JP2003207888A - Dye-containing negative curable composition, and color filter including the same, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-containing negative curable composition having high sensitivity, a high transmittance and a wide development latitude, obtaining high resolution, free of leaching of the dye, color mixture, heat deterioration and light deterioration and ensuring high productivity and to provide a color filter including the same and a method for producing the same. <P>SOLUTION: The dye-containing negative curable composition which contains an organic solvent-soluble dye and causes a radical polymerization reaction under a photopolymerization initiator, is characterized in that the ratio Ad/Ai of the absorbance Ad of the organic solvent-soluble dye to the absorbance Ai of the photopolymerization initiator at the wavelength of radiated light for initiating radical polymerization is ≤10.0, and the color filter including the same and the method for producing the same are also provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention includes a dye-containing negative curable composition suitable for forming a colored image forming a color filter used in a liquid crystal display device or a solid-state image pickup device, and the curable composition. The present invention relates to a color filter and a manufacturing method thereof.

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state image pickup device, a dyeing method, a printing method, an electrodeposition method and a pigment dispersion method are known. The dyeing method is a method of producing a color filter by dyeing a dyeing base material made of a natural resin such as gelatin, glue, or casein or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. In the dyeing method, since a dye is used, there is a problem in light resistance, heat resistance, moisture resistance, and the like, and it is difficult to uniformly control dyeing and fixing properties on a large screen, and thus color unevenness easily occurs, and In dyeing, there is a problem that the process is complicated because a dye-proof layer is required.

In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, a resin containing a pigment dissolved or dispersed in a solvent is ionized, and a voltage is applied to form a colored image in a pattern. This is a method of producing a color filter. The electrodeposition method requires a photolithography process including a film formation of a transparent electrode for forming a color filter and an etching process in addition to a transparent electrode for display, but if there is a short circuit at that time, a line defect occurs and the yield decreases. Come on. In addition to the stripe arrangement, it is difficult to apply it to a mosaic arrangement in principle, and it is difficult to manage the transparent electrodes.

The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, since the ink that can be used has a high viscosity, it is difficult to filter, dust, foreign matter, and defects due to gelled parts of the ink binder are likely to occur, and the positional accuracy, line width accuracy, and plane smoothness that accompany printing accuracy are high. I have a problem with.

The pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various radiation-sensitive compositions. This method is stable to light, heat, etc. because it uses a pigment, and at the same time has sufficient positional accuracy because it is patterned by the photolithography method, and is suitable for the production of color filters for large screens and high-definition color displays. .

To prepare a color filter by the pigment dispersion method, a colored radiation-sensitive composition is applied on a glass substrate by a spin coater, a roll coater or the like and dried to form a coating film, and the coating film is patterned. A colored pixel is obtained by exposing and developing, and a color filter can be obtained by repeating this operation according to the number of colors.

As a pigment dispersion method, there is disclosed in JP-A-1-1024.
69, JP-A-1-152499, and JP-A-2-181.
704, JP-A-2-199403, JP-A-4-76.
062, JP-A-5-273411, and JP-A-6-18.
No. 4482 and JP-A No. 7-140654, a negative photosensitive composition using a photopolymerizable monomer as an alkali-soluble resin and a photopolymerization initiator is disclosed.

However, in recent years, further high definition has been desired in color filters for solid-state image pickup devices. However, in the conventional pigment dispersion system, the resolution is not essentially improved, and there are problems such as color unevenness due to coarse particles of the pigment. Therefore, for applications requiring a fine pattern such as a solid-state image sensor. It wasn't suitable. In order to solve the above problems, a technique using a dye has been proposed in JP-A-6-75375. However, since the dye essentially acts as a light absorber, it absorbs the irradiation light and suppresses the light absorption of the photopolymerization initiator and the subsequent decomposition and radical generation. It was difficult to obtain sufficient curability with the curable composition.

In order to avoid this "action of the dye as a radical light absorber" and to accelerate the crosslinking reaction (curing reaction) as much as possible, the exposure energy is increased and a post-crosslinking agent is added. "Inappropriate solutions" have been implemented in the past. However, according to the method of increasing the exposure energy, there are disadvantages such as a decrease in practicality such as an increase in load on the irradiation device and a long process time, and further photodeterioration of the dye also results. Even by the method of adding a post-crosslinking agent by light or heat, deterioration of components such as dyes and binders in the composition by light or heat cannot be avoided.

For example, as described in Japanese Patent Application Laid-Open No. 6-75375, a thermosetting agent is conventionally used because it has sufficient curability and can suppress the elution of dyes when a second or subsequent resist is applied. The method of adding a light curing agent has been adopted. However, even if this method is adopted, the elution of the dye cannot be completely suppressed, and a method for curing the pattern to a higher degree has been desired. Further, if a method of sufficiently curing the pattern after development by adding the heat curing agent or the light curing agent is adopted, the thermal deterioration and the light deterioration of the dye are caused secondarily, and these various problems are caused. The development of a method for solving the above has been eagerly desired.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. The present invention provides a sufficient degree of curing with high sensitivity,
Negative curable composition containing a dye having a high transmittance, a wide development latitude, a high resolution image and high productivity without dye elution, heat deterioration and photodegradation, and the negative dye containing the dye. An object of the present invention is to provide a color filter which contains a curable composition, has a high transmittance, a high resolution, a wide development latitude, and is free from heat deterioration and light deterioration and has high productivity. Also provided is a method for producing the color filter, which is highly sensitive and can be sufficiently cured, and which has a productivity capable of producing with high efficiency without elution of dye, heat deterioration and light deterioration. The purpose is to do.

[0012]

The concrete means for solving the above-mentioned problems are as follows, and the above-mentioned object is achieved. (1) In a dye-containing negative curable composition containing an organic solvent-soluble dye and causing a radical polymerization reaction by a photopolymerization initiator, the absorbance of the organic solvent-soluble dye at the wavelength of irradiation light for initiating radical polymerization The ratio Ad / Ai between Ad and the absorbance Ai of the photopolymerization initiator is 10.
It is a negative curable composition containing a dye, which is 0 or less.

(2) The dye-containing negative curable composition as described in (1) above, which contains an alkali-soluble binder, an organic solvent-soluble dye, a photopolymerization initiator, a monomer, and a solvent. (3) The negative curable composition containing a dye according to the above (1) or (2), which further contains a crosslinking agent. (4) The dye-containing negative according to (2) or (3), wherein the alkali-soluble binder is at least one selected from acrylic resins, acrylamide resins, polyhydroxystyrene resins, and polysiloxane resins. It is a mold-curable composition.

(5) The dye-containing negative curable composition as described in (3) or (4) above, wherein the crosslinking agent is a polyfunctional epoxy resin. (6) The dye-containing negative curable composition according to any one of (1) to (5), wherein the higher the absorbance at the wavelength of irradiation light for initiating radical polymerization, the more the photopolymerization initiator. is there.

(7) A color filter comprising the dye-containing negative curable composition as described in any one of (1) to (6) above. (8) A step of applying the negative curable composition containing a dye according to any one of the above (1) to (6) on a support, exposing through a mask, and developing to form a negative pattern. A method of manufacturing a color filter, comprising: In the method of manufacturing a color filter, the above steps are repeated for a desired number of hues when manufacturing a color filter having a desired hue. Moreover, an aspect having a step of curing the negative pattern by heating and / or exposure is also suitable, if necessary.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The dye-containing negative curable composition of the present invention, a color filter using the same and a method for producing the same will be described in detail below. The dye-containing negative curable composition of the present invention (hereinafter, also simply referred to as “curable composition”) comprises at least an organic solvent-soluble dye and a photopolymerization initiator. Preferably, it comprises an alkali-soluble binder, a monomer and a solvent together with an organic solvent-soluble dye and a photopolymerization initiator, and optionally further comprises a crosslinking agent. It may also contain other components.

As described above, since the dye essentially acts as a light absorber, when the dye is added to the curable composition utilizing radical polymerization, it is not possible with the prior art to obtain sufficient curability. It was possible. Therefore, the present inventor diligently studied the curability in forming an image using a dye-containing composition, and as a result, when irradiating exposure energy in a practically suitable range, the efficiency of the photopolymerization initiator was increased. In consideration of various decomposition and generation of initiation radicals, the ratio Ad / when the absorbance of the dye (organic solvent-soluble dye) is Ad and the absorbance of the photopolymerization initiator is Ai at the wavelength of irradiation light for initiating polymerization We have found that Ai needs to be 10.0 or less.

In the present invention, as a dye-containing negative curable composition, an organic solvent-soluble dye (hereinafter, also simply referred to as "dye") in the composition at the wavelength (exposure wavelength) of irradiation light for initiating polymerization is used. When the absorbance of (i.e.) is Ad and the absorbance of the photopolymerization initiator is Ai, by using a curable composition having an Ad / Ai ratio of 10.0 or less,
Higher sensitivity (higher curing rate), higher transmittance, higher resolution, wider development latitude than conventional dye-containing curable composition, no elution of dye, heat deterioration and light deterioration, and higher productivity be able to.

Among them, the dye in the curable composition at the wavelength of the irradiation light for initiating the polymerization is similar to the reason why it is preferable that the dye does not inhibit the absorption of the irradiation light by the photopolymerization initiator in terms of the polymerization sensitivity. It is preferable that the absorbance ratio of (Ad) / photopolymerizable initiator (Ai) is also smaller. Specifically, the Ad
The / Ai ratio is preferably 8.0 or less, more preferably 7.0 or less, and particularly preferably 6.0 or less.

Further, if some dyes are used, even if a film having a film thickness of 2 μm or less is prepared at a concentration suitable for practical use, Ad / A
It was found that the i ratio can be maintained at 10.0 or less. As described above, "a dye capable of maintaining an Ad / Ai ratio of 10.0 or less even when a film having a film thickness of 2 μm or less at a concentration suitable for practical use is maintained" (hereinafter, referred to as "dye according to the present invention"). Is not particularly limited as long as it satisfies the above conditions, but in consideration of solubility, spectral characteristics, heat resistance, and light resistance, in the case of yellow dyes, Valifast Y
ellow1108, same3108, same3120, same41
20, Same 1151, Same 3150, Oil Yellow
129, in the red dye, Valifast Red13
06, same 1308, same 1360, same 3304, same 331
1, 2230, 3305, 3320, Valif
As the ast Pink 2310N, PCRed 136P, and blue dyes, Valifast Blue 2610, 1603, 1605, 2620, 2606 (all manufactured by Orient Chemical Industry, Nippon Kayaku Co., Ltd.) and the like can be preferably mentioned.

Above all, Valifast Yellow
1108, 3120, 1151, Valifast
Red 1360, same 3304, same 3311, Vali
fast Pink2310N, PCRed136P,
Valifast Blue 2610, the same 2620, the same 2606, etc. are more preferable, and the Valifast Ye
low 3120, same 1151, Valifast R
ed1360, same 3304, same 3311, Valifa
st Pink2310N, ValifastBlue
2610, 2620, 2606, etc. are particularly preferable.

Next, the use concentration of the organic solvent-soluble dye will be described. The concentration of the organic solvent-soluble dye in all the solid components of the dye-containing negative curable composition of the present invention varies depending on the dye, but is preferably 0.5 to 80% by mass, more preferably 0.5 to 60% by mass. Preferably 0.5 to 50
Mass% is particularly preferred.

Next, the alkali-soluble binder will be described. The alkali-soluble binder used in the present invention is not particularly limited as long as it is alkali-soluble, but it is preferably selected from the viewpoint of heat resistance, developability, availability and the like. The alkali-soluble binder is preferably a linear organic polymer, which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As such a linear organic high molecular polymer, a polymer having a carboxylic acid in its side chain, for example, JP-A-59-44615 and JP-B-54-3.
No. 4327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-
25957, JP-A-59-53836, JP-A-59.
-71048, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers. Examples thereof include polymers, and similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, etc. Polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, a hydrophilic monomer may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate and hydroxyalkyl (meth).
Acrylate, glycerol (meth) acrylate,
(Meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl Examples thereof include (meth) acrylate, ethyl (meth) acrylate, branched or straight-chain propyl (meth) acrylate, branched or straight-chain butyl (meth) acrylate, and phenoxyhydroxypropyl (meth) acrylate.

In addition, as the hydrophilic monomer, tetrahydrofurfuryl group, phosphoric acid, phosphoric acid ester,
A monomer containing a quaternary ammonium salt, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid and its salt, a morpholinoethyl group and the like are also useful.

Further, in order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Is. Examples of the polymer having a polymerizable group include KS Resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P series (manufactured by Daicel Chemical Industry Co., Ltd.). Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.

Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, acrylic / acrylamide copolymer resin are preferable, and from the viewpoint of developing property control. Therefore, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

As the acrylic resin, a copolymer of monomers selected from benzyl (meth) acrylate, (meth) acrylic, hydroxyethyl (meth) acrylate, (meth) acrylamide, KS Resist-106 (Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries Ltd.) and the like are preferable.

The alkali-soluble binder has a weight average molecular weight (polystyrene conversion value measured by GPC method).
Is preferably a polymer of 1000 to 2 × 10 ⁵ ,
More preferably a polymer of ~1 × 10 ^5, 5000 ~5 ×
Particularly preferred are 10 ⁴ polymers. The content of the alkali-soluble binder in the dye-containing negative curable composition is 10 with respect to the total solid content (mass) of the composition.
To 90 mass% is preferable, 20 to 80 mass% is more preferable, and 30 to 70 mass% is particularly preferable.

Next, the crosslinking agent will be described. INDUSTRIAL APPLICABILITY The present invention uses a dye capable of maintaining the Ad / Ai ratio of 10.0 or less, and further advances the curing reaction in the curable composition to a higher degree as compared with the prior art, and a film having good curability is obtained. It is the gist of the invention, but it is also possible to obtain a more highly cured film by additionally using a crosslinking agent. The cross-linking agent used in the present invention is not particularly limited as long as it can cure the film by a cross-linking reaction, and includes, for example, (a) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxymethyl group. A melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from (c)
Examples thereof include a phenol compound, a naphthol compound, or a hydroxyanthracene compound, which is substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among them, the multi-sensitive epoxy resin is preferable.

The above-mentioned (a) epoxy resin may be any as long as it has an epoxy group and is crosslinkable, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether,
Butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester,
Divalent glycidyl group-containing low molecular weight compounds such as N, N-diglycidylaniline, as well as trivalent typified by trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether and TrisP-PA triglycidyl ether. Glycidyl group-containing low molecular weight compounds, likewise pentaerythritol tetraglycidyl ether, tetramethylol bisphenol A tetraglycidyl ether, and other tetravalent glycidyl group-containing low molecular weight compounds, likewise dipentaerythritol pentaglycidyl ether, dipenta Low molecular weight compounds containing polyvalent glycidyl groups such as erythritol hexaglycidyl ether, polyglycidyl (meth) acrylate, 2,2
1,2-bis (hydroxymethyl) -1-butanol
-Glycidyl group-containing polymer compounds represented by epoxy-4- (2-oxiranyl) cyclohexane adduct and the like,
Etc.

The number of methylol groups, alkoxymethyl groups and acyloxymethyl groups contained in the cross-linking agent (b) is 2 to 6 for melamine compounds, glycoluril compounds, guanamine compounds and urea compounds. In the case of a melamine compound, it is 5 to 6, and in the case of a glycoluril compound, a guanamine compound, and a urea compound, it is 3 to 4. Hereinafter, the melamine compound, the guanamine compound, the glycoluril compound and the urea compound (b) are collectively referred to as the compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) according to (b).

The compound containing a methylol group according to (b) is obtained by heating the compound containing an alkoxymethyl group according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. To be (B)
The acyloxymethyl group-containing compound according to (2) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with an acyl chloride in the presence of a basic catalyst.

Specific examples of the compound (b) having the above substituent will be given below. Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 5 of the methylol groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or a mixture thereof.

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

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

Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolurea or a mixture thereof, and tetramethoxyethylurea. 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, which is substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, is Similar to the case of the agent (b), it is intended to suppress the intermixing with the overcoat photoresist by thermal crosslinking and further increase the film strength. Hereinafter, these compounds may be collectively referred to as a compound containing a methylol group, an alkoxymethyl group or an acyloxymethyl group according to (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the cross-linking agent (c) must be at least two per molecule, and from the viewpoint of thermal cross-linkability and storage stability, the skeleton A compound in which the 2-position and 4-position of the phenol compound to be The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent. In addition, the naphthol compound and the hydroxyanthracene compound, which are the skeletons, are
A compound in which all ortho positions and para positions of the H group are substituted is preferable. The naphthol compound may be unsubstituted or may have a substituent except the ortho position of the OH group.

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

Examples of the skeletal compound in the cross-linking agent (c) include phenol compounds, naphthols and hydroxyanthracene compounds in which the ortho or para position of the phenolic OH group is not substituted, and for example, isomers of phenol and cresol. Bisphenols such as body, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol-A,
4,4'-bishydroxybiphenyl, TrisP-P
A (manufactured by Honshu Chemical Industry Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

Specific examples of the cross-linking agent (c) include phenol compounds such as trimethylolphenol, tri (methoxymethyl) phenol, and a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, and a diamine such as 2,6-dimethylol-4-cresol. Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl -4,4'-Bishydroxybiphenyl, hexamethylol form of TrisP-PA, Tri
Hexamethoxymethyl form of sP-PA, TrisP-P
Examples thereof include a compound in which 1 to 5 methylol groups of the hexamethylol compound of A are methoxymethylated, bishydroxymethylnaphthalenediol, and the like.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene and the like, and examples of the acyloxymethyl group-containing compound include the methylol group of the above methylol group-containing compound. Examples thereof include compounds partially or wholly acyloxymethylated.

Among these compounds, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, hexamethylol form of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their compounds. Phenol compounds in which a methylol group is substituted with an alkoxymethyl group and both a methylol group and an alkoxymethyl group are mentioned. These compounds according to (c) may be used alone or in combination.

The total content of the crosslinking agents (a) to (c) in the dye-containing negative curable composition of the present invention is as follows.
Solid content (mass) of the curable composition, depending on the material
1 to 70 mass% is preferable, and 5 to 50 mass%
Is more preferable, and 7 to 30 mass% is particularly preferable.

Next, the monomer will be described. As the polymerizable monomer, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, or other polyfunctional alcohol to which ethylene oxide or propylene oxide has been added, followed by (meth) acrylate conversion. What was done, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 5
No. 0-6034, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as the described polyester acrylates, epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Furthermore, the Journal of Japan Adhesion Association, Vol.
20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

Next, the photopolymerization initiator will be described. The photopolymerization initiator is not particularly limited as long as it can polymerize the above-mentioned monomer, but is preferably selected from the viewpoints of characteristics, 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 and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and acetophenone. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like.

As the active halogen compound which is a halomethyloxadiazole compound, 2-halomethyl-5-vinyl-1,3,4 described in JP-B-57-6096 is known.
-Oxadiazole compounds, 2-trichloromethyl-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 can be mentioned.

As the active halogen compound which is a halomethyl-s-triazine type compound, Japanese Patent Publication No. 59-1281 is available.
Vinyl-halomethyl-s-triazine compounds described in JP-A No. 53-133428,
(Naphth-1-yl) -4,6-bis-halomethyl-s
-Triazine compound and 4- (p-aminophenyl)-
2,6-di-halomethyl-s-triazine compounds and the like.

Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,6-bis (trichloromethyl) -4- (3,3.
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 -(Naft-1-
Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-s-triazine, 2-
(4-Ethoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1- Il] -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- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, 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- (p-N -Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s
-Triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl)
-S-triazine, 4- [p-N, N-di (phenyl)
Aminophenyl] -2,6-di (trichloromethyl)-
s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)
-S-triazine,

4- [p-N- (p-methoxyphenyl)
Carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-
Di (trichloromethyl) -s-triazine, 4- [m-
Bromo-p-N, N-di (ethoxycarbonylmethyl)
Aminophenyl] -2,6-di (trichloromethyl)-
s-triazine, 4- [m-chloro-p-N, 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-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-fluoro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p-N , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p-N, 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-p-N, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-fluoro-p-N, 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-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-
Ethoxycarbonylmethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (o-
Chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine,

4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-
N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-
p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Bromo-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-(O-chloro-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-chloroethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine and the like.

In addition, TAZ series manufactured by Midori Kagaku Co. (for example, TAZ-107, TAZ-110, TAZ-10
4, TAZ-109, TAZ-140, TAZ-20
4, TAZ-113, TAZ-123, TAZ-10
4), T series manufactured by PANCHIM (for example, T-
OMS, T-BMP, TR, TB), IRGACURE series manufactured by Ciba-Geigy (for example IRGACURE 6)
51, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg 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-methoxyphenyl) -4,5
-Diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- ( Also useful are p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like.

A sensitizer and a light stabilizer may be used in combination with these photopolymerization initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone and 2-bromo-.
9-anthrone, 2-ethyl-9-anthrone, 9,1
0-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) phenyl styryl ketone,
p- (Dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, etc.
Examples thereof include benzothiazole compounds described in JP-A 1-448516, Tinuvin 1130, and 400.

In addition to the above-mentioned photopolymerizable initiator, other known initiators can be used in the dye-containing negative curable composition of the present invention. Specifically, US Pat.
67,660, a vicinal polyketolualdonyl compound disclosed in US Pat. No. 2,367,66.
1- and 2,367,670 disclosed .alpha.-carbonyl compounds, US Pat. No. 2,448,82.
Acyloin ether disclosed in US Pat. No. 8, α disclosed in US Pat. No. 2,722,512
-Hydrocarbon substituted aromatic acyloin compounds, U.S. Pat. Nos. 3,046,127 and 2,951,758
Disclosed in US Pat. No. 3,549,367, triallyl imidazole dimer / p-aminophenyl ketone combination disclosed in US Pat. Benzothiazole compound / trihalomethyl-s
-Triazine compounds and the like.

The total amount of the photopolymerization initiator (and known initiator) used is based on the solid content (mass) of the monomer.
0.01% by mass to 50% by mass is preferable, and 1% by mass to 3%
0 mass% is more preferable, and 1 mass% to 20 mass% is particularly preferable. If the amount used is less than 0.01% by mass, the polymerization may be difficult to proceed, and if it exceeds 50% by mass,
Although the polymerization rate increases, the molecular weight may decrease and the film strength may decrease.

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-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

The solvent used in preparing the dye-containing negative curable composition of the present invention is basically a solvent as long as the solubility of each component and the coatability of the dye-containing negative curable composition are satisfied. Although not limited, it is particularly preferably selected in consideration of the solubility of the dye and the binder, coatability, and safety. Examples of the solvent include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate,
Isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyethyl acetate, methoxy Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-Oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, etc .; 2-Oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, 2 -Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2 -Methoxy-2-me Methyl Rupuropion acid, 2
Ethyl ethoxy-2-methylpropionate, etc .; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone,
Cyclohexanone, 2-heptanone, 3-heptanone,
Etc .; Aromatic hydrocarbons such as toluene, xylesi,
Etc. are preferred.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter 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.

In the dye-containing negative curable composition of the present invention, if necessary, various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, and ultraviolet rays are used. Absorbers, anti-aggregation agents, etc. may be added.

Specific examples of the above 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; nonion. -Based, cationic, 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) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 Adhesion promoters such as -chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6- Antioxidants such as di-t-butylphenol; 2- (3-t-butyl-
Examples thereof include UV absorbers such as 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

Further, in order to promote the alkali solubility of the unirradiated area and further improve the developability of the dye-containing negative curable composition of the present invention, 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, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, aliphatic monocarboxylic acids such as 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 camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid
Other carboxylic acids such as hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid are included.

In the method for producing a color filter of the present invention, the dye-containing negative curable composition described above is applied onto a support by a coating method such as spin coating, cast coating or roll coating, and the resulting radiation-sensitive composition. A negative composition colored pattern is formed by forming a positive composition layer, exposing the layer through a predetermined mask pattern, and developing with a developing solution (image forming step). Further, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure may be included. In the production of the color filter, the image forming step (and the step of curing if necessary) is repeated for a desired number of hues to produce a color filter having a desired hue. Ultraviolet rays such as g-rays, h-rays and i-rays are preferably used as the radiation used in this case.

Examples of the support include soda glass, Pyrex (R) glass, quartz glass used in liquid crystal display elements and the like, those obtained by attaching a transparent conductive film thereto, and photoelectric conversion used in image pickup elements and the like. Element substrates such as silicon substrates and complementary metal oxide semiconductors (CM
OS) and the like. These substrates may be formed with black stripes that separate each pixel.
If necessary, an undercoat layer may be provided on these supports for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the substrate surface.

As the developer, any developer can be used as long as it has a composition that dissolves the unirradiated portion of the dye-containing negative curable composition of the present invention, but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when the negative dye-containing curable composition of the present invention is prepared.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide and tetraethyl. Ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.
[0] -7-undecene and other alkaline compounds are preferably dissolved in the solution to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. When a developer made of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0076]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, "part" is based on mass unless otherwise specified. In this example, the organic solvent-soluble dye is simply referred to as "dye".

[0077] (Example 1) 1) Preparation of resist solution   ・ Propylene glycol monomethyl ether acetate ... 19.20 parts     (PGMEA)   ・ Ethyl lactate ... 36.67 parts   ・ Benzyl methacrylate / methacrylic acid copolymer ... 30.51 parts     (Molar ratio: 75/25) 36% PGMEA solution   ・ Dipentaerythritol hexaacrylate ... 12.20 parts   ・ Polymerization inhibitor (p-methoxyphenol) ... 0.0061 parts   ・ Fluorosurfactant ... 0.83 parts   Photoinitiator TAZ-107 (Midori Kagaku Co., Ltd.) ... 0.586 parts Were mixed and dissolved to prepare a resist solution.

2) Preparation of Glass Substrate with Undercoat Layer A glass substrate (Corning 1737) was ultrasonically washed with 1% NaOH water, washed with water and dehydrated and baked (200 ° C./30).
Minutes). Then, the resist solution of the above 1) is applied onto a glass substrate after washing so as to have a film thickness of 2 μm by using a spin coater, and dried by heating at 220 ° C. for 1 hour,
A cured film (undercoat layer) was formed. 3) Preparation of dye resist solution 9.9 parts of the resist solution obtained in 1) above and 0.1 part of yellow dye Valifast Yellow 1108 (manufactured by Nippon Kayaku Co., Ltd.) were mixed and dissolved to obtain a dye resist solution (dye). To obtain a negative curable composition).

4) Exposure / Development of Dye Resist (Image Forming Step) The dye resist solution obtained in 3) above is applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in 2) to give a film thickness of 2
Apply using a spin coater so that
Prebaked at 0 ° C. for 120 seconds. Then, using an exposure device, the coating film was irradiated with light having a wavelength of 365 nm through a 20 μm mask at each exposure dose of 25, 50, and 100 mJ / cm ² . After irradiation, using a 12.5% CD-2000 (manufactured by FUJIFILM Arch Co.) developer, at 2 ° C. for 2 hours.
Development was performed for each time of 0, 40 and 60 seconds. Then, after rinsed with running water for 20 seconds, it was spray-dried to obtain a yellow pattern image.

For the pattern image, an optical microscope and S
It was confirmed by an ordinary method by EM photograph observation. In addition, the chromaticity, transmission spectrum, and absorbance of the image can be measured by the colorimeter MCP.
It was measured with D-1000 (manufactured by Otsuka Electronics Co., Ltd.). Further, the yellow dye used in the dye resist solution of 3) above was replaced with a different color dye, a second color was applied, and dye elution and color mixing during the application were evaluated by the change in absorbance before and after image formation of the second color.

The dye fixation ratio of the yellow pattern image (effect of suppressing dye elution) was evaluated by the change in absorbance before and after immersion of the coating film in acetone for 5 minutes. In addition, the residual rate of the double bond of the monomer (1430-1380 cm ^-1
(Peak area ratio) of the dye resist solution is applied on a glass substrate and dried to form a coating film having a film thickness of 2 μm.
After exposure with each energy of 00 mJ / cm ² , it was measured with a Fourier transform infrared spectrophotometer (manufactured by Horiba Ltd.). The results measured and evaluated as described above are shown in Table 1 below.

(Examples 2 to 9) 3) In Example 1, the preparation of the dye resist solution was performed in the same manner as in Example 1 except that the composition was changed as shown in Table 1 below. still,
As the cross-linking agent in Examples 8 and 9, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol was used, and post development was carried out at 230 ° C. It was baked (curing step). Then, the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1 below together with Example 1.

[0083]

[Table 1]

As is clear from the results shown in Table 1 above, the absorbance of the dye at the wavelength of the irradiation light used in the examples is represented by A
d, the ratio Ad / A when the absorbance of the photopolymerization initiator is Ai
By adopting a dye / photopolymerization initiator combination in which i is 10.0 or less, the dye elution and the dye fixing rate at the time of second color application can be significantly improved without containing a post-crosslinking agent. I was able to. It is shown that there is a significant improvement effect on the polymerizability as compared with Comparative Example 1 described later.

In Examples 5 and 7, the dye fixation rate was slightly lower than that in the other Examples. this is,
Even when an organic solvent-soluble dye (dye according to the present invention) having an absorbance ratio with the photopolymerization initiator of 10.0 or less is used, if the concentration used is high, the optical filter effect essentially possessed by the dye is obtained. Shows that the irradiation light is absorbed, the generation of initiator radicals is suppressed, and the polymerization is suppressed. In this case, as shown in Examples 8 and 9,
As a supplementary measure, for example, a thermal cross-linking agent (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol adduct) is used in combination to further cure. It is also possible to improve the property easily.

(Examples 10 to 19) Pattern images were obtained by performing the same operations as in Examples 1 to 9 except that the glass substrate used in Examples 1 to 9 was replaced with a silicon wafer substrate. The same results as in Examples 1 to 9 were obtained for the image forming property and the dye elution resistance. Examples 10 to 19 are different from Examples 1 to 9 in that a silicon wafer substrate is used, but since the dye resist solution is applied on the undercoat layer through Examples 1 to 20, it is substantially The same performance was obtained without any difference.

Example 20 A pattern image was formed in the same manner as in Example 6 except that the amount of the photopolymerization initiator was changed to 3 times. As a result, the dye did not elute at the time of application of the second color, and the dye fixation ratio was 97%. Very excellent results were obtained without using the post-crosslinking agent. In addition, no difference in spectrum was observed between this example and the case where the photopolymerization initiator was used in an amount 3 times that of Example 6. Further, in this example, there was no spectrum change before and after post-baking. From the above results, if the amount of the photopolymerization initiator is increased as the absorbance of the film at the wavelength of the irradiation light is increased, the harmful effect due to yellow coloring is not involved,
It can be seen that good image formability is obtained. Further, good curability was obtained without using a post-crosslinking agent or a complicated post-crosslinking process as in the case of using a conventional dye, and a remarkable improvement effect was observed in practical use.

(Example 21) A pattern image was formed in the same manner as in Example 20, except that the dye was changed to Valifast Yellow 1151.
As a result, the dye did not elute at the time of application of the second color, and the dye fixation ratio of 97% was obtained.
Very good results have been obtained.

Example 22 A pattern image was formed in the same manner as in Example 20, except that the dye was changed to Valifast red 3304. As a result, the dye did not elute at the time of application of the second color, and the dye fixation ratio of 98% was obtained. Very good results were obtained without using the post-crosslinking agent.

(Example 23) A pattern image was formed in the same manner as in Example 20, except that the dye was changed to Valifast blue 2620. As a result, the dye did not elute at the time of application of the second color, and the dye fixation ratio was 97%. Very excellent results were obtained without using the post-crosslinking agent.

Example 24 In Example 3, the photopolymerization initiator was replaced with 2- (O-benzoyloxime) -1- [4
A pattern image was formed in the same manner as in Example 3 except that-(phenylthio) phenyl] -1,2-octanedione was used instead. As a result, the same results as in Example 3 were obtained,
It has been found that very good results are obtained without the use of post-crosslinking agents.

Example 25 A pattern image was formed in the same manner as in Example 3 except that 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone was used as the photopolymerization initiator. As a result, the same results as in Example 3 were obtained, and it was found that extremely excellent results were obtained without using a post-crosslinking agent.

(Example 26) In Example 3, the binder was (benzyl methacrylate)-(methacrylic acid)-
A pattern image was formed in the same manner as in Example 3 except that (2-hydroxyethyl methacrylate) copolymer [molar ratio = 60: 17: 23] was used. As a result, the same results as in Example 3 were obtained, and it was found that extremely excellent results were obtained without using a post-crosslinking agent.

(Comparative Examples 1 and 2) 3) The pattern image was formed in the same manner as in Example 1 except that the composition was changed as shown in Table 1 in the preparation of the dye resist solution in Example 1. Further, the same measurement and evaluation as in Example 1 were performed, and the results are also shown in Table 1. As a result, in Comparative Example 1, although the dye did not elute, the degree of polymerization was relatively low and the dye fixation ratio was inferior. Further, in Comparative Example 2 in which the ratio Ad / Ai is 10.0 or more when the absorbance of the dye at the wavelength of the irradiation light is Ad and the absorbance of the photopolymerization initiator is Ai, the polymerization rate of the system is 0%, No cured image was obtained.

From the results shown in Table 1 above, the use of an organic solvent-soluble dye (dye according to the present invention) having an absorbance ratio with the photopolymerization initiator of 10.0 or less (at normal working concentrations ) Even without using a crosslinking agent, sufficient polymerizability and curability can be obtained with high sensitivity (high resolution), dye elution does not occur, and a dye-containing negative curable composition having a good dye fixation rate can be obtained. Further, it is clear that a remarkable improvement effect is exhibited in the simplification of the manufacturing process that a crosslinking agent is unnecessary. Therefore, the formed image has excellent light transmittance,
The heat / light deterioration can also be prevented.

[0096]

EFFECTS OF THE INVENTION According to the present invention, since high polymerizability is obtained, high sensitivity, high transmittance, wide development latitude, high resolution image can be obtained, and dye elution, color mixing, Dye-containing negative curable composition having high productivity without heat deterioration and photodegradation, and the dye-containing negative curable composition, having high transmittance, high resolution, wide development latitude, heat deterioration and It is possible to provide a color filter which is free from light deterioration and has high productivity. Further, according to the present invention,
It is possible to provide a method for producing a color filter which is highly sensitive and can be sufficiently cured, is simple and has high cost performance (provides productivity that can be produced with high efficiency), without being accompanied by elution of dye, heat deterioration and light deterioration. .

Claims (3)

[Claims] 1. A negative curable composition containing a dye, which contains an organic solvent-soluble dye and undergoes a radical polymerization reaction with a photopolymerization initiator, wherein the organic solvent-soluble dye is at a wavelength of irradiation light for initiating radical polymerization. The negative curable composition containing a dye, wherein the ratio Ad / Ai between the absorbance Ad of 1. and the absorbance Ai of the photopolymerization initiator is 10.0 or less. 2. A color filter comprising the negative curable composition containing a dye according to claim 1. 3. A color comprising a step of applying the negative curable composition containing a dye according to claim 1 on a support, exposing through a mask, and developing to form a negative pattern. Filter manufacturing method.