JP4384581B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing negative curable composition for a color filter suitable for forming a colored image of a color filter used for a liquid crystal display element (LCD) or a solid-state image sensor (CCD, CMOS, etc.), and The present invention relates to a color filter and a manufacturing method thereof.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion 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. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithographic method, it has been widely used as a suitable method for producing a color filter for a large screen, high-definition color display with high positional accuracy.

  In order to produce a color filter by the pigment dispersion method, first, a radiation-sensitive composition is applied onto a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then the coating film is patterned. Color filters can be produced by forming colored pixels by exposure and development, and performing this operation for each color.

  As the pigment dispersion method, specifically, a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin has been conventionally known (for example, Patent Documents 1 to 4). reference.).

  On the other hand, in recent years, in applications such as a solid-state imaging device, further enhancement of the color filter is desired. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there are also problems such as uneven color due to coarse pigment particles. For this reason, the pigment dispersion method is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

  In view of such a problem, techniques for using dyes instead of pigments have been proposed (see, for example, Patent Documents 5 and 6). However, the dye-containing curable composition has a problem that it is generally inferior to the pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity. In particular, in the case of use for producing a color filter for a solid-state imaging device, the film thickness is required to be 1.5 μm or less. Therefore, it is necessary to obtain a sufficient concentration with a film thickness of 1.5 μm or less. For this reason, a large amount of dye must be added to the curable composition, which may result in insufficient adhesion to the substrate. If sufficient curing cannot be obtained or the dye is lost even in the exposed area, there is a problem that pattern formation is extremely difficult.

Due to the above-mentioned problems, it has been difficult to satisfy practical performance requirements regarding fine and thin colored patterns for high-definition color filters.
For this reason, development of the dye and curable composition which can solve the above-mentioned problem was desired.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP 54-63903 A

  Accordingly, an object of the present invention is to provide a dye-containing negative curable composition suitable for the use of a dye. Specifically, it is highly sensitive and has no residue in an unexposed portion, and forms a rectangular fine pattern. It is an object of the present invention to provide a dye-containing negative-type curable composition that is capable of achieving high heat fastness and light fastness. At the same time, it is an object of the present invention to provide a color filter excellent in pattern formability and high in cost performance, particularly a color filter for a solid-state imaging device and a manufacturing method thereof.

Specific means for solving the above problems are as follows.
<1> A dye containing at least an (A) alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a radical polymerizable monomer, and (E) an organic solvent. A negative curable composition, wherein the organic solvent-soluble dye (B) is at least one dye represented by the following general formula (1) and at least one dye represented by the following general formula (2): 1 type of dye containing negative curable composition characterized by the above-mentioned.

〔一般式（１）中、Ａは、５員複素環を表す。Ｂ¹およびＢ²は、各々−ＣＲ²⁰¹＝および−ＣＲ²⁰²＝、或いは、いずれか一方が窒素原子を表し、他方が−ＣＲ²⁰¹＝または−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また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および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，芳香族基また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、または、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、および、Ｒ²⁰⁵とＲ²⁰⁶は、結合して５〜６員環を形成してもよい。］

[In 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 sulfamoyl. Represents a group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, 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, 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, alkyl A sulfonyl 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. ]

〔一般式（２）中、Ｒ¹〜Ｒ⁴は各々独立して、水素原子、ハロゲン原子、−Ｓ−Ｒ⁵または−Ｓ−Ｒ⁶を表す。Ｓは硫黄原子を表し、Ｒ⁵は酸素原子をエーテル結合の形で含むアルキル基を表し、更に置換基としてヒドロキシ基を有してもよい。Ｒ⁶はヒドロキシ基を有するアルキル基を表す。ただしＲ¹〜Ｒ⁴のうち少なくとも１つは−Ｓ−Ｒ⁵を表す。〕

[In General Formula (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ . ]

  <2> The dye-containing negative curable composition according to <1>, wherein the (C) photopolymerization initiator is an oxime compound.

  <3> The dye-containing negative curable composition according to <1> or <2>, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain.

  <4> The dye-containing negative curable composition according to <1> to <3>, wherein the (E) solvent contains a cyclic ketone solvent.

  <5> A color filter comprising the dye-containing negative curable composition according to <1> to <4>.

  <6> A color comprising the steps of applying the dye-containing negative curable composition of the above <1> to <4> on a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method of a filter.

  According to the present invention, a highly sensitive and rectangular pattern can be formed (particularly when a pattern is formed by stepper exposure), and there is no residue in an unexposed portion, and the dye has excellent heat fastness and light fastness. A negative-type curable composition can be provided. In addition, according to the present invention, it is possible to provide a color filter having excellent pattern forming properties and high cost performance, and a method for manufacturing the color filter.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention comprises (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a radical polymerizable monomer, (E A dye-containing negative curable composition containing at least an organic solvent, wherein the organic solvent-soluble dye (B) is at least one dye represented by the following general formula (1), and the following general formula: It is characterized by containing at least one of the dyes represented by (2) (hereinafter, these may be collectively referred to as “the dyes in the present invention”). Since the coloring matter in the present invention has a particularly high color value, the amount of the coloring matter can be reduced. Thereby, the content of other additives can be increased, and various performances of the resist can be improved, so that a rectangular fine pattern can be formed, and heat fastness and light fastness are also excellent. Furthermore, according to the composition of the present invention, it is possible to improve the developability of the unexposed area and the remaining film ratio of the exposed area, so that good pattern formability can be exhibited.

〔一般式（１）中、Ａは、５員複素環を表す。Ｂ¹およびＢ²は、各々−ＣＲ²⁰¹＝および−ＣＲ²⁰²＝、或いは、いずれか一方が窒素原子を表し、他方が−ＣＲ²⁰¹＝または−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また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および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，芳香族基また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、または、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、および、Ｒ²⁰⁵とＲ²⁰⁶は、結合して５〜６員環を形成してもよい。〕

〔一般式（２）中、Ｒ¹〜Ｒ⁴は各々独立して、水素原子、ハロゲン原子、−Ｓ−Ｒ⁵または−Ｓ−Ｒ⁶を表す。Ｓは硫黄原子を表し、Ｒ⁵は酸素原子をエーテル結合の形で含むアルキル基を表し、更に置換基としてヒドロキシ基を有してもよい。Ｒ⁶はヒドロキシ基を有するアルキル基を表す。ただしＲ¹〜Ｒ⁴のうち少なくとも１つは−Ｓ−Ｒ⁵を表す。〕

[In 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 sulfamoyl. Represents a group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, 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, 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, alkyl A sulfonyl 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 (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ . ]

The dye-containing negative curable composition of the present invention may be exposed by any of a proximity method, a mirror projection method, and a stepper method, and in particular, a stepper method (reduction using a reduction projection exposure machine). It is preferable to perform exposure by a projection exposure method. Such a stepper method forms a pattern by performing exposure while varying the exposure amount stepwise, and the rectangularity of the pattern, which is one of the effects of the present invention, particularly when performing such stepper exposure. Can be good.
As an exposure apparatus used for the stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

(A) Alkali-soluble binder First, the alkali-soluble binder in the present invention will be described. The alkali-soluble binder in the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

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

  In addition, as the alkali-soluble binder in the present invention, a polymer obtained by copolymerizing a monomer having a hydrophilic group can also be used. Examples of the monomer having a hydrophilic group include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, Dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) ) Acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

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

  The alkali-soluble binder in the present invention preferably has an unsaturated double bond in the side chain in order to improve the crosslinking efficiency. As an unsaturated double bond couple | bonded with the side chain of alkali-soluble resin in this invention, an allyl group, a (meth) acryl group, an allyloxyalkyl group, a vinyl group etc. are mentioned, for example, an allyl group, (meth) Acrylic groups are preferred. These unsaturated double bonds may be introduced by copolymerizing the unit having the unsaturated double bond or may be introduced later by a polymer reaction. As the alkali-soluble binder having an unsaturated double bond in the side chain, for example, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are suitable. Used for.

  As the alkali-soluble binder in the present invention, an acrylic resin is preferable among the various binders, and examples of the acrylic resin include benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. A copolymer comprising a monomer selected from KS-resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P-series and the like are preferable.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and is preferably 2000 to 1 × 10 ⁵ . A polymer is more preferable, and a 5000 to 5 × 10 ⁴ polymer is particularly preferable.

  The content of the alkali-soluble binder is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass with respect to the total solid content in the composition from the viewpoint of developability and the like. preferable.

(B) Organic solvent-soluble dye The organic solvent-soluble dye in the present invention comprises at least one selected from the following general formula (1) and at least one selected from the general formula (2). To do.
Details are described below.

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

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 G, the same substituent as 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 each represent —CR ²⁰¹ ═ and —CR ²⁰² ═, or one of them represents a nitrogen atom, and the other represents —CR ²⁰¹ ═ or —CR ²⁰² ═. As B ¹ and B ² , those representing —CR ²⁰¹ ═ and —CR ²⁰² ═, respectively, are 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, compound Ring 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 may be 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).

  Specific examples of the pigment represented by the general formula (1) (dyes ma-1 to ma-7, mb-1 to mb-7, mc-1 to mc-7, md-1 to md-7, me- 1 to me-7, mf-1 to mf7, and mx-1 to mx-6, and a-1 to a-36, b-1 to b-8, c-1 to c-5, d-1 to d-5, e-1 to e-5, and f-1 to f-33) are shown below, but the dye used in the present invention is not limited to the following examples.

-Dye represented by general formula (2)-
Next, the dye represented by the general formula (2) (quinophthalone dye) will be described in detail.
The compound represented by the following general formula (2) is a compound that satisfies high light resistance and high heat resistance, both of which have not been conventionally used, and can be freely dissolved in water or a solvent if necessary. .

In the general formula (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ .

Further, in the general formula (2), R ⁵ is preferably an alkyl group having 2 to 16 carbon atoms in total containing 1 to 6 oxygen atoms in the form of an ether bond, and R ² and R ³ are —S—. R ⁵ and R ¹ and R ⁴ are preferably a hydrogen atom or a halogen atom. Note that one of the structural features of the dye represented by the general formula (2) in the present invention is that it has at least one alkyl group having an ether bond in the benzene ring on the phthaloyl side of the quinophthalone skeleton.

In the general formula (2), examples of the halogen atom represented by R ^{1 to} R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom and a bromine atom.
In the case where R ^{1 to} R ⁴ are —S—R ⁵ , R ⁵ is preferably an alkyl group having 1 to 6 oxygen atoms in the form of an ether bond and having 2 to 16 carbon atoms in total, particularly an oxygen atom. Alkyl groups having 2 to 12 carbon atoms in total in the form of 2 to 4 ether bonds are preferred. Here, the alkyl group may be linear or branched, and may have a ring-forming part.

Examples of R ⁵ include 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 3-ethoxypropyl group, 2-ethoxy-1-methylpropyl. Group, 3-propoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 4-methoxybutyl group, 4-propoxybutyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 2,3-dimethoxypropyl Group, 2,3-diethoxypropyl group, 2,3-dipropoxypropyl group, 2,3-diisopropoxypropyl group, 2,3-dibutoxypropyl group, 2,3-dicyclohexylpropyl group,

2,3-di (2-ethoxyethoxy) propyl group, 2,3-di (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxy) -3- (2-ethoxyethoxyethoxy) propyl group, 2- (2-ethoxyethoxyethoxy) -3- (2-propoxyethoxyethoxy) propyl group, 2,3-di (1,3-dioxolan-2-yl-ethoxy) propyl group, (2,2-dimethyl- 1,3-dioxolan-4-yl) methyl group, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl group, (2,2-diethyl-1,3-dioxolane-4- Yl) methyl group, (2-propyl-1,3-dioxolan-4-yl) methyl group, (2,2-dipropyl-1,3-dioxolan-4-yl) methyl group, (2-propyl-1, - dioxolan-4-yl) methyl group, (2-pentyl-1,3-dioxolan-4-yl) methyl group,

2- (tetrahydrofurfuryloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylethyloxy) ethyl group, 2- (1,3-dioxolan-2-ylmethyloxy) propyl group, 2- (tetrahydropyran-2-methyloxy) ethyl group, 2- (1,3-dioxan-2-ylethyloxy) ethyl group, 2 -(1,3-dioxan-2-ylethyloxy) propyl group, hydroxyethoxyethyl group, hydroxyethoxyethoxyethyl group, 2- (hydroxyethoxy) propyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy -3-Ethoxypropyl group, 2-hydroxy-3-butoxypropyl group, 2-hydroxy-3- (ethoxyethoxy) Propyl group, and the like.

In case R ¹ to R ⁴ is -S-R ^6, preferably 1 to 4 comprises a total alkyl group having 2 to 12 carbon a hydroxy group as R ^6, in terms of the optical density of the dye, hydroxy An alkyl group having 1 to 3 groups and 2 to 8 carbon atoms in total is particularly preferable.

Examples of R ⁶ include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-1-methylpropyl group, 4-hydroxybutyl group, Examples include 2,3,4-trihydroxybutyl group, 2,3,4,5-tetrahydropentyl group, 6-hydroxyhexyl group, 11-hydroxyundecanyl group, 12-hydroxydodecanyl group and the like.

In the dye represented by the general formula (2) and tautomers thereof, the total number of oxygen atoms as ether bonds contained in R ^{1 to} R ⁴ is preferably 1 to 16, From the viewpoint of optical density, 2 to 12 is particularly preferable.
In addition, the total number of oxygen atoms contained in R ^{1 to} R ⁴ including the oxygen atom contained in the hydroxy group is preferably 2 to 24, and particularly preferably 3 to 16.
In addition, the dye represented by the general formula (2) and the tautomer thereof preferably have a structure in which —S—R ⁵ is introduced into R ² and / or R ³ in view of the absorption characteristics of the dye.

  The dye represented by the general formula (2) [the following dye (2)] has tautomers of structures such as dyes (2 ′) and (2 ″) as shown below. Variants are also included in the scope of the present invention.

  Hereinafter, specific examples (specific examples 1 to 227) of the compound (quinophthalone compound) represented by the general formula (2) in the present invention are shown in the table. However, these specific examples do not limit the scope of the compounds in the present invention.

(Method for producing the dye represented by the general formula (2))
The manufacturing method of the compound (quinophthalone compound) represented by General formula (2) in this invention is demonstrated below. The outline of the typical production method (first and second production methods) is as follows.

-First manufacturing method-
As the first production method, first, in an organic solvent, 1 to 16 mols of the following compound (B) is used with 1 to 16 mols of the alkali compound with respect to 1 mol of the following compound (A). And 20 to 200 ° C. for 1 to 8 hours.

[In the compound (A), R ⁷ represents a halogen atom, and R ⁸ represents a hydrogen atom. a represents the number of introduced R ⁷ and represents an integer of 1 to 4. b represents the number of introduced R ⁸ and represents an integer of 0 to 3. However, a + b is 4. ]

HS-R ⁵ (B)
[In the compound (B), R ⁵ is the same as that in the general formula (2). ]

  In this case, N-methylpyrrolidone, DMI, sulfolane, DMF, DMAC, toluene, ethyl acetate, etc. are used as the organic solvent, and potassium carbonate, calcium carbonate, sodium hydroxide and potassium hydroxide are used as the alkaline compound. Etc. are used. After the reaction, the reaction solution is discharged into water, extracted with an organic solvent such as ethyl acetate, washed with water, concentrated, and then purified by column chromatography as necessary, and expressed by the general formula (2). A dye (quinophthalone compound) can be obtained.

-Second manufacturing method-
As a second production method, first, 1 to 16 moles of the following compound (C) and 20 to 20 moles of an alkali compound are used in an organic solvent with respect to 1 mole of the compound (A). The reaction is performed at ˜200 ° C. for 1 to 24 hours.

HS-R ⁶ (C)
[In the compound (C), R ⁶ represents the same as in general formula (2). ]

  Next, the solution is discharged into water, neutralized with dilute hydrochloric acid or acetic acid, collected by filtration and washed with water to obtain the following compound (D). At this time, as the organic solvent and the alkali compound used in the above reaction, those similar to those used in the first production method are used.

[In the compound (D), R ⁷ and R ⁸ represent the same as those in the compound (A), and R ⁶ represents the same as in the general formula (2). Moreover, a-c represents 0-3, b represents 0-3, c represents 1-4. However, (a−c) + c + b is 4. ]

  Next, by reacting the compound (D) in an organic solvent with an alkali compound in an amount of 1 to 24 mol and 1 to 24 mol of the following compound (E) at 20 to 200 ° C. for 1 to 24 hours. The target compound represented by the general formula (2) is obtained. As said organic solvent and said alkali compound, the thing similar to what was used by said 1st manufacturing method is used.

Z-R ⁹ (E)
[In the compound (E), Z represents a halogen atom, a toluenesulfonyloxy group or a methanesulfonyloxy group, and R ⁹ represents an alkyl group which may contain an oxygen atom in the form of an ether bond or a hydroxy group. . ]

Further, even when the compound (D) and the compound (E) are reacted in a two-phase system using a phase transfer catalyst and an aqueous alkali solution in an organic solvent, the dye represented by the general formula (2) is similarly obtained. Can be manufactured. As the organic solvent and alkali compound used in the above reaction, those similar to those used in the first production method are used.
Further, as the phase transfer catalyst, tetrabutylammonium bromide, tetramethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, etc. are used.
When R ⁶ of the compound (D) is an alkyl group having an α, β-dihydroxy group, the following compound (F) and an acid catalyst such as p-toluenesulfonic acid are dehydrated and refluxed in an organic solvent. Thus, the target compound represented by the general formula (2) can be obtained.

[In the compound (F), R ¹⁰ represents a hydrogen atom or an alkyl group, R ¹¹ represents an alkyl group, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. ]

(Other organic solvent soluble dyes)
In the present invention, the pigments in the present invention may be used in combination with the same pigments, other organic solvent-soluble dyes, salts of other organic solvent-soluble dyes with metals or nitrogen-containing compounds, complexes, other organic solvents. You may use it simultaneously with the derivative of a solvent soluble dye, etc.
As other organic solvent soluble dyes, known direct dyes, acid dyes, mordant / acid mordant dyes, bases described in COLOR INDEX (SOCIETY OF DYES AND COLORISTS) and dyeing notes (published by Color Dyeing Co., Ltd.) Dyes, vat dyes, sulfur dyes, azoic dyes, disperse dyes, reactive dyes, fluorescent brighteners, other dyes, pigment resin colors, pigments, near infrared absorbing dyes, and the like.
As these organic solvent-soluble dyes, for example,
CISolvent Blue 25,
CISolvent Blue 55,
CISolvent Blue 67,
CISolvent Blue 38,
CISolvent Yellow82,
CISolvent Yellow 162,
CISolvent Orange 56,
CI Acid Violet 17,
CI Acid Violet 49,
CI Direct Blue 86,
These may be used alone or in combination of two or more.

~ Acid dye ~
The acid dye will be described. The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in organic solvents and developers, salt-forming properties, absorbance, and other components in the curable composition. Are selected in consideration of all the required performances such as the interaction, light resistance, heat resistance and the like.
Although the specific example of the said acidic dye is given to the following, it is not limited to these. For example, acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,108,112,113, 120, 129, 138, 147, 158, 171, 182, 192, 249;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50;
acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95;
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 266, 274;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,40,42,54,65,72,73,76,79,98,99,111,112,114, 116, 169, 243;
Food Yellow 3; and derivatives of these dyes.

Among these, as the acid dye,
acid black 24;
acid blue 7, 23, 25, 29, 62, 83, 86, 87, 90, 92, 108, 138, 158, 249;
acid green 3, 5, 9, 16, 25, 27, 50;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217;
acid violet 7;
Acid yellow 17, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and the like and derivatives of these dyes are preferred.

Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferable. I. Solvent Blue 44, 38, C.I. I. Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl] ulyl] , Etc. and derivatives of these dyes are also preferably used.
As the derivative of the acid dye, a compound obtained by converting the sulfonic acid of the acid dye into a sulfonic acid amide or a sulfonic acid ester can be used effectively.

~ About atomic groups that form salts with acid dyes ~
The atomic group that forms a salt with the acidic dye is not limited as long as it is a cationic group that forms a salt with the anion of the acidic dye. Examples of such atomic groups include Li, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Ni, Cu, Co, Fe, or a cation composed of a nitrogen-containing compound. Is mentioned.

  The nitrogen-containing compound that forms a counter salt with the acid dye will be described. In the present invention, the nitrogen-containing compound that forms a salt with the acidic dye has all of the solubility in organic solvents and developer, the salt-forming property, the absorbance of the dye, the interaction with other components in the curable composition, etc. Selected in consideration. When selected only from the viewpoint of absorbance, those having a molecular weight as low as possible are preferable. Among them, the molecular weight is preferably 245 or less, more preferably 240 or less, and particularly preferably 230 or less.

  In addition, in order to prevent dye fading and to improve heat resistance, a nitrogen-containing compound generally known as an anti-fading agent may be used. In this respect, a compound having a lower oxidation potential (lower ionization potential) Tertiary amine compounds, aliphatic cyclic amine compounds, aniline compounds, hydrazine compounds, and the like are preferable.

~ Mole ratio (L) of atomic group / acid dye forming salt with acid dye ~
The molar ratio of the atomic group forming the salt with the acid dye / acid dye (hereinafter sometimes referred to as “L”) will be described. The L is a value that determines the molar ratio between the acid dye molecule and the atomic group that is a counter ion, and can be freely selected depending on the salt forming conditions of the acid dye atomic group. Specifically, it is a numerical value between 0 ≦ L ≦ 10, solubility in organic solvents and developers, salt formation, absorbance, interaction with other components in the curable composition, light resistance, heat resistance It is selected in consideration of all necessary performance priorities such as sex. From the standpoint of absorbance or color value alone, L is preferably a numerical value between 0 ≦ L ≦ 7, more preferably a numerical value between 0 ≦ L ≦ 6, and 0 ≦ L ≦ 5. It is particularly preferable to take a numerical value between.

~ Use concentration ~
Next, the use concentration of the organic solvent-soluble dye contained in the composition of the present invention (including other dyes in the case of using other dyes such as an acid dye in addition to the colorant in the present invention) will be described. The concentration of the organic solvent-soluble dye in the total solid component in the composition of the present invention varies depending on the type of the dye, but is preferably 0.5 to 80% by mass, more preferably 0.5 to 60% by mass, and 5-50 mass% is especially preferable. When mixing two or more dyes to adjust the color, the amount of the dye added in the smallest amount is preferably at least 10% of the total amount when the total dye amount is 100%.

  In addition, there is no restriction | limiting in particular in mass ratio [(1) / (2)] of the pigment | dye represented by the said general formula (1) and the said general formula (2), According to spectral characteristics etc. In addition, when an acid dye other than the colorant of the present invention is used in combination with the colorant of the present invention, the mass ratio of the dye to be used is arbitrarily set in consideration of the target spectral characteristics. can do.

<(C) Photopolymerization initiator>
Next, the photopolymerization initiator will be described. A photoinitiator is contained with the below-mentioned radically polymerizable monomer in the dye-containing negative curable composition of the present invention. The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize the radical polymerizable monomer, but is preferably selected from the viewpoints of characteristics, starting 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 and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

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

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

  Specific examples of the halomethyl-s-triazine compound 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- (naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-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-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) 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- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, 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) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

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

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

  Among these photopolymerization initiators, oxime compounds are preferable. For example, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O— Acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl- 9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyl Examples include tyryl 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, and the like. Can be mentioned.

In addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound / trimethyl disclosed in Japanese Patent Publication No. 51-48516 And halomethyl-s-triazine compounds.

  As total content of the said photoinitiator, 0.01 mass%-50 mass% are preferable with respect to the said radical polymerizable monomer solid content (mass), 1 mass%-30 mass% are more preferable, 1 A mass% to 20 mass% is particularly preferred. When the content of the photopolymerization initiator is in the range of 0.01 to 50% by mass, the polymerization is easy to proceed, and the film strength can be sufficiently improved.

<(D) Radical polymerizable monomer>
Next, the radical polymerizable monomer will be described. As the radical polymerizable monomer used in the present invention, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. The ethylenic double bond is preferably (meth) acrylate. By containing with the above-mentioned photoinitiator etc., the composition of this invention can be comprised in a negative type.

  Examples of the radical polymerizable monomer 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 , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane and then (meth) acrylated after addition of ethylene oxide or propylene oxide; Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, Polyester acrylates described in JP-B Nos. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof; Can be mentionedFurthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers. The radical polymerizable monomer in the present invention is preferably a polyfunctional (meth) acrylic compound.

  As content of the said radically polymerizable monomer, it is preferable that it is 1-60 mass% with respect to the total solid in a composition, and it is still more preferable that it is 10-50 mass%. When the content of the radical polymerizable monomer is in the range of 1 to 60% by mass, the curability of the exposed part is sufficient, and the elution property of the unexposed part can be improved.

-Crosslinking agent-
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

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

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) above are collectively referred to as a methylol group-containing compound according to (b), an alkoxymethyl group-containing compound according to (b) or an acyloxy according to (b). Sometimes referred to as a methyl group-containing compound.

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

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

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

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

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a methylol group-containing compound according to (c), an alkoxymethyl group-containing compound according to (c), or an acyloxymethyl group-containing compound according to (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
Also in the said naphthol compound, except the ortho position of OH group, it may be unsubstituted or may have a substituent.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group is a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) is obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid.
The acyloxymethyl group-containing compound according to (c) is obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated from 1 to 5 methylol groups, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the dye-containing negative curable composition varies depending on the material, but from the viewpoint of improving curability, it is 1 to 70 with respect to the solid content (mass) of the curable composition. % By mass is preferable, 5 to 50% by mass is more preferable, and 7 to 30% by mass is particularly preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. For example, 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-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

<(E) Organic solvent>
The organic solvent that can be used in the present invention is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but in particular, the solubility and coating property of the dye and binder. In view of safety, it is preferably selected, for example, a cyclic ketone solvent is preferable. Moreover, when preparing the dye-containing negative curable composition of this invention, it is preferable to use the mixed solvent containing at least 2 type of organic solvent.

  Moreover, when using the mixed solvent which mixed 2 or more types of organic solvent, as this mixed solvent, it is preferable that it is a mixed solvent of cyclic ketone solvent and another 1 type of organic solvent. Examples of the cyclic ketone solvent include cyclopentanone, cyclohexanone, and cycloheptanone, and cyclohexanone is particularly preferable.

  Examples of the solvent other than the cyclic ketone include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, as the other organic solvent used in combination with the cyclic ketone solvent, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate are preferable, ethyl lactate, Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

  When the cyclic ketone solvent and another organic solvent are mixed, the content of the cyclic ketone solvent in the total amount of the mixed solvent is preferably 40% by mass or more, and more preferably 60% by mass or more. .

  The amount of the organic solvent used in the present invention is preferably such that the total solid concentration of the dye-containing negative curable composition of the present invention is 5 to 80% by mass from the viewpoint of coatability, and 5 to 60. More preferably, it is more preferably 10 to 50% by weight.

<Various additives>
In the dye-containing negative curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An anti-aggregation agent or the like can be blended.

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

Further, when the alkali solubility of the non-image area is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids 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.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used.
The dye-containing negative curable composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is formed into a predetermined mask pattern. And a negative coloring pattern is formed by developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.
In the present invention, the exposure is preferably performed by the above-described stepper exposure at the time of the exposure.

  In the production of a color filter, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) for the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

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

  Any developer can be used as long as it has a composition that dissolves the uncured part of the dye-containing negative curable composition of the present invention but does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

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

  The color filter of the present invention can be used for a solid-state 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 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.

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

1) Preparation of dye-containing negative curable composition Each compound was mixed and dissolved in the composition shown below to prepare the dye-containing negative curable composition of the present invention.
〔composition〕
・ Ethyl lactate (organic solvent) 67.3g
・ Resin C 7.9g
(Benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])
Monomer A (radical polymerizable monomer) 4.8 g
(DPHA (main component: dipentaerythritol hexaacrylate), manufactured by Nippon Kayaku Co., Ltd.)
・ 2.1g of photopolymerization initiator
(Product name: TAZ-107, manufactured by Midori Chemical Co., Ltd.)
-6.6 g of a dye represented by the general formula (1)
(Organic solvent soluble dye, the above dye ma-1)
-Dye represented by general formula (2) 2.2 g
(Organic solvent soluble dye, specific example 39 above)

2) Production of silicon wafer with undercoat layer A resist solution (trade name: CT-2000L, manufactured by Fuji Film Arch Co., Ltd.) was applied onto a silicon wafer using a spin coater so as to have a film thickness of 2 μm, and 220 ° C. And dried for 1 hour to form a cured film (undercoat layer).

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition obtained in 1) above is applied on the undercoat layer of the silicon wafer with an undercoat layer obtained in 2) above using a spin coater so that the film thickness becomes 1 μm. The sample was pre-baked at 100 ° C. for 120 seconds to prepare a sample in which a resist layer was formed on the substrate.

[Examples 2 to 9]
In Example 1, a dye-containing negative curable composition was prepared in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 12 below. A sample was formed.

[Comparative Example 1]
In Example 1, a dye-containing negative curable composition for comparison was used in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 12 below. Was prepared to form a sample.

4) Evaluation (1) Sensitivity For the samples formed in each of the examples and comparative examples, using an i-line reduction projection exposure apparatus, the exposure amount was passed through a coating film at a wavelength of 365 nm through a mask of 2 μm length × 2 μm width. Irradiated. After irradiation, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. The image formation was confirmed by an ordinary method using an optical microscope and SEM photograph observation.
At this time, the exposure amount at which the width of the pixel pattern of 2 μm in length × 2 μm in width and the space between the pixel patterns was 1: 1 was determined as the appropriate exposure amount, and the exposure amount was defined as the sensitivity. Smaller numbers are preferable because of higher sensitivity. The results are shown in Table 2 below.

(2) Profile In (1) above, the pattern cross section of the pixel pattern formed at the appropriate exposure amount was observed on the SEM image. At this time, a good rectangular profile is evaluated as “◯”, a slightly round top (round head) shape is evaluated as “△”, and a completely round top shape is evaluated as “×”. It was evaluated. The results are shown in Table 2 below.

(3) Unexposed portion residue In (1) above, the pattern cross section of the pixel pattern formed at the appropriate exposure amount was observed with an SEM image. At this time, the case where no residue was found in the unexposed area was evaluated as “◯”, the case where the residue was slightly recognized in the unexposed area was evaluated as “△”, and the case where there was no practical problem was evaluated as “△”. Those in which residues were clearly observed in the part were evaluated as “x”. The results are shown in Table 2 below.

(4) Heat resistance On the silicon wafer produced separately, the dye containing negative curable composition obtained by said 1) was apply | coated so that it might become a film thickness of 1 micrometer. The silicon wafer on which the coating film was formed was left on a hot plate at 200 ° C. for 1 hour, and then the spectral change was measured using a spectrophotometer (trade name: MS-1500, manufactured by Shimadzu Corporation). From the measured values, ΔE ^* ab was calculated by a color analysis program and evaluated for heat resistance. The results are shown in Table 2 below.

(5) Light resistance The separately prepared silicon wafer was coated with the dye-containing negative curable composition obtained in 1) so as to have a film thickness of 1 μm, and the coated film was coated with a xenon irradiation weather meter (trade name: SX75, manufactured by Suga Test Instruments Co., Ltd.) irradiated for 20 hours (200,000 lux · h), and then measured the spectral change using a spectrophotometer (trade name: MS-1500, manufactured by Shimadzu Corporation) did. From this measured value, ΔE ^* ab was calculated by a color analysis program and evaluated for light resistance. The results are shown in Table 2 below.

※アルカリ可溶性バインダー
・樹脂Ａ：商品名 ＡＣＡ２５０、ダイセル化学工業（株）製
（化合物名：メタクリル酸−４−アクリロイルオキシメチル−２−ヒドロキシシクロヘキシルエステル／メタクリル酸アルキル共重合体）
・樹脂Ｂ：商品名 ＡＣＡ３００、ダイセル化学工業（株）製
（化合物名：メタクリル酸−４−アクリロイルオキシメチル−２−ヒドロキシシクロヘキシルエステル／メタクリル酸アルキル共重合体）
・樹脂Ｃ：ベンジルメタクリレート／メタクリル酸共重合体（＝６０／４０〔モル比〕）
※ラジカル重合性モノマー
・モノマーＡ：日本化薬（株）製、ＤＰＨＡ（主成分：ジペンタエリスリトールヘキサアクリレート）
※光重合開始剤
・「ＴＡＺ−１０７」：みどり化学（株）製
・オキシムＡ：２−（Ｏ−ベンゾイルオキシム）−１−［４−（フェニルチオ）フェニル］−１，２−オクタンジオン、チバ・スペシャルティ・ケミカル（株）製

* Alkali-soluble binder / resin A: Trade name ACA250, manufactured by Daicel Chemical Industries, Ltd. (Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
Resin B: Trade name ACA300, manufactured by Daicel Chemical Industries, Ltd. (Compound name: Methacrylic acid-4-acryloyloxymethyl-2-hydroxycyclohexyl ester / alkyl methacrylate copolymer)
Resin C: benzyl methacrylate / methacrylic acid copolymer (= 60/40 [molar ratio])
* Radically polymerizable monomer / Monomer A: Nippon Kayaku Co., Ltd., DPHA (main component: dipentaerythritol hexaacrylate)
* Photopolymerization initiator “TAZ-107” manufactured by Midori Chemical Co., Ltd. • Oxime A: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, Ciba・ Specialty Chemical Co., Ltd.

  From the said Table 13, in the Example using the pigment | dye in this invention, it was excellent in the sensitivity, the rectangularity of the pattern was also favorable, and the residue was not confirmed by the unexposed part. On the other hand, in the comparative example which did not use the pigment | dye in this invention, both the sensitivity and the rectangular shape of a pattern were bad, and also the residue was recognized in the unexposed part, and it was inferior to heat resistance and light resistance.

Claims (6)

Dye-containing negative curing comprising at least: (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerization initiator, (D) a radical polymerizable monomer, and (E) an organic solvent. The organic solvent-soluble dye (B) is at least one dye represented by the following general formula (1), and at least one dye represented by the following general formula (2): A dye-containing negative curable composition comprising:

[In 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 sulfamoyl. Represents a group. These may further have a substituent. G, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, 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, 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, alkyl A sulfonyl 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 (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, —S—R ⁵ or —S—R ⁶ . S represents a sulfur atom, R ⁵ represents an alkyl group containing an oxygen atom in the form of an ether bond, and may further have a hydroxy group as a substituent. R ⁶ represents an alkyl group having a hydroxy group. However, at least one of R ^{1 to} R ⁴ represents —S—R ⁵ . ]   The dye-containing negative curable composition according to claim 1, wherein the photopolymerization initiator (C) is an oxime compound.   The dye-containing negative curable composition according to claim 1 or 2, wherein the (A) alkali-soluble binder is a resin having an unsaturated double bond in a side chain.   The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the solvent (E) contains a cyclic ketone solvent.   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 4.   A process comprising applying a dye-containing negative curable composition according to any one of claims 1 to 4 on a support, exposing through a mask, and developing to form a pattern. A method for producing a color filter.