect to the solution in which the alkali-soluble resin and the crosslinking agent are dissolved. Is preferred.

"Color filter"
The color filter of the present invention is produced using the composition of the present invention. The color filter of the present invention forms a radiation-sensitive composition layer by applying the composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like, through a predetermined mask pattern. And then developing with a developer to form a colored pattern. Moreover, the manufacturing method of the color filter of this invention may include the process of hardening the said resist pattern by heating and / or exposure as needed. As radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  As the support, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, a photoelectric conversion element substrate used for an imaging element, etc. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These supports may be formed with black stripes that separate pixels.

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

  As the developer used in the method for producing the color filter of the present invention, any developer can be used as long as it dissolves the composition of the present invention and does not dissolve the radiation irradiated 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 adjusting the 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.

  In addition, the color filter of the present invention can be used for a solid-state imaging 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 that exceeds 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.

[Example 1]
1) Preparation of colorant-containing curable composition (negative type)
(I) Preparation of resist solution The following composition was mixed and dissolved to prepare a resist solution.
〔composition〕
Propylene glycol monomethyl ether acetate 5.20 parts (PGMEA)
Ethyl lactate (EL) 52.6 parts Binder (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) copolymer (molar ratio = 60: 20: 20) 41% EL solution 30.5 parts Dipentaerythritol hexaacrylate 10.2 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.006 parts ・ Fluorosurfactant 0.80 parts (trade name: 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 Glass substrate (trade name: Corning 1737, manufactured by Corning) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). .
Next, a glass substrate with an undercoat layer is formed by applying the resist solution of 1) above onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and drying by heating at 220 ° C. for 1 hour to form a cured film. Got.

3) Preparation of dye-containing resist solution 9.4 g of the resist solution obtained in the above 1) and 0.80 g of the yellow dye in the present invention (pigment represented by the general formula (2): the exemplified compound (ya-1)) And magenta dye in the present invention (pigment represented by formula (1): the above exemplary compound (ma-1)) 0.70 g were mixed and dissolved to prepare a dye-containing resist solution.

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

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

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

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

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

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

[Comparative Examples 1-6]
In Example 1 3) Preparation of the dye-containing resist solution, the same evaluation was performed in the same manner as in Example 1 except that each dye was changed to the dye shown in Table 1 below. The results are shown in Table 1.

  From the results of Table 1, the colorant-containing curable composition of the present invention is excellent in stability over time, and the pattern (color filter) formed using the colorant-containing curable composition of the present invention is heat resistant. In addition, it is understood that the light resistance is excellent.

[Example 11]
1) Preparation of colorant curable composition (positive type)
The following composition was mixed and dissolved to prepare a positive colorant-containing curable composition.
〔composition〕
• 30 parts of ethyl lactate (EL) • 3.0 parts of resin (P-1) (below) • 1.8 parts of naphthoquinonediazide compound (N-1) (below) • Hexamethoxymethylolated melamine (crosslinking agent) 6 parts, photoacid generator 1.2 parts (trade name: TAZ-107 (manufactured by Midori Chemical)
・ Fluorosurfactant 0.0005 parts (trade name: F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Yellow dye (the above exemplified compound (ya-1)) 1.5 parts ・ Magenta dye (the above exemplified compound (ma-1)) 1.5 parts

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

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

(Synthesis of Resin (P-1))
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl, and 600 g of 2-methoxypropanol, and a stirrer, a reflux condenser and a thermometer were added thereto. Under an attached nitrogen stream, 0.5 g of a polymerization initiator (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin (P-1). When the molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

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

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

Claims (5)

A colorant-containing curable composition comprising a dye represented by the following general formula (1) and a pyridone azo dye.

[In said general formula (1), A represents a 5-membered heterocyclic ring. B ¹ and B ² are —CR ²⁰¹ ═ and —CR ²⁰² ═, respectively, or one of them represents a nitrogen atom and the other represents —CR ²⁰¹ ═ or —CR ²⁰² ═. R ²⁰⁵ and R ²⁰⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. Represents a group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aromatic group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic ring Thio group, alkyls Honiru group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or a sulfo group. Each group may be further substituted. R ²⁰² and R ²⁰⁵ , and R ²⁰⁵ and R ²⁰⁶ may combine to form a 5- to 6-membered ring. ] The said pyridone azo pigment | dye is represented by following General formula (2), The coloring agent containing curable composition of Claim 1 characterized by the above-mentioned.

[In the above general formula (2), R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, or a carboxyl group. Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio Group, alkylsulfonyl group, Reel-sulfonyl group, alkylsulfinyl group, arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. Q represents an aromatic ring or a heterocyclic ring, which may be further substituted. ] The colorant-containing curable composition according to claim 1, wherein the pyridone azo dye is represented by the following general formula (3).

[In the above general formula (3), R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ and R ³⁰⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a cyano group. , Carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, Heterocyclic thio group, alkyl sulfo Group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a thiol group, or a sulfo group. Each group may be further substituted. n represents an integer of 0 to 5. ]   A color filter comprising the colorant-containing curable composition according to claim 1.   A color comprising a step of applying a colorant-containing curable composition according to any one of claims 1 to 3 on a support, exposing through a mask, and developing to form a pattern. Manufacturing method of the filter.