JP4401196B2 - Dye-containing curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device, a solid-state imaging device, and the like, a color filter using the dye-containing curable composition, and a production thereof Regarding the method.

  As a method for producing a color filter used for a liquid crystal display device, a solid-state imaging device or the like, a dyeing method, a printing method, an electrodeposition method, or a pigment dispersion method is 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. This method is stable to light and heat due to the use of pigments, and is patterned by a photolithographic method, so that sufficient positional accuracy can be secured and suitable for the production of color filters for large screens and high-definition color displays. It has been widely used as a new method.

  In order to produce a color filter by the pigment dispersion method, a radiation sensitive composition is applied on a substrate with a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development. Thus, a colored filter can be obtained by obtaining colored pixels and repeating this operation for the hue.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 7). However, in recent years, color filters for solid-state imaging devices have been demanded to have higher definition, and it is difficult to further improve the resolution with conventional pigment dispersion systems, and color unevenness due to coarse pigment particles is difficult. Due to problems such as occurrence, it is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

  In view of such a problem, a technique for using a dye instead of a pigment has been proposed. However, a composition containing a dye has a problem that light resistance is generally inferior to that of a pigment.

  Proposed methods for improving light resistance include adding alcohol-soluble Ni and Co metal compounds in glassy colored filters and adding metal complexes to triphenylmethane dyes in resin patterns. (For example, see Patent Documents 8 to 9). However, these are all related to a system that does not require alkali development. The light resistance of the dye tends to be slightly lower than that when these processes are not required by going through the process of exposure / alkaline development / post-heating, and an additive that can give excellent light resistance even after alkali development Technology was sought.

  Furthermore, unlike a semiconductor manufacturing application or the like, particularly in the case of a color filter manufacturing application for a solid-state imaging device, a thin film of 1.5 μm or less is required. Therefore, in order to obtain a sufficient color density, a large amount of dye must be added to the composition. With this, in both the negative type and the positive type, when the pattern is formed by alkali development, the development of the pattern portion is resistant to development. Insufficient properties have been obtained, and there has been a problem that the remaining film ratio is reduced by the development process.

JP-A-1-102469 JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 Japanese Patent No. 2986796 Japanese Patent Laid-Open No. 11-223720

This invention is made | formed in view of the above, and makes it a subject to achieve the following objective. That is, the present invention
The purpose is to provide a dye-containing curable composition having high light resistance even after alkali development and having a good residual film ratio after development,
An object of the present invention is to provide a color filter composed of the dye-containing curable composition, excellent in hue and resolving power, and having high light resistance.
An object of the present invention is to provide a method for producing a color filter using the dye-containing curable composition and capable of producing a color filter having good hue and resolving power and high light fastness by suppressing a decrease in the remaining film ratio due to alkali development. To do.

  Specific means for achieving the above-described problems are as follows. Based on the following means, a dye-containing curable composition particularly suitable for color filter production is provided to achieve the object of the present invention. Can do.

<1> (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) at least one of a photopolymerization initiator and a photoacid generator , (D) nickel (II) acetylacetonate, cobalt (II) acetyl Acetonate, cobalt (II) hexafluoroacetylacetonate hydrate, dichlorobis (triethylphosphine) palladium (II), dichlorotetrakis (triphenylphosphine) ruthenium (II), tris (triphenylphosphine) copper (I) chloride Bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, tetrakispyridine iron (II) bromide, tris (2,2'-bipyridyl) ruthenium (II) chloride hexahydrate, manganese tetrachloride Hydrates, di-n-butyldithiocarbamate copper (II), and di-n-butyldithiocarbamate Seen at least contains at least one nickel (II), a dye-containing curable composition characterized in that it is configured to negative.

< 2 > A color filter using the dye-containing curable composition according to <1 > .
< 3 > A method for producing a color filter, comprising: applying the dye-containing curable composition according to <1 > above onto a support, exposing through a mask, and developing to form a pattern image. It is.
In the method for producing a color filter, when producing a color filter having a desired hue, the above process is repeated for the desired number of hues. Moreover, the aspect which has the process of hardening | curing the said pattern image by heating and / or exposure as needed is also suitable.

  According to the present invention, a dye-containing curable composition having high light resistance even after alkali development and having a good residual film ratio after development can be provided. Moreover, it is comprised using the dye-containing curable composition of this invention, The color filter which is excellent in hue and resolving power, and has high light resistance can be provided. Furthermore, the dye-containing curable composition of the present invention is used, and the production of a color filter capable of producing a color filter with good hue and resolution and high light fastness while suppressing a decrease in the remaining film ratio due to alkali development. A method can be provided.

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

<< Dye-containing curable composition >>
The dye-containing curable composition of the present invention comprises (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) at least one of a photopolymerization initiator and a photoacid generator , and (D) nickel (II). Acetylacetonate, cobalt (II) acetylacetonate, cobalt (II) hexafluoroacetylacetonate hydrate, dichlorobis (triethylphosphine) palladium (II), dichlorotetrakis (triphenylphosphine) ruthenium (II), tris (tri Phenylphosphine) copper (I) chloride, bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, tetrakispyridine iron (II) bromide, tris (2,2′-bipyridyl) ruthenium (II) chloride Hexahydrate, manganese chloride tetrahydrate, di-n-butyldithiocarbamate copper (II), and It comprises at least one of di-n-butyldithiocarbamate nickel (II) and generally comprises an organic solvent . Also, it may also contain other components such as a monomer or a crosslinking agent.

~ (A) Alkali-soluble binder ~
The dye-containing curable composition of the present invention contains at least one alkali-soluble binder. The alkali-soluble binder according to the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like. Hereinafter, the alkali-soluble binder will be described.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. 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 also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol, etc. are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (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 examples of the hydrophilic monomer include tetrahydrofurfuryl group, phosphoric acid, phosphoric ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, and morpholinoethyl group. Useful.

  In addition, in the case of constituting a negative type, from the viewpoint of improving the crosslinking efficiency, it may have a polymerizable group in the side chain, and contains an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Also useful are polymers and the like. Hereinafter, examples of the polymer containing these polymerizable groups are shown, but the polymer is not limited thereto as long as it contains an alkali-soluble group such as a COOH group, an OH group, and an ammonium group and an unsaturated bond between carbon atoms.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.

  As the compound having reactivity with the OH group, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of compounds having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd.); Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Yu) CB Co., Ltd.).

  In the case of constituting a positive type, examples of the alkali-soluble binder include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde cocondensation resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, N In addition to-(4-hydroxyphenyl) methacrylamide copolymer, hydroquinone monomethacrylate copolymer, sulfonylimide polymer described in JP-A-7-28244, carboxyl group described in JP-A-7-36184 And containing polymers. In addition, an acrylic resin containing a phenolic hydroxyl group described in JP-A No. 51-34711, an acrylic resin having a sulfonamide group described in JP-A No. 2-866, a urethane resin, etc. Alkali-soluble polymer compounds can also be used. These alkali-soluble binders may be used singly or in combination of two or more.

In addition, a resin in which an alkali-soluble group is protected with an acid-decomposable group can be used in combination with a photoacid generator. This resin is a compound having a —C—O—C— or —C—O—Si— bond, and examples thereof include the following compounds.
(A) including those selected from the group consisting of at least one orthocarboxylic acid ester and carboxylic acid amide acetal, the compound of which can have polymerizability, the above group as a bridging element in the main chain or on the side A compound which can occur as a side substituent,
(B) an oligomeric compound or a polymer compound containing in the main chain a compound selected from the group of repeating acetals and ketals;
(C) a compound comprising at least one enol ester or N-acylamino carbonate group,
(D) β-ketoester or β-ketoamide cyclic acetal or ketal,

(E) a compound containing a silyl ether group,
(F) a compound containing a silyl enol ether group,
(G) a monoacetal or monoketal in which the aldehyde or ketone component has a solubility of 0.1 to 100 g / liter with respect to the developer;
(H) tertiary alcohol ethers, and
(I) Carboxylic acid esters and carbonates of tertiary allylic or benzylic alcohols.

The compounds (a) that can be cleaved by the above acids are described in German Patent Publication Nos. 2,610,842 and 2,928,636. Mixtures containing the compound (b) are described in German Patents 2,306,248 and 2,718,254. The compound (c) is described in European Patent Publication Nos. 0,006,626 and 0,006,627. The compound (d) is described in European Patent Publication No. 0,202,196, and the compound used as (e) is described in German Patent Publication Nos. 3,544,165 and 3,601. , 264. The compound (f) is described in German Patent Publication Nos. 3,730,785 and 3,730,783, and the compound (g) is described in German Patent Publication No. 3,730,783. In the issue. The compound (h) is described in, for example, US Pat. No. 4,603,101, and the compound (i) is described in, for example, US Pat. No. 4,491,628 and JM Frechet et al. ImagingSci. 30, 59-64 (1986)).
The content of the compound protected with these acid-decomposable groups in the dye-containing curable composition is usually 1 to 60% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition. %.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, acrylic resins, polyhydroxystyrene resins More preferred are resins and polysiloxane resins. Further, from the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

  In particular, acrylic resins (binders that may contain a polymerizable group) are preferred. Examples of the acrylic resins include benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like Copolymers comprising monomers selected from: Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation), and Dial NR series (Mitsubishi Rayon) Manufactured by Co., Ltd.), Biscoat R264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) 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 , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.
Moreover, as content in the dye-containing curable composition of an alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% Is particularly preferred.

~ (B) Organic solvent soluble dye ~
The dye-containing curable composition of the present invention contains at least one organic solvent-soluble dye (hereinafter also simply referred to as a dye). The organic solvent-soluble dye is not particularly limited, and conventionally known dyes for color filters can be used.

  For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 The dyes described in JP-A-6-194828 can be used. As the chemical structure, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes and anthrapyridone dyes.

  When the resist system is subjected to water or alkali development, at least one of acid dyes and derivatives thereof may be preferably used in that the binder and / or dye are completely removed by development. In addition, it is also useful to select and use at least one selected from direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof. is there.

  Hereinafter, the acid dye and its derivative will be described. The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer used for the preparation of a composition or a development process, It is selected in consideration of all required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 108,112,113,120,129,138,147,150,158,171,182,192,210,242,243,249,256,259,267,278,280,285,290,296,315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;

acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;
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, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

acid violet 6B, 7, 9, 17, 19, 49;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3, Solvent Yellow 14, 82, 94, 162; Solvent Orange 2, 7, 11, 15, 26, 56; Solvent Blue 25, 35, 37, 38, 55, 59, 67; Solvent Red 49;
And derivatives of these dyes.

Among these, acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25 ;, and the like, and derivatives of these dyes are preferred.

  Further, azo, xanthene and phthalocyanine acid dyes other than those mentioned above are also preferred. 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] And the like and derivatives of these dyes are also preferred.

When the acid dye is contained as a component of the composition, it may be better to use it as a derivative of the acid dye because the acid dye may not be sufficiently soluble in the organic solvent used for the preparation.
As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like can be used. Although it will not specifically limit if it can melt | dissolve in the solution of the dye containing curable composition to be prepared, the solubility with respect to the developing solution used at the time of an organic solvent or image development processing, light absorbency, other in dye containing curable composition It is selected in consideration of all necessary performance such as interaction with components, light resistance, heat resistance and the like.

  The salt of said acidic dye and a nitrogen-containing compound is demonstrated. The method of forming a salt with an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

A nitrogen-containing compound that forms a salt with an acid dye and a nitrogen-containing compound that forms an amide bond with an acid dye to obtain a sulfonamide of the acid dye will be described.
The nitrogen-containing compound is a salt or amide compound that is soluble in an organic solvent or developer used during preparation or development processing, salt-forming properties, dye absorbance / color value, and other components in the dye-containing curable composition. Is selected in consideration of all of the interaction with the colorant, heat resistance as a colorant, light resistance, and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, particularly preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

  Hereinafter, specific examples of the nitrogen-containing compound will be given. However, the present invention is not limited to these. In the following compounds, those having no “—NH— group” are not nitrogen-containing compounds forming an amide bond.

  The molar ratio of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound (hereinafter referred to as “n”) will be described. The molar ratio n is a value that determines the molar ratio between the acidic dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, n is a numerical value satisfying 0 <n ≦ 10 among the number of functional groups of acid in acid dyes in practical use, solubility in organic solvents and developers, salt formation, absorbance, dye content It can be selected in consideration of all necessary performances such as interaction with other components in the curable composition, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a numerical value satisfying 0 <n ≦ 4.5, more preferably a numerical value satisfying 0 <n ≦ 4, and particularly preferably a numerical value satisfying 0 <n ≦ 3.5. .

  The content concentration of the organic solvent-soluble dye will be described. The concentration of the organic solvent-soluble dye in the total solid component of the dye-containing curable composition 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 0 0.5 to 50% by mass is particularly preferable.

~ (C) Radiation sensitive compound ~
The dye-containing curable composition of the present invention contains at least one radiation-sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as radical generation, acid generation, base generation, etc., against radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film is alkali-developed by insolubilizing the above-mentioned alkali-soluble binder by a reaction such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, etc. It is used for the purpose of making it insoluble in liquid.

Dye-containing curable composition of the present invention is configured to negative, a photopolymerization initiator and / or photoacid generator. When applied to the positive type, it preferably contains an o-quinonediazide compound or a photoacid generator.

  The photopolymerization initiator used in the case of forming the negative type will be described. The photopolymerization initiator is not particularly limited as long as it can cause a monomer having a polymerizable group to undergo a polymerization reaction, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like. In addition, you may further contain in the positive type | system | group containing said o-quinonediazide compound, In this case, the hardening degree of the pattern formed can be promoted more.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from 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 which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 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.

  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.

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

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

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

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

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B, etc.), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819) manufactured by Ciba Geigy , Irgacure 261, etc.), 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- Morpholinobyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4 , 5-Diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer , 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, etc. are also useful.

  These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer. Specific examples thereof include benzoin, benzoin methyl ether, 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, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p -Methyl styryl ketone, benzophenone, p- ( Methylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, and benzanthrone, etc., benzothiazole compounds described in JP-B-51-48516, etc., Tinuvin 1130, the 400, and the like.

  Other well-known photoinitiators other than the said photoinitiator can be used together with the dye-containing curable composition of this invention. Specifically, the vicinal polyketol aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in U.S. Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned. The

  The content of the photopolymerization initiator in the dye-containing curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and more preferably 1 to 20% with respect to the solid content (mass) of the monomer. Mass% is particularly preferred.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  Next, an o-quinonediazide compound suitable for a positive structure will be described. An o-quinonediazide compound is a compound having at least one o-quinonediazide group. For example, esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with phenol-formaldehyde resin or cresol-formaldehyde resin; 1,2-naphthoquinone described in US Pat. No. 3,635,709 Ester of 2-diazido-5-sulfonyl chloride and pyrogallol acetone resin; 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-benzaldehyde resin described in JP-B-63-13528 An ester with;

An ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-pyrogallol / acetone co-condensation resin described in JP-B-62-44,257; A polyester having 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride esterified to a polyester having a hydroxyl group at its terminal; N- (4- Hydroxyphenyl) methacrylamide homopolymer or copolymer with other copolymerizable monomers esterified with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride; Japanese Patent Publication No. Sho 54-29,922 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and bisphenol 1,2-naphthoquinone-2-ester with a homopolymer of p-hydroxystyrene or another copolymerizable monomer described in JP-B-52-36,043 An esterified diazide-5-sulfonyl chloride; an ester of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride and polyhydroxybenzophenone, and the like.

  Other known o-quinonediazide compounds that can be used in the present invention include JP-A-63-80,254, JP-A-58-5,737, JP-A-57-111,530, JP-A-57. -111,531, JP-A-57-114,138, JP-A-57-142,635, JP-A-51-36,129, JP-B-62-3,411, JP-B-62-51 No. 459, Japanese Patent Publication No. 51-483, and the like.

  The content of the o-quinonediazide compound in the dye-containing curable composition is usually 5 to 60% by mass, preferably 10 to 40% by mass, based on the total solid content (mass) of the composition. .

  Next, the photoacid generator will be described. Known photoacid generators can be used. For example, diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal etal, Polymer, 21, 423 (1980), U.S. Pat. 3-140140 ammonium salt, DCNecker etal, Macromolecules, 17, 2468 (1984), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo, Oct (1988), USA Phosphonium salts described in Patent Nos. 4,069,055 and 4,069,056, etc., JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-965514, etc., JV Crivello etal, Polymer J. 17, 73 (1985), JV Crivello etal. J. Org. Chem., 43, 3055 (1978), WR Wattetal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivelloetal, Polymer Bull., 14, 279 (1985) ), JV Crivello etal, Macromorecules, 14 (5), 1141 (1981), JV Cr ivello etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent 370,693, US Patent 3,902,114, European Patents 233,567, 297,443, 297,442, US Patent 4,933,377, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Korean Patents 2,904,626, 3,604,580, 3,604,581, etc.,

Selenium salts described in JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), JV Crivelloetal, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281 JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63 -70243, JP-A 63-298339, etc., organic halogen compounds, K. Meier etal, J. Rad. Curing, 13 (4), 26 (1986), TP Gill etal, Inorg. Chem., 19 , 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), JP-A-2-16145, and the like,

S. Hayase etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis etal, J. PholymerSci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron Lett., (24), 2205 (1973), DHR Barton etal, J. Chem Soc., 3571 (1965), PM Collins etal, J. Chem. SoC., Perkin I, 1695 (1975), M. Rudinstein etal, Tetrahedron Lett., (17), 1445 (1975), JW Walker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusman etal, J. Imaging Technol., 11 (4), 191 (1985), HMHoulihan etal, Macormolecules, 21, 2001 (1988), PMCollinsetal, J. Chem. Soc., Chem. Commun., 532 ( 1972), S. Hayasetal, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21, 2001 ( 1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53- O-Nitrobenzyl described in No. 133022, etc. A photoacid generator having a type protecting group,

M. TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner etal, J. Rad. Curing, 13 (4), WJ Mijs etal, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, U.S. Patent Nos. 4,618,564, 4,371,605 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-140109, etc., and compounds that generate sulfonic acid by photolysis, such as iminosulfonate And disulfone compounds described in JP-A-61-166544.

  The content in the dye-containing curable composition of the photoacid generator that decomposes upon irradiation with actinic rays or radiation is usually based on the total mass of the composition (excluding the coating solvent). It is 0.001-40 mass%, Preferably it is 0.01-20 mass%, More preferably, it is 0.1-5 mass%.

~ (D) Transition metal complex ~
The dye-containing curable composition of the present invention contains at least one transition metal complex having a maximum molar extinction coefficient ε in the visible light region smaller than that of the organic solvent-soluble dye. This transition metal complex is one in which a negative, neutral or positive monodentate ligand or polydentate ligand is coordinated around a transition metal atom or a transition metal ion. In addition to effectively improving the light resistance of a color filter formed using the above, it is possible to effectively improve the residual film ratio after development.

  The transition metal complex in the present invention preferably has a molar extinction coefficient ε in the visible light region (380 to 780 nm) of 0 or more and 8000 or less in terms of color sharpness. Further, as the transition metal complex, more preferably, the maximum value of the molar extinction coefficient ε in the wavelength range is from 0 to 6000, and even more preferably from 0 to 3000.

  Transition metal atoms and transition metal ions constituting transition metal complexes include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhe Um (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and the like.

  Preferred examples of the transition metal complex include those in which the transition metal belongs to the first series (that is, the fourth period), that is, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn). , Iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu).

More preferable examples of the transition metal complex include those in which the transition metal belongs to the fourth period and a divalent transition metal ion, that is, Ti ²⁺ , V ²⁺ , Cr ²⁺ , Mn ²⁺ , Fe ²⁺ , Examples thereof include those composed of Co ²⁺ , Ni ²⁺ and Cu ²⁺ .
Particularly preferable examples of the transition metal complex include Co ²⁺ and Ni ²⁺ , and the most preferable example includes Co ²⁺ .

  As the ligand of the transition metal complex, the ligand alone preferably has a maximum molar extinction coefficient ε in the visible light region of 0 or more and 3000 or less, and more preferably has a maximum value of ε of 0 or more and 2000 or less. It is particularly preferable that the maximum value of ε is 0 or more and 1000 or less.

  The molecular weight of one ligand in the transition metal complex is preferably 20 or more and less than 300.

As the ligand in the transition metal complex, all general ligands can be used, and any of monodentate ligands and polydentate ligands can be suitably used.
Specific examples of the ligand include fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxo, peroxo, carbonyl, carbonate, oxalato, acetato, ethanolato, 1-butanethiolato Thiophenolato, 2,2′-thiobis (4-t-octyl) phenolate, acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate, trifluoroacetylacetonate, hexafluoroacetylacetate Nato, ethyl acetoacetonate, thiocyanato, isothiocyanato, diethyl dithiocarbamate, di-n-butyldithiocarbamate, cyano, amine, dimethylamine, diethylamine, tetraethylammonium Piperidine, N-methylaniline, pyridine, 2-phenylpyridine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2′-bipyridine, 1,10-phenanthroline , Ethylenediaminetetraacetato, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro, nitrito, phosphato, diisopropyldithiophosphate, diethyldithiophosphate, triethylphosphine, tributylphosphine, Tricyclohexylphosphine, dimethylphenylphosphine, triphenylphosphine, diphenylphosphine, tricyclohexylphosphine, cyclopentadiene, pentamethylcyclopentadiene, cyclo Punctuation, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, benzene, naphthalene, allyl and the like.

  Preferred examples of the ligand include those that do not contain an aromatic ring in the ligand. Specifically, fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, Oxo, peroxo, carbonyl, carbonato, oxalato, acetate, ethanolate, 1-butanethiolato, acetylacetonato, 2,2,6,6-tetramethyl-3,5-heptanedionate, trifluoroacetylacetonato, hexafluoroacetylacetonato , Ethyl acetoacetonate, thiocyanate, isothiocyanate, diethyl dithiocarbamate, di-n-butyldithiocarbamate, cyano, amine, dimethylamine, diethylamine, tetraethylammonium, ethylenediamine, , N, N ′, N′-tetramethylethylenediamine, 1,2-diaminocyclohexane, ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro , Nitrito, phosphato, diisopropyldithiophosphate, diethyldithiophosphate, triethylphosphine, tributylphosphine, tricyclohexylphosphine, cyclooctene, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, And allyl.

  More preferable examples of the ligand include acetate, acetylacetonate, hexafluoroacetylacetonate, thiocyanate, diethyldithiocarbamate, and di-n-butyldithiocarbamate.

  The content of the transition metal complex in the dye-containing curable composition is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the organic solvent-soluble dye. Preferably it is 0.5-15 mass%.

Hereinafter, although the specific example of the transition metal complex which concerns on this invention is given, in this invention, it is not limited to these. For example,
α-methylferrocenemethanol, titanium chloride (III) tetrahydrofuran complex, titanium chloride (IV) tetrahydrofuran complex, zirconium chloride (IV) tetrahydrofuran complex, hafnium chloride tetrahydrofuran complex, vanadium chloride (III) tetrahydrofuran complex, 1-butanethiol copper (I ) Salt, tetra (dimethylamino) titanium, tetra (diethylamino) titanium, thiophenol copper (I) salt, μ-dichlorotetraethylenedirhodium, trichloro (ethylene) platinum (II) potassium salt monohydrate, allyl palladium Chloride dimer, chloro (1,5-hexadiene) rhodium (I) dimer, chlorobis (cyclooctene) rhodium (I) dimer, chlorobis (cyclooctene) iridium (I) dimer, (1, 5-cyclooctadiene) Dimethylplatinum (II), dichloro (1,5-cyclooctadiene) ruthenium (II) polymer, dichloro (1,5-cyclooctadiene) palladium (II), dichloro (1,5-cyclooctadiene) platinum (II ), Dibromo (1,5-cyclooctadiene) platinum (II), (1,5-cyclooctadiene) diiodoplatinum (II), bis (1,5-cyclooctadiene) rhodium (I) tetrafluoroboron, Bis (1,5-cyclooctadiene) nickel (0), chloro (1,5-cyclooctadiene) rhodium (I) dimer, chloro (1,5-cyclooctadiene) iridium (I) dimer ,

(Bicyclo [2.2.1] hepta-2,5-diene) dichlororuthenium (II) polymer, bis (bicyclo [2.2.1] hepta-2,5-diene) rhodium (I) perchlorate, ( Bicyclo [2.2.1] hepta-2,5-diene) chlororhodium (I) dimer, (bicyclo [2.2.1] hepta-2,5-diene) dichloropalladium (II), titanium ( III) Chloride ethylene glycol dimethyl ether complex, niobium (III) chloride ethylene glycol dimethyl ether complex, niobium (III) bromide ethylene glycol dimethyl ether complex, nickel (II) bromide ethylene glycol dimethyl ether complex, niobium (IV) chloride tetrahydrofuran complex, chromium (III) chloride tetrahydrofuran complex, copper (I) bromide dimethyl sulfide complex, cis-bis (Diethyl sulfide) platinum (II) chloride, (dimethyl sulfide) gold (I) chloride, tris (ethylenediamine) cobalt (III) chloride dihydrate, tris (ethylenediamine) rhodium (III) chloride trihydrate Dichloro (ethylenediamine) palladium (II), dichloro (ethylenediamine) platinum (II), dichlorobis (ethylenediamine) palladium (II), dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium (II), Bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, (1,2-diaminocyclohexane) platinum (II) chloride, titanium (IV) (triethanolaminate) isopropoxide, bis (tetraethyl) Ammonium) tetrabromocopper (II), bis (tetraethylammonium) te Love Romo manganese (II), bis (tetraethylammonium) tetrabromocobalt (II),

Tetraphenylphosphonium acetate dichlorodioxol ruthenium (IV), copper (II) acetylacetonate, lanthanum acetylacetonate hydrate, cerium (III) acetylacetonate hydrate, europium (III) acetylacetonate hydrate, Gadolinium (III) acetylacetonate hydrate, yttrium acetylacetonate hydrate, titanium oxide (IV) acetylacetonate, zirconium (IV) acetylacetonate, vanadium (III) acetylacetonate, vanadyl acetylacetonate, chromium (III) acetylacetonate, bis (acetylacetonate) molybdenum dioxide (IV), manganese (II) acetylacetonate, manganese (III) acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetate , Cobalt (III) acetylacetonate, nickel (II) acetylacetonate, ruthenium (III) acetylacetonate, rhodium (III) acetylacetonate, palladium (II) acetylacetonate, iridium (III) acetylacetonate, Platinum (II) acetylacetonate, (1,5-cyclooctadiene) (2,4-pentanedionato) rhodium (I), (bicyclo [2.2.1] hepta-2,5-diene) (2 , 4-pentanedionato) rhodium (I), titanium diisopropoxide bis (2,4-pentanedionato),

Copper bis (2,2,6,6-tetramethyl-3,5-heptanedionate), yttrium tris (2,2,6,6-tetramethyl-3,5-heptanedionate), neodymium tris (2,2,6 , 6-tetramethyl-3,5-heptanedionato), erbium tris (2,2,6,6-tetramethyl-3,5-heptaneedionato), samarium tris (2,2,6,6-tetramethyl-3, 5-heptanedionate), thulium tris (2,2,6,6-tetramethyl-3,5-heptanedionate), nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptanedionate), Lanthanum tris (2,2,6,6-tetramethyl-3,5-heptanedionate), praseodymium tris (2,2,6,6-tetramethyl-3,5-heptanedio) G), europium tris (2,2,6,6-tetramethyl-3,5-heptanedionato), gadolinium tris (2,2,6,6-tetramethyl-3,5-heptaneedionato), dysprosium tris (2, 2,6,6-tetramethyl-3,5-heptanedionato), holmium tris (2,2,6,6-tetramethyl-3,5-heptaneedionato), ytterbium tris (2,2,6,6-tetramethyl) -3,5-heptanedionate), thallium (I) trifluoroacetylacetonate, copper (II) trifluoroacetylacetonate, zirconium (IV) trifluoroacetylacetonate, thallium (I) hexafluoroacetylacetonate, copper ( II) Hexafluoroacetylacetonate hydrate, yttrium hexafluoroa Cetylacetonate dihydrate, manganese (II) hexafluoroacetylacetonate trihydrate, cobalt (II) hexafluoroacetylacetonate hydrate, nickel (II) hexafluoroacetylacetonate hydrate, palladium ( II) hexafluoroacetylacetonate, (acetylacetonate) (1,5-cyclooctadiene) iridium (I),

Praseodymium tris [3- (trifluoro-methylhydroxymethylene)-(+)-camphorate], europium tris [3- (trifluoro-methylhydroxymethylene)-(+)-camphorate], erbium tris [3- (trifluoro -Methylhydroxymethylene)-(+)-camphorate], ytterbium tris [3- (trifluoro-methylhydroxymethylene)-(+)-camphorate], bis [3- (heptafluoropropylhydroxymethylene)-(+)- Camphorate] oxovanadium, praseodymium tris [3- (heptafluoropropylhydroxymethylene)-(+)-camphorate], praseodymium tris [3- (heptafluoropropylhydroxymethylene)-(−)-camphorate], europium tris [ -(Heptafluoropropylhydroxymethylene)-(+)-camphorate], europium tris [3- (heptafluoropropylhydroxymethylene)-(-)-camphorate], erbium tris [3- (heptafluoropropylhydroxymethylene)-( +)-Camphorate], erbium tris [3- (heptafluoropropylhydroxymethylene)-(−)-camphorate], ytterbium tris [3- (heptafluoropropylhydroxymethylene)-(+)-camphorate], ytterbium tris [3 -(Heptafluoropropylhydroxymethylene)-(-)-camphorate],

Diamine (1,1-cyclobutanedicarboxylate) platinum (II), titanium (IV) bis (ammonium lactate) dihydroxide, titanium (IV) bis (ethylacetoacetate) diisopropoxide, [1,2,3 4-tetrakis (methoxycarbonyl) -1,3-butadiene-1,4-diyl] platinum, bis (acetonitrile) dichloropalladium (II), bis (acetonitrile) chloronitropalladium (II), bis (acetonitrile) molybdenum (IV ) Chloride, tetrakis (acetonitrile) palladium (II) tetrafluoroborate, cis-bis (acetonitrile) dichloroplatinum (II), tetrakis (acetonitrile) copper (I) hexafluorophosphate, tetraethylammonium bis (acetonitrile) tetrachlororutheni (III), bis (diethyldithiocarbamate) dioxomolybdenum (VI), dichlorobis (triethylphosphine) palladium (II), cis-dichlorobis (triethylphosphine) platinum (II), trans-dichlorobis (triethylphosphine) platinum (II) ), Dichlorobis (tributylphosphine) nickel (II), dibromobis (tributylphosphine) nickel (II), oxalatebis (triethylphosphine) platinum (II) hydrate, dichlorobis (tricyclohexylphosphine) palladium (II), iodo ( Trimethyl phosphite) copper (I), iodo (triethyl phosphite) copper (I),

Chloro (pyridine) bis (dimethylglyoximate) cobalt (III), benzeneruthenium (II) chloride dimer, dichloro (p-cymene) ruthenium (II) dimer, (+)-di-μ-chlorobis {2- [1- (dimethylamino) ethyl] phenyl-C, N, -dipalladium, di-μ-chlorobis {2- [1- (dimethylamino) ethyl] phenyl-C, N-dipalladium, di- μ-chlorobis {2- [dimethylamino] methyl} phenyl-C, N-dipalladium, bis (salicylaldehyde) cobalt (II) dihydrate, tris (dibenzylideneacetone) dipalladium (0), tris (di Benzoylmethanate) iron (III), bis (benzonitrile) dichloropalladium (II), cis-bis (benzonitrile) dichloroplatinum (II), trichlorotris (dimethyl) Tilphenylphosphine) rhenium (III), [tris (dimethylphenylphosphine)] (2,5-norbornadiene) rhodium (I) hexafluorophosphate, tetrakis (methyldiphenylphosphine) palladium (0), (1,5-cycloocta Diene) bis (methyldiphenylphosphine) iridium (I) hexafluorophosphate, tris (triphenylphosphine) copper (I) chloride, bis (triphenylphosphine) copper (I) nitrate, chloro (triphenylphosphine) gold ( I), trichlorooxobis (triphenylphosphine) rhenium (V), iododioxobis (triphenylphosphine) rhenium (V),

Dichlorobis (triphenylphosphine) cobalt (II), chlorotris (triphenylphosphine) cobalt (I), tetrakis (triphenylphosphine) nickel (0), dichlorobis (triphenylphosphine) nickel (II), dibromobis (triphenylphosphine) Nickel (II), dichlorotris (triphenylphosphine) ruthenium (II), dichlorotetrakis (triphenylphosphine) ruthenium (II), trans-dibromobis (triphenylphosphine) palladium (II), chlorotris (triphenylphosphine) rhodium ( I), bromotris (triphenylphosphine) rhodium (I), nitrosyltris (triphenylphosphine) rhodium (I), dichlorobis (triphenylphosphine) palladium (I I), tetrakis (triphenylphosphine) palladium (0), tetrakis (triphenylphosphine) platinum (0), cis-dichlorobis (triphenylphosphine) platinum (II), trans-dichlorobis (triphenylphosphine) platinum (II) , Dioxobis (triphenylphosphine) platinum (IV), ethylenebis (triphenylphosphine) platinum (0), (bicyclo [2.2.1] hepta-2,5-diene) [bis (triphenylphosphine)] rhodium (I) hexafluorophosphate, bis (acetate) bis (triphenylphosphine) palladium (II), trans-benzyl (chloro) bis (triphenylphosphine) palladium (II), dichlorobis [methylenebis (diphenylphosphine)] dipalladium,

[1,2-bis (triphenylphosphino) ethane] iron (II) chloride, [1,2-bis (diphenylphosphino) ethane] cobalt (II) chloride, [1,2-bis (diphenylphosphine) Fino) ethane] nickel (II) chloride, [1,2-bis (diphenylphosphino) ethane] palladium (II) chloride, bis [1,2-bis (diphenylphosphino) ethanepalladium (0), [ 1,1,1-tris (diphenylphosphinomethyl) ethane] rhodium (I) chloride, (N-3-allyl) [(2S, 3S)-(+)-bis (diphenylphosphino) butane] palladium ( II) perchlorate, (bicyclo [2.2.1] hepta-2,5-diene) [(2S, 3S)-(+)-bis (diphenylphosphino) butane] rhodium (I) perchlorate, [1 , 3-bis (dipheny Phosphino) propane] dichloronickel (II), [(R)-(+)-2,2′-bis (diphenylphosphino) 1,1′-binaphthyl] chloro (p-cumene) ruthenium chloride, [(S )-(−)-2,2′-bis (diphenylphosphino) 1,1′-binaphthyl] chloro (p-cumene) ruthenium chloride, bis [(R)-(−)-2,2′-bis (Diphenylphosphino) 1,1′-binaphthyl] rhodium (I) perchlorate, [(R)-(+)-2,2′-bis (diphenylphosphino) 1,1′-binaphthyl] (1,5 -Cyclooctadiene) rhodium (I) perchlorate, [(S)-(-)-2,2'-bis (diphenylphosphino) 1,1'-binaphthyl] (1,5-cyclooctadiene) rhodium ( I) Perchlorate, [(R)-(+) 2,2'-bis (diphenylphosphino) 1,1'-binaphthyl] palladium (II) chloride, tetrakis (triphenyl phosphite) nickel (0),

Tris [N- (diphenylphosphinyl) -P, P-diphenylphosphinicamidate-O, O ′] praseodymium, bis (1,5-cyclooctadiene) bis (1H-pyrazolate) diiridium, tetrakis ( Pyridine) cobalt (II) bis (chromate), cis-dichlorobis (pyridine) platinum (II), (1,5-cyclooctadiene) (pyridine) (tricyclohexylphosphine) iridium (I) hexafluorophosphate, trichlorobis ( 2-phenylpyridine) rhodium (III) dimer, tris (2,2′-bipyridine) iron (II) hexafluorophosphate, cis-bis (2,2′-bipyridine) dichlororuthenium (II) hydrate, Tris (2,2′-bipyridyl) ruthenium (II) chloride hexahydrate, (2,2′-bipyridine) dic Ropalladium (II), (2,2′-bipyridine) dichloroplatinum (II), dichloro (2,2 ′, 6 ′, 2 ″ -terpyridine) platinum (II) dihydrate, dichloro (1,10 -Phenanthroline) copper (II), dibromo (1,10-phenanthroline) copper (II), dinitrate (1,10-phenanthroline) copper (II), tris (1,10-phenanthroline) iron (II) hexafluoro Phosphate, tris (1,10-phenanthroline) iron (III) hexafluorophosphate, tris (1,10-phenanthroline) ruthenium (II) chloride hydrate, dichloro (1,10-phenanthroline) palladium (II), dichloro (1,10-phenanthroline) platinum (II),

N, N′-bis (salicylidene) ethylenediaminocobalt (II), N, N′-bis (salicylidene) ethylenediaminonickel (II), bis (salicylideneiminate-3-propyl) methylaminocobalt (II), (R, R)-(−)-N, N′-bis (3,5-di-t-butylsalicylidene) -1,2-cyclohexanediaminomanganese (III) chloride, (S, S) — (+)-N, N′-bis (3,5-di-t-butylsalicylidene) -1,2-cyclohexanediaminomanganese (III) chloride, N, N′-bis (salicylidene) dianilinocobalt (II), N, N′-bis (salicylidene) -1,2-phenylenediaminocobalt (II) monohydrate, tris (cyclopentadienyl) scandium, bis (cyclopentadienyl) vanadium, Bis (cyclopentadienyl) chromium, ferrocene, ferrocenium hexafluorophosphate, ferrocenium hexafluoroborate, bis (cyclopentadienyl) cobalt, bis (cyclopentadienyl) nickel, bis (cyclopentadienyl) Ruthenium, cyclopentadienyl titanium trichloride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium pentasulfide, bis (cyclopentadienyl) titanium bis (trifluoromethanesulfonate), bis (cyclopenta Dienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) Na indium dichloride, bis (cyclopentadienyl) niobium dichloride, bis (cyclopentadienyl) molybdenum chloride,

Bis (pentamethylcyclopentadienyl) manganese, 1,1′-dimethylferrocene, bis (pentamethylcyclopentadienyl) iron, 1,2-diferroceneethane, butylferrocene, vinylferrocene, bis (2,4- Cyclopentadien-1-yl) [(4-methylbicyclo [2.2.1] heptane-2,3-diyl) methylene] titanium, ferrocenemethanol, 1,1′-ferrocenedimethanol, (dimethylaminomethyl) ferrocene (R)-(+)-N, N-dimethyl-1-ferrocenylethylamine, (S)-(−)-N, N-dimethyl-1-ferrocenylethylamine, ferrocenecarboxaldehyde, acetylferrocene, 1,1′-diacetylferrocene, ferrocenecarboxylic acid, 1,1′-ferrocenedicarboxylic acid, Dimethyl 1,1′-ferrocene dicarboxylate, 1,1 ″-[(4,4′-bipiperidine) -1,1′-diyldicarbonyl] bis [1 ′-(methoxycarbonyl) ferrocene], ferrocene acetonitrile Benzoylferrocene, 1,1′-bis (diphenylphosphino) ferrocene,

(-)-(R) -1-[(S) -2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, (+)-(S) -1-[(R) -2- (diphenylphosphino) Ferrocenyl] ethyl methyl ether, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II), (−)-(R) —N, N-dimethyl-1-[(S) -2- ( Diphenylphosphino) ferrocenyl] ethylamine, (+)-(S) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine, dichloro [(R) -N, N- Dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine] palladium, dichloro [(S) -N, N-dimethyl-1-[(R) -2- (diphenylphosphino) ferrocenyl] ethyl Amine] palladium, (−)-(R) —N, N-dimethyl-1-[(S) -1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine, (+)-(S) —N, N-dimethyl-1-[(R) -1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine, trans-4- [2- (1-ferrocenyl) -vinyl] -1-methylpyridinium iodide, chloro Cyclopentadienylbis (triphenylphosphine) ruthenium (II), (bicyclo [2.2.1] hepta-2,5-diene) [1,1′-bis (diphenylphosphino) ferrocene] ruthenium (I) Park Loreto,

Bis (pentamethylcyclopentadienyl) zirconium dichloride, pentamethylcyclopentadienylruthenium (III) chloride polymer, pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyliridium (III) chloride , Cyclohexadienyl iron (0) tricarbonyl tetrafluoroborate, cycloheptatriene chromium tricarbonyl, cycloheptatriene molybdenum tricarbonyl, cyclooctatetraene iron tricarbonyl, bicyclo [2.2.1] hepta-2, 5-dienemolybdenum tetracarbonyl, tricarbonyl (4-methoxy-1-methylcyclohexadiene) iron tetrafluoroborate, tricarbonyl (2-methoxycyclohexadiene) iron tetrafluoro Borate, tetramethylammonium (1-hydroxyethylidene) pentacarbonylchromium, cis-tetracarbonylbis (piperidine) molybdenum, (acetylacetonate) dicarbonylrhodium (I), (acetylacetonate) dicarbonyliridium (I), cyclo Pentadienylmolybdenum tricarbonyl dimer, cyclopentadienyl tungsten tricarbonyl dimer, cyclopentadienyl manganese tricarbonyl, cyclopentadienyl rhenium tricarbonyl, cyclopentadienyl iron dicarbonyl iodide, cyclopentadiene Enyl iron dicarbonyl dimer, cyclopentadienyl cobalt dicarbonyl, cyclopentadienyl nickel carbonyl dimer, methyl cyclopentadienyl molybdenum tricarbonyl Dimer, (methylcyclopentadienyl) -manganese tricarbonyl, dicarbonylcyclopentadienyl (dimethylsulfonium ethylide) iron tetrafluoroborate, benzene chromium tricarbonyl, mesitylene chromium tricarbonyl, mesitylene tungsten tricarbonyl, 1, 2,3,4-tetrahydronaphthalene chromium tricarbonyl, naphthalene chromium tricarbonyl, anisole chromium tricarbonyl, N-methylaniline chromium tricarbonyl, o-toluidine chromium tricarbonyl, (methylbenzoate) chromium tricarbonyl,

Di-n-butyldithiocarbamate nickel (II), n-butylamino [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), n-butylamino [2,2′-thiobis ( 4-t-octyl) phenolate] cobalt (II), bis [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), [2,2′-thiobis (4-t-octyl) ) Phenolate] nickel (II) hydrate, [2,2′-thiobis (4-t-octyl) phenolate] nickel (II) ethylamine, bis (butyl-3,5-di-t-butyl-4) -Hydroxobenzylphosphonate) Nickel (II), Nickel chloride hexahydrate, Cobalt chloride hexahydrate, Manganese chloride tetrahydrate, Di-n-butyldithiocarbamate cobalt (II), Di-n-butyldi Thiocarbamate copper (II), diisopropyldithiophosphate nickel (II), diethyldithiophosphate palladium, diethyldithiophosphate platinum, tetrakispyridine iron (II) chloride, tetrakispyridine iron (II) bromide, tetrakisisoquinoline iron (II) chloride , Tetrakisisoquinoline iron (II) bromide, tetrakisisoquinoline iron (II) iodide, tetrakispyridine iron (II) isocyanate, tetrakis β-picoline iron (II) bromide, tetrakis γ-picoline iron (II) bromide and the like.

Of these, the transition metal is particularly preferably belonging to the fourth period.
Specifically, α-methylferrocenemethanol, titanium chloride (III) tetrahydrofuran complex, titanium chloride (IV) tetrahydrofuran complex, vanadium chloride (III) tetrahydrofuran complex, 1-butanethiol copper (I) salt, tetra (dimethylamino) Titanium, tetra (diethylamino) titanium, thiophenol copper (I) salt, bis (1,5-cyclooctadiene) nickel (0), titanium (III) chloride ethylene glycol dimethyl ether complex, nickel (II) bromide ethylene glycol dimethyl ether Complex, chromium (III) chloride tetrahydrofuran complex, copper (I) bromide dimethyl sulfide complex, tris (ethylenediamine) cobalt (III) chloride dihydrate, bis (cis-1,2-diaminocyclohexane) nickel (II) Chloride, titanium IV) (triethanolaminato) isopropoxide, bis (tetraethylammonium) tetrabromo copper (II), bis (tetraethylammonium) tetrabromobisphenol manganese (II), bis (tetraethylammonium) tetrabromocobalt (II),

Copper (II) acetylacetonate, titanium oxide (IV) acetylacetonate, vanadium (III) acetylacetonate, vanadyl acetylacetonate, chromium (III) acetylacetonate, manganese (II) acetylacetonate, manganese (III) Acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) acetylacetonate, titanium diisopropoxide bis (2,4-pentanedionato ), Copper bis (2,2,6,6-tetramethyl-3,5-heptanedionato), nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptaneedionato), copper (II ) Trifluoroacetylacetonate, copper (II) hexafluoroacetylacetonate water Japanese, manganese (II) hexafluoroacetylacetonate trihydrate, cobalt (II) hexafluoroacetylacetonate hydrate, nickel (II) hexafluoroacetylacetonate hydrate, bis [3- (heptafluoro Propylhydroxymethylene)-(+)-camphorate] oxovanadium, titanium (IV) bis (ammonium lactate) dihydroxide, titanium (IV) bis (ethylacetoacetate) diisopropoxide, tetrakis (acetonitrile) copper (I) hexa Fluorophosphate, dichlorobis (tributylphosphine) nickel (II), dibromobis (tributylphosphine) nickel (II), iodo (trimethylphosphite) copper (I), iodo (triethylphosphite) copper (I),

Chloro (pyridine) bis (dimethylglyoximate) cobalt (III), bis (salicylaldehyde) cobalt (II) dihydrate, tris (dibenzoylmethanate) iron (III), tris (triphenylphosphine) copper ( I) Chloride, bis (triphenylphosphine) copper (I) nitrate, dichlorobis (triphenylphosphine) cobalt (II), chlorotris (triphenylphosphine) cobalt (I), tetrakis (triphenylphosphine) nickel (0) , Dichlorobis (triphenylphosphine) nickel (II), dibromobis (triphenylphosphine) nickel (II), [1,2-bis (triphenylphosphino) ethane] iron (II) chloride, [1,2-bis (Diphenylphosphino) ethane] cobalt (II) chloride, [1,2-bis (di Enylphosphino) ethane] nickel (II) chloride, tetrakis (pyridine) cobalt (II) bis (chromate), tris (2,2′-bipyridine) iron (II) hexafluorophosphate, dichloro (1,10-phenanthroline) copper (II), dibromo (1,10-phenanthroline) copper (II), dinitrate (1,10-phenanthroline) copper (II), tris (1,10-phenanthroline) iron (II) hexafluorophosphate, tris ( 1,10-phenanthroline) iron (III) hexafluorophosphate, N, N′-bis (salicylidene) ethylenediaminocobalt (II), N, N′-bis (salicylidene) ethylenediaminonickel (II), bis (salicyle) Deniminate-3-propyl) methylaminocobalt (II),

(R, R)-(−)-N, N′-bis (3,5-di-t-butylsalicylidene) -1,2-cyclohexanediaminomanganese (III) chloride, (S, S) — (+)-N, N′-bis (3,5-di-t-butylsalicylidene) -1,2-cyclohexanediaminomanganese (III) chloride, N, N′-bis (salicylidene) dianilinocobalt (II), N, N′-bis (salicylidene) -1,2-phenylenediaminocobalt (II) monohydrate, tris (cyclopentadienyl) scandium, bis (cyclopentadienyl) vanadium, bis (cyclo Pentadienyl) chromium, ferrocene, ferrocenium hexafluorophosphate, ferrocenium hexafluoroborate, bis (cyclopentadienyl) cobalt, bis (cyclopentadienyl) Nickel, cyclopentadienyl titanium trichloride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium pentasulfide, bis (cyclopentadienyl) titanium bis (trifluoromethanesulfonate), bis (cyclopenta Dienyl) vanadium dichloride, bis (pentamethylcyclopentadienyl) manganese, 1,1′-dimethylferrocene, bis (pentamethylcyclopentadienyl) iron, 1,2-diferroceneethane, butylferrocene, vinylferrocene, Bis (2,4-cyclopentadien-1-yl) [(4-methylbicyclo [2.2.1] heptane-2,3-diyl) methylene] titanium, ferrocenemethanol, 1,1′-ferrocenedimethanol, (Dimethylaminomethyl) ferroce ,

(R)-(+)-N, N-dimethyl-1-ferrocenylethylamine, (S)-(−)-N, N-dimethyl-1-ferrocenylethylamine, ferrocenecarboxaldehyde, acetylferrocene, 1 , 1′-diacetylferrocene, ferrocene carboxylic acid, acetyl ferrocene, 1,1′-ferrocene dicarboxylic acid, dimethyl 1,1′-ferrocene dicarboxylate, 1,1 ″-[(4,4′-bipiperidine)- 1,1′-diyldicarbonyl] bis [1 ′-(methoxycarbonyl) ferrocene], ferroceneacetonitrile, benzoylferrocene, 1,1′-bis (diphenylphosphino) ferrocene, (−)-(R) -1- [(S) -2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, (+)-(S) -1-[(R) -2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, (-)-(R) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine, (+)- (S) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine, (-)-(R) -N, N-dimethyl-1-[(S) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethylamine, (+)-(S) -N, N-dimethyl-1-[(R) -1', 2-bis (diphenylphosphino) ferrocenyl] ethylamine, Trans-4- [2- (1-ferrocenyl) -vinyl] -1-methylpyridinium iodide, cyclohexadienyliron (0) tricarbonyltetrafluoroborate,

Cycloheptatriene chromium tricarbonyl, cyclooctatetraene iron tricarbonyl, tricarbonyl (4-methoxy-1-methylcyclohexadiene) iron tetrafluoroborate, tricarbonyl (2-methoxycyclohexadiene) iron tetrafluoroborate, tetramethylammonium (1-hydroxyethylidene) pentacarbonylchromium, cyclopentadienyl manganese tricarbonyl, cyclopentadienyl iron dicarbonyl iodide, cyclopentadienyl iron dicarbonyl dimer, cyclopentadienyl cobalt dicarbonyl, cyclopentadiene Enil nickel carbonyl dimer, (methylcyclopentadienyl) -manganese tricarbonyl, dicarbonylcyclopentadienyl (dimethylsulfonium ethylide) iron teto Fluoroborate, benzene chromium tricarbonyl, mesitylene chromium tricarbonyl, 1,2,3,4-tetrahydronaphthalene chromium tricarbonyl, naphthalene chromium tricarbonyl, anisole chromium tricarbonyl, N-methylaniline chromium tricarbonyl, o-toluidine chromium tri Carbonyl, (methylbenzoate) chromium tricarbonyl,

Di-n-butyldithiocarbamate nickel (II), n-butylamino [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), n-butylamino [2,2′-thiobis ( 4-t-octyl) phenolate] cobalt (II), bis [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), [2,2′-thiobis (4-t-octyl) ) Phenolate] nickel (II) hydrate, [2,2′-thiobis (4-t-octyl) phenolate] nickel (II) ethylamine, bis (butyl-3,5-di-t-butyl-4) -Hydroxobenzylphosphonate) Nickel (II), Nickel chloride hexahydrate, Cobalt chloride hexahydrate, Manganese chloride tetrahydrate, Di-n-butyldithiocarbamate cobalt (II), Di-n-butyldi Thiocarbamate copper (II), diisopropyldithiophosphate nickel (II), tetrakispyridine iron (II) chloride, tetrakispyridine iron (II) bromide, tetrakisisoquinoline iron (II) chloride, tetrakisisoquinoline iron (II) bromide, tetrakis Examples thereof include isoquinoline iron (II) iodide, tetrakispyridine iron (II) isocyanate, tetrakis β-picoline iron (II) bromide, and tetrakis γ-picoline iron (II) bromide.

  More preferably, the transition metal is a divalent metal ion. Specifically, α-methylferrocenemethanol, nickel (II) bromide ethylene glycol dimethyl ether complex, bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, bis (tetraethylammonium) tetrabromocopper (II), Bis (tetraethylammonium) tetrabromomanganese (II), bis (tetraethylammonium) tetrabromocobalt (II), copper (II) acetylacetonate, manganese (II) acetylacetonate, cobalt (II) acetylacetonate, nickel ( II) Acetylacetonate, copper bis (2,2,6,6-tetramethyl-3,5-heptanedionate), nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptanedionate) , Copper (II) trifluoroacetylacetonate, copper (II Hexafluoroacetylacetonate hydrate, manganese (II) hexafluoroacetylacetonate trihydrate, cobalt (II) hexafluoroacetylacetonate hydrate, nickel (II) hexafluoroacetylacetonate hydrate, dichlorobis (Tributylphosphine) nickel (II), dibromobis (tributylphosphine) nickel (II), bis (salicylaldehyde) cobalt (II) dihydrate, dichlorobis (triphenylphosphine) cobalt (II), dichlorobis (triphenylphosphine) Nickel (II), dibromobis (triphenylphosphine) nickel (II), [1,2-bis (triphenylphosphino) ethane] iron (II) chloride, [1,2-bis (diphenylphosphino) ethane] Cobalt (II) chloride, [1,2-bis (diph Enylphosphino) ethane] nickel (II) chloride,

Tetrakis (pyridine) cobalt (II) bis (chromate), tris (2,2′-bipyridine) iron (II) hexafluorophosphate, dichloro (1,10-phenanthroline) copper (II), dibromo (1,10-phenanthroline) ) Copper (II), dinitrate (1,10-phenanthroline) copper (II), tris (1,10-phenanthroline) iron (II) hexafluorophosphate, N, N′-bis (salicylidene) ethylenediaminocobalt ( II), N, N′-bis (salicylidene) ethylenediaminonickel (II), bis (salicylideneiminate-3-propyl) methylaminocobalt (II), N, N′-bis (salicylidene) dianilinocobalt ( II), N, N′-bis (salicylidene) -1,2-phenylenediaminocobalt (II) monohydrate Bis (cyclopentadienyl) vanadium, bis (cyclopentadienyl) chromium, ferrocene, bis (cyclopentadienyl) cobalt, bis (cyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) manganese 1,1′-dimethylferrocene, bis (pentamethylcyclopentadienyl) iron, 1,2-diferroceneethane, butylferrocene, vinylferrocene, ferrocenemethanol, 1,1′-ferrocenedimethanol, (dimethylaminomethyl) ) Ferrocene, (R)-(+)-N, N-dimethyl-1-ferrocenylethylamine, (S)-(−)-N, N-dimethyl-1-ferrocenylethylamine, ferrocenecarboxaldehyde,

Acetyl ferrocene, 1,1′-diacetyl ferrocene, ferrocene carboxylic acid, acetyl ferrocene, 1,1′-ferrocene dicarboxylic acid, dimethyl 1,1′-ferrocene dicarboxylate, 1,1 ″-[(4,4 ′ -Bipiperidine) -1,1'-diyldicarbonyl] bis [1 '-(methoxycarbonyl) ferrocene], ferroceneacetonitrile, benzoylferrocene, 1,1'-bis (diphenylphosphino) ferrocene, (-)-(R ) -1-[(S) -2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, (+)-(S) -1-[(R) -2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, (-)-(R) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethyla (+)-(S) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine, (-)-(R) -N, N-dimethyl-1- [(S) -1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine, (+)-(S) —N, N-dimethyl-1-[(R) -1 ′, 2-bis (diphenylphos Fino) ferrocenyl] ethylamine, trans-4- [2- (1-ferrocenyl) -vinyl] -1-methylpyridinium iodide, cyclopentadienyliron dicarbonyl iodide,

Cyclopentadienyliron dicarbonyl dimer, di-n-butyldithiocarbamate nickel (II), n-butylamino [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), n -Butylamino [2,2′-thiobis (4-t-octyl) phenolate] cobalt (II), bis [2,2′-thiobis (4-t-octyl) phenolate] nickel (II), [2 , 2′-thiobis (4-t-octyl) phenolate] nickel (II) hydrate, [2,2′-thiobis (4-t-octyl) phenolate] nickel (II) ethylamine, bis (butyl- 3,5-di-t-butyl-4-hydroxobenzylphosphonate) nickel (II), nickel chloride hexahydrate, cobalt chloride hexahydrate, manganese chloride tetrahydrate, di-n-butyldithio Rubamate cobalt (II), di-n-butyldithiocarbamate copper (II), diisopropyldithiophosphate nickel (II), tetrakispyridine iron (II) chloride, tetrakispyridine iron (II) bromide, tetrakisisoquinoline iron (II) Chloride, tetrakisisoquinoline iron (II) bromide, tetrakisisoquinoline iron (II) iodide, tetrakispyridine iron (II) isocyanate, tetrakis β-picoline iron (II) bromide, tetrakis γ-picoline iron (II) bromide It is done.

More preferably, a transition metal complex in which the transition metal is Co ²⁺ or Ni ²⁺ is used. Specifically, nickel (II) bromide ethylene glycol dimethyl ether complex, bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, bis (tetraethylammonium) tetrabromocobalt (II), cobalt (II) acetyl Acetonate, nickel (II) acetylacetonate, nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptanedionate), cobalt (II) hexafluoroacetylacetonate hydrate, nickel ( II) Hexafluoroacetylacetonate hydrate, dichlorobis (tributylphosphine) nickel (II), dibromobis (tributylphosphine) nickel (II), bis (salicylaldehyde) cobalt (II) dihydrate, dichlorobis (triphenylphosphine) ) Cobalt (II), dichlorobis (triphenylphosphine) nickel (II), dibromobis (triphenylphosphine) nickel (II), [1,2-bis (diphenylphosphino) ethane] cobalt (II) chloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) chloride, tetrakis (pyridine) cobalt (II) bis (chromate), N, N′-bis (salicylidene) ethylenediaminocobalt (II), N , N′-bis (salicylidene) ethylenediaminonickel (II), bis (salicylideneiminate-3-propyl) methylaminocobalt (II), N, N′-bis (salicylidene) dianilinocobalt (II), N , N′-bis (salicylidene) -1,2-phenylenediaminocobalt (II) Hydrates, bis (cyclopentadienyl) cobalt, bis (cyclopentadienyl) nickel, di-n-butyldithiocarbamate nickel (II), n-butylamino [2,2′-thiobis (4-t- Octyl) phenolate] nickel (II), n-butylamino [2,2′-thiobis (4-t-octyl) phenolate] cobalt (II), bis [2,2′-thiobis (4-t-octyl) ) Phenolate] Nickel (II), [2,2′-thiobis (4-t-octyl) phenolate] Nickel (II) hydrate, [2,2′-thiobis (4-t-octyl) phenolate ] Nickel (II) ethylamine, bis (butyl-3,5-di-t-butyl-4-hydroxobenzylphosphonate) nickel (II), nickel chloride hexahydrate, cobalt chloride Hexahydrate, di -n- butyl dithiocarbamate cobalt (II), include diisopropyl dithiophosphate nickel (II) is.

More preferably, the transition metal complex whose ligand does not contain an aromatic ring is mentioned. Specifically, nickel (II) bromide ethylene glycol dimethyl ether complex, bis (cis-1,2-diaminocyclohexane) nickel (II) chloride, bis (tetraethylammonium) tetrabromocobalt (II), cobalt (II) acetyl Acetonate, nickel (II) acetylacetonate, nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptanedionate), cobalt (II) hexafluoroacetylacetonate hydrate, nickel ( II) hexafluoroacetylacetonate hydrate, dichlorobis (tributylphosphine) nickel (II), dibromobis (tributylphosphine) nickel (II), di-n-butyldithiocarbamate nickel (II), nickel chloride hexahydrate, Cobalt chloride Hexahydrate, di -n- butyl dithiocarbamate cobalt (II), include diisopropyl dithiophosphate nickel (II) is.
Among these, particularly preferred transition metal complexes are cobalt (II) acetylacetonate, cobalt (II) hexafluoroacetylacetonate hydrate, nickel (II) acetylacetonate, and di-n-butyldithiocarbamate nickel (II). is there.
The most preferred transition metal complexes are cobalt (II) acetylacetonate and cobalt (II) hexafluoroacetylacetonate hydrate.

~ (E) Other ingredients ~
[monomer]
When the dye-containing curable composition of the present invention is configured as a negative type, it is preferable to contain a monomer. As the monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth) Monofunctional acrylates and methacrylates such as acrylate, polypropylene glycol mono (meth) acrylate, 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 Ethylene oxide or propylene oxide to polyfunctional alcohols such as silicate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane (Meth) acrylates, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B-49-43191 and JP-B-52-30490 And a mixture of these Mention may be made of things. Furthermore, the Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  As content in the dye-containing curable composition of the said monomer, 0.1-90 mass% is preferable with respect to solid content of this composition, 1.0-80 mass% is more preferable, 2.0-70 Mass% is particularly preferred.

[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 that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and acyloxymethyl 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 the group A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) 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, 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) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b).

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

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

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

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

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These 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, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups 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.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

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

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 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, as a phenol compound or a naphthol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like 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, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

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

  In the present invention, it is not always necessary to contain the crosslinking agent. When contained, the total content of the crosslinking agents (a) to (c) in the dye-containing curable composition varies depending on the material, but 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.

[Organic solvent]
In preparing the dye-containing curable composition of the present invention, an organic solvent (also simply referred to as “solvent” in the present specification) is generally contained. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the dye-containing curable composition are satisfied. However, the solvent is particularly selected in consideration of the solubility, coating property, and safety of the dye and the alkali-soluble binder. It is preferable that

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

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

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

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

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

[Various additives]
In the dye-containing 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, and an aggregation preventive agent are optionally added. An 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 curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. A molecular weight organic carboxylic acid 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, camphoric 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 Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The dye-containing curable composition of the present invention is used for forming a colored pixel such as a color filter or an electroluminescence color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS). And can be suitably used for producing printing inks, inkjet inks, paints, and the like.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the manufacturing method of the color filter of this invention, a color filter can be suitably produced using the dye-containing curable composition of this invention as stated above. That is,
When the dye-containing curable composition of the present invention is configured as a negative type, the negative type dye-containing curable composition is applied on a support by a coating method such as spin coating, cast coating, roll coating, etc. A radiation composition layer is formed, the layer is exposed through a predetermined mask pattern, and developed with a developer to form a negative colored pattern (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  When the dye-containing curable composition of the present invention is constituted as a positive type, the positive type dye-containing curable composition is applied on a support by a coating method such as spin coating, cast coating, roll coating, etc. After forming a radiation composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer, a positive colored pattern is formed (image forming step), and then the formed colored pattern Is heated to cure (post-bake).

In the production of the color filter, in the case of the negative type, the image forming step (and the curing step if necessary) is repeated by the desired number of hues. In the case of the positive type, the image forming step and post-baking are performed as desired. By repeating the number of hues, a color filter having a desired hue can be produced.
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 (R) glass, and quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, and the like. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  As the developer, any developer may be used as long as it has a composition that dissolves the uncured portion of the dye-containing curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As an organic solvent here, the above-mentioned organic solvent used when preparing the dye-containing 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 liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), and is particularly suitable for a high-resolution CCD element, CMOS, etc. exceeding 1 million pixels. is there. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

Example 1
1) Preparation of resist solution-Ethyl lactate-75 parts-Binder-7.0 parts [Benzyl methacrylate / methacrylic acid copolymer (= 7/3 [molar ratio])]
・ Polymerization inhibitor (p-methoxyphenol): 0.005 part ・ Fluorosurfactant: 0.4 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Dipentaerythritol hexaacrylate 9.8 parts (photopolymerizable compound)
Photopolymerization initiator (TAZ-107, manufactured by Midori Chemical Co., Ltd.) 1.2 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, and then washed with water and dehydrated (200 ° C./30 minutes). Next, the resist solution obtained in 1) above was applied onto a glass substrate after washing using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to form a cured film (undercoat layer). Formed.

3) Preparation of Negative Dye-Containing Curable Composition A-1-Ethyl lactate-75 parts-Binder-7.0 parts [Allyl methacrylate / methacrylic acid copolymer (= 5/5 [molar ratio])]
-Yellow dye (Valifast Yellow 1101)-6.0 parts-Polymerization inhibitor (p-methoxyphenol)-0.005 part-Fluorosurfactant-0.4 part (F-475, Dainippon Ink & Chemicals, Inc. ( Made by)
-Dipentaerythritol hexaacrylate (monomer) 9.8 parts-Photopolymerization initiator (CGI-124, manufactured by Ciba Geigy) ... 1.2 parts-Nickel (II) acetylacetonate-0.6 parts It melt | dissolved and negative-type dye containing curable composition A-1 was prepared.

4) Exposure and development of dye-containing curable composition (image forming process)
Using a spin coater, the dye-containing curable composition A-1 obtained in 3) above is formed on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) so that the film thickness becomes 1.3 μm. And prebaked at 120 ° C. for 120 seconds.

Then, using an exposure apparatus, the entire surface of the coating film was irradiated with a wavelength of 365 nm and an exposure amount of 500 mJ / cm ² . After irradiation, development was performed at 23 ° C. for 60 seconds using a 50% CD-2000 (Fuji Film Arch Co., Ltd.) developer. Subsequently, after rinsing with running water for 20 seconds and spray drying, heating (post-baking) was further performed at 200 ° C. for 300 seconds to obtain a yellow colored filter film.

5) Evaluation With respect to the yellow colored filter film obtained as described above, the light resistance and the post-development residual film ratio were evaluated as follows.
The light resistance was evaluated by irradiating a glass substrate with an undercoat layer on which a yellow filter film was formed with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux · h), That is, ΔEab value was measured and evaluated based on the measured value. A smaller ΔEab value indicates better light resistance.
The post-development residual film ratio is the ratio [%] of the absorbance value of the filter film after development and before development, and the visible light absorption spectrum before and after the development of the coated filter film is measured by the chromaticity meter MCPD-1000 (Otsuka Each was measured using an electron), and the absorbance ratio at the maximum absorption wavelength λmax of the dye was evaluated as an index. A larger value indicates a better pattern shape.

(Examples 2 to 13, Comparative Examples 1 to 3)
In Example 1, the yellow dye (Valifast Yellow 1101) and the transition metal complex (nickel (II) acetylacetonate) used in “3) Preparation of negative dye-containing curable composition A-1” are shown in the following table. Negative type dye-containing curable compositions A-2 to A-13 and A-14 to A-16 were prepared in the same manner as in Example 1 except that the dyes and transition metal complexes shown in 1 were used. A colored filter film was formed and the same evaluation was performed. The evaluation results are shown in Table 1 below.

  As shown in the results of Table 1 above, the colored filter films formed using the negative dye-containing curable compositions A-1 to A-13 of the present invention all exhibit high light resistance and remain after development. The film rate was also good. On the other hand, the colored filter film using the comparative curable compositions A-14 to A-16 was inferior in both the light resistance and the remaining film ratio after development.

( Reference Example 14)
In Example 1, the negative type dye-containing curable composition A-1 prepared in 3) above was replaced with the positive type dye-containing curable composition B-1 prepared in 6) below, and the above 4 ) A colored filter film is formed in the same manner as in Example 1 except that the entire surface of the coating film is exposed at a wavelength of 193 nm in the exposure and development (image forming step) of the dye-containing curable composition. Evaluation was performed. The evaluation results are shown in Table 2 below.

6) Preparation of positive type dye-containing curable composition B-1-Ethyl lactate 75 parts-Binder P-1 below 14.0 parts-Yellow dye (CI Acid Yellow 29) ... 6.0 parts・ The following photoacid generator PAG-1: 4.0 parts ・ Fluorosurfactant: 0.4 parts (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Diisopropyl dithiophosphate nickel (II) ... 0.6 part was mixed and melt | dissolved, and positive type dye containing curable composition B-1 was obtained.

( Reference Examples 15-22, Comparative Examples 4-6)
In Reference Example 14, yellow dye (CI Acid Yellow 29) and transition metal complex (diisopropyldithiophosphate nickel (II)) used in “6) Preparation of Positive Dye-Containing Curable Composition B-1” Were replaced with the dyes and transition metal complexes shown in Table 2 below, in the same manner as in Reference Example 14 , positive dye-containing curable compositions B-2 to B-9 and B-10 to B-12 And a colored filter film was formed, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

  As shown in the results of Table 2 above, the colored filter films formed by using the dye-containing curable compositions B-1 to B-9 of the present invention for the positive type all show high light resistance, and the residual film after development. The rate was also good. On the other hand, the colored filter films using the comparative curable compositions B-10 to B-12 were inferior in both the light resistance and the remaining film ratio after development.

( Reference Example 23)
In Example 1, except that the negative dye-containing curable composition A-1 prepared in 3) above was replaced with the positive dye-containing curable composition C-1 prepared in 7) below. In the same manner as in Example 1, a colored filter film was formed, and the same evaluation was performed. The evaluation results are shown in Table 3 below.

7) Preparation of Positive Type Dye-Containing Curable Composition C-1 Ethyl lactate 75 parts Binder 14.0 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (= 6 / 3/1 [molar ratio])]
・ Yellow dye (CI Acid Yellow 65) 6.0 parts ・ Esterified product of 2,3,4-trihydroxybenzophenone and o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate 80 mol%; quinonediazide compound) 4.0 parts ・ Fluorosurfactant 0.4 parts (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
Bis (salicylaldehyde) cobalt (II) dihydrate: 0.6 part was mixed and dissolved to obtain a positive dye-containing curable composition C-1.

( Reference Examples 24-35, Comparative Examples 7-9)
In Reference Example 23, yellow dye (CI Acid Yellow 65) and transition metal complex (bis (salicylaldehyde) cobalt (II)) used in “7) Preparation of Positive Dye-Containing Curable Composition C-1” ) Dihydrate) in the same manner as in Reference Example 23 except that the dyes and transition metal complexes shown in Table 3 below were used, and positive dye-containing curable compositions C-2 to C-13 and C −14 to C-16 were prepared to form a colored filter film, and the same evaluation was performed. The evaluation results are shown in Table 3 below.

  As shown in the results of Table 3 above, in the positive type, all of the colored filter films using the dye-containing curable compositions C-1 to C-13 of the present invention exhibit high light resistance, and the residual film after development. The rate was also good. On the other hand, in the colored filter film using comparative curable compositions C-14 to C-16, both the light resistance and the post-development residual film ratio were inferior.

Claims (3)

(A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) at least one of a photopolymerization initiator and a photoacid generator , (D) nickel (II) acetylacetonate, cobalt (II) acetylacetonate, Cobalt (II) hexafluoroacetylacetonate hydrate, dichlorobis (triethylphosphine) palladium (II), dichlorotetrakis (triphenylphosphine) ruthenium (II), tris (triphenylphosphine) copper (I) chloride, bis ( Cis-1,2-diaminocyclohexane) nickel (II) chloride, tetrakispyridine iron (II) bromide, tris (2,2'-bipyridyl) ruthenium (II) chloride hexahydrate, manganese chloride tetrahydrate , Di-n-butyldithiocarbamate copper (II), and di-n-butyldithiocarbamate nickel Le least saw including at least one of (II), dye-containing curable composition characterized in that it is configured to negative. A color filter comprising the dye-containing curable composition according to claim 1 . A method for producing a color filter, comprising: applying a dye-containing curable composition according to claim 1 onto a support, exposing the film through a mask, and developing to form a pattern image.