JP2007277386A - Colored curable composition, color filter and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition having high resolution and high permeability properties, as well as excellent in heat fastness, light fastness and storage stability, and to provide a color filter using it and a manufacturing method thereof. <P>SOLUTION: This colored curable composition comprises a dye represented by general formula (1) (wherein R<SB>1</SB>and R<SB>2</SB>are each a substituted or an unsubstituted alkyl group, R<SB>3</SB>is a hydrogen atom or a substituted group, Z<SB>1</SB>is -N= or -CR<SB>4</SB>=, Z<SB>2</SB>is -N= or -CR<SB>5</SB>=, R<SB>4</SB>and R<SB>5</SB>are each a hydrogen atom or a substituted group, and A is an aromatic heterocycle of 5-members or 6-members). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  A color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to the same plane on the substrate as a color filter formed on the element to colorize a solid-state image sensor or a liquid crystal display element A color filter including a filter, a red filter layer, a green filter layer, and a blue filter layer is known. In the filter layer, a belt-like pattern or a mosaic pattern is formed.

  Various methods for producing a color filter have been proposed. In particular, a so-called color resist method in which a photosensitive resin composition containing a dye is exposed and developed to repeatedly perform a patterning process a required number of times has been widely put into practical use.

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

  In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied onto a glass substrate using a spin coater, a roll coater, etc., a coating film is formed, and the coating film is subjected to pattern exposure and development. Thus, a colored pixel is obtained, and this operation is performed for each color to obtain a color filter. As the pigment dispersion method, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator in an alkali-soluble resin is disclosed.

  However, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, the conventional pigment dispersion system does not improve resolution, and has problems such as color unevenness due to coarse pigment particles, so that a fine pattern such as a solid-state imaging device is required. Not suitable for use. In order to solve this problem, the use of dyes has been proposed in the past, and positive photosensitive compositions have been disclosed.

  However, dye-containing colored curable compositions have the following problems, and further improvements are required.

  1) Dyes are generally inferior in heat resistance and light resistance compared to pigments, and further improvement in fastness is required.

  2) When the molar extinction coefficient of the dye is low, a large amount of dye must be added. For this purpose, other components such as a polymerizable compound, a binder and a photopolymerization initiator in the colored curable composition are added. There is a need to improve the problems such as reduction in curability of the composition, heat resistance after curing, developability of the non-cured portion, and the like.

  3) Dyes often exhibit an interaction with other components in the colored curable composition, and it is difficult to adjust the developability (solubility) of the cured part and the cured part. It has been.

  As described above, the dyes conventionally used in the photosensitive composition are not particularly satisfactory in fastness, and further, the solubility in the photosensitive composition is low and it is difficult to contain the dye at a high concentration. There was a need for improvement.

On the other hand, it is known that a violet dye is used for a blue filter array of a color filter (see, for example, Patent Document 1). However, the violet dye used in the patent is insufficient in heat resistance and light resistance, and further improvement is desired. Similarly, in a color filter including a yellow filter layer, a magenta filter layer, and a cyan filter layer, further improvement in fastness of the magenta dye used in the magenta filter layer is desired. In addition, a color filter containing a pyrazoloazole-based azomethine dye is disclosed (for example, see Patent Documents 2 to 4). Similarly, the dyes shown in these are desired to have improved solubility and fastness.
Japanese Patent Laid-Open No. 2002-14222 JP 2002-256164 A JP 2005-88332 A JP 2005-189802 A

  An object of the present invention is to provide a colored curable composition having high resolution and high transmittance characteristics, and excellent in heat fastness, light fastness, and storage stability, and a color filter using the same and a method for producing the same. It is to provide.

  In the present invention, various dye compounds having a good hue and high fastness to light and heat are examined in detail, and a dye having a specific structure particularly improves fastness such as heat resistance and light resistance. The knowledge that it was useful was obtained, and based on this knowledge, a colored curable composition, a color filter, and a production method thereof having the following constitution were provided, and the object was achieved. The object of the present invention has been achieved by the following constitution.

  1. A colored curable composition comprising a dye represented by the following general formula (1).

(Wherein R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, R ₃ represents a hydrogen atom or a substituent, Z ₁ represents —N═ or —CR ₄ ═, and Z ₂ represents —N = Or -CR ₅ =, R ₄ and R ₅ represent a hydrogen atom or a substituent, and A represents a 5-membered or 6-membered aromatic heterocyclic ring.
2. 2. The colored curable composition as described in 1 above, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (2).

_{(Wherein, R 1, R 2, R} 3, Z 1 and Z ₂ R ₁ in the general formula _{(1), R 2, R} 3, the same meaning as Z ₁ and Z ₂ .R ₆ substituent Z ₃ represents —N═ or —CR ₇ ═, Z ₄ represents —N═ or —CR ₈ ═, and at least one of Z ₃ and Z ₄ represents —N═, R ₇ And R ₈ represents a hydrogen atom or a substituent, and m represents an integer of 0 to 3.)
3. 3. The colored curable composition as described in 2 above, wherein the dye represented by the general formula (2) is a dye represented by the following general formula (3).

(Wherein, R _1, R ₂ and R ₃ R _1, R ₂ and R ₃ as synonymous .R ₅ and R ₈ in the general formula (1) represents a hydrogen atom or a substituent.)
4). 2. The colored curable composition as described in 1 above, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (4).

_{(Wherein, R 1, R 2, R} 3, Z 1 and Z ₂ R ₁ in the general formula _{(1), R 2, R} 3, Z 1 and Z ₂ as synonymous .R ₉ is hydrogen Or represents a substituent.)
5). A colored curable composition comprising at least one metal chelate dye having a dye selected from the general formulas (1) to (4) as a ligand.

  6). 6. A color filter comprising the colored curable composition according to any one of 1 to 5 above.

  7). A method for producing a color filter, comprising: applying a colored curable composition according to any one of 1 to 5 above onto a support, exposing through a mask, and developing to form a pattern. .

  According to the present invention, a colored curable composition having high resolution and high transmittance characteristics, high heat fastness and light fastness, and excellent storage stability can be provided. In addition, the color filter configured using the colored curable composition has high resolution and high transmittance characteristics and high heat fastness and light fastness, and can exhibit excellent storage stability. Furthermore, the manufacturing method of this color filter which can be produced with high productivity was able to be provided.

  Hereinafter, although the colored curable composition of this invention, a color filter, and its manufacturing method are demonstrated, this invention is not limited to these.

(Colored curable composition)
The colored curable composition of the present invention contains at least one dye represented by the general formula (1), and preferably contains a binder, a radiation sensitive compound, and a polymerizable monomer. Moreover, generally, it can be further constituted by using a solvent, and if necessary, it can be constituted by using other components such as a crosslinking agent. This dye has a good hue, does not precipitate over time when it is in the form of a liquid preparation or a coated film, has excellent storage stability, and has particularly high heat and light fastness.

  Next, the dye represented by the general formula (1) according to the present invention will be described in detail.

In the general formula (1), R ₁ and R ₂ represent a substituted or unsubstituted alkyl group. Examples of the alkyl group represented by R ₁ and R ₂ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, and n-pentyl. Group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, An isohexadecyl group, n-octadecyl group, etc. can be mentioned.

When R ₁ and R ₂ represent an alkyl group having a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group). Pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), aryl group (eg, phenyl group, naphthyl group etc.), acylamino group ( For example, acetylamino group, benzoylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkenyl group (eg, vinyl group, 2-propenyl group). , 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl -3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg, propargyl group etc.), heterocyclic group ( For example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl A group (for example, a methylsulfinyl group), an arylsulfinyl group (for example, a phenylsulfinyl group), a phosphono group, an acyl group (for example, an acetyl group, a pivaloyl group, a benzoyl group, etc.), a carbamoyl group (for example, an aminocarbonyl group, Methylaminocarbonyl group, di Tilaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group) Group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group) , Benzenesulfonamido group, etc.), cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, Enoxy group, naphthyloxy group, etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (eg, Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group) , Naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido) Group, 2- Pyridylaminoureido group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg , Phenoxycarbonyl group, etc.), heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxyl group, mercapto group, nitro group and the like. These substituents may be further substituted with the same substituent.

The alkyl groups represented by R ₁ and R ₂ may be bonded to each other to form a ring. Examples of the ring include a piperidine ring, a pyrrolidine ring, a piperazine ring, a morpholine ring, and a thiomorpholine ring. _One or both of the alkyl groups represented by R ₁ and R ₂ may be bonded to A in the general formula (1) to form a ring.

As the alkyl group represented by R ₁ and R ₂ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an isobutyl group are preferable, and a methyl group, an ethyl group, n- A propyl group, an n-butyl group, and an isobutyl group are more preferable, and an ethyl group is particularly preferable.

In the general formula (1), R ₃ represents a hydrogen atom or a substituent. When R ₃ represents a substituent, examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ and R ₂ may have. R ₃ is preferably an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group or an amino group, more preferably an alkyl group, an aryl group, an alkoxycarbonyl group or a carbamoyl group, and an alkyl group Is particularly preferred.

In the general formula _(1), Z 1 represents -N = or -CR ₄ =, Z ₂ represents -N = or -CR ₅ =, R ₄ and R ₅ represents a hydrogen atom or a substituent. When R ₄ and R ₅ represent a substituent, examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ and R ₂ may have. R ₄ and R ₅ are preferably an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. R ₄ and R ₅ may be bonded to each other to form a ring.

In general formula (1), it is preferable that only _one of Z ₁ and Z ₂ represents —N═.

In the general formula (1), A represents a 5-membered or 6-membered aromatic heterocyclic ring. The 5-membered or 6-membered aromatic heterocycle represented by A includes various aromatic rings having a ring atom as a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Well, specific examples of such aromatic heterocycle include, for example, acridine ring, isoxazole ring, isoquinoline ring, isothiazole ring, imidazopyridine ring, imidazole ring, indazole ring, indolizine ring, indole ring, oxadiazole. Ring, oxazole ring, carbazole ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thionaphthene ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, naphthimidazole ring, naphthoxazole ring, naphtho Thiazole ring, pyrazine ring, pyrazole ring, pyridine ring, Rings such as lidazine ring, pyrimidine ring, pyrrole ring, phthalazine ring, furan ring, purine ring, phenanthridine ring, benzimidazole ring, benzoxazole ring, benzoisoxazole ring, benzoisothiazole ring, benzothiazole ring, benzofuran ring Can be mentioned. The 5-membered or 6-membered aromatic heterocyclic ring represented by A may further have a substituent, and the substituent may have the alkyl group represented by R ₁ and R _2. The same group as a substituent can be mentioned.

  The 5-membered or 6-membered aromatic heterocycle represented by A is preferably a thiazole ring, thiophene ring, pyrazine ring, pyridine ring, pyridazine ring or pyrimidine ring, more preferably a thiazole ring, pyridazine ring or pyridine ring. A ring is particularly preferred.

  Examples of the general formula (1) include those represented by the following general formula, but the present invention is not limited thereto.

In Formula _{D-1~56, R 1, R} 2, R 3, Z 1 and Z ₂ have the same meanings as _{R 1, R 2, R 3} , Z 1 and Z ₂ in the general formula (1) . Moreover, the part corresponding to the aromatic heterocyclic ring A in the general formula (1) in the general formulas D-1 to 56 is a substituent that the alkyl group represented by the R ₁ and R ₂ may have. It may have a similar group.

  The dye represented by the general formula (1) is preferably represented by the general formula (2).

In the general formula _{(2), R 1, R} 2, R 3, Z 1 and Z ₂ have the same meanings as _{R 1, R 2, R 3} , Z 1 and Z ₂ in the general formula (1).

In the general formula (2), R ₆ represents a substituent, and examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ and R ₂ may have.

In the general formula (2), Z ₃ represents —N═ or —CR ₇ ═, Z ₄ represents —N═ or —CR ₈ ═, R ₇ and R ₈ represent a hydrogen atom or a substituent, At least one of Z ₃ and Z ₄ represents -N =. When R ₇ and R ₈ represent a substituent, examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ and R ₂ may have. And an alkyl group, an amino group, an anilino group, an alkoxy group, an acylamino group, a sulfonamide group, a ureido group, and an alkoxycarbonylamino group are preferable.

  In General formula (2), m represents the integer of 0-3.

  The dye represented by the general formula (2) is more preferably represented by the general formula (3).

In the general formula (3), wherein, R _1, R ₂ and R ₃ have the same meanings as R _1, R ₂ and R ₃ in formula (1). R ₅ and R ₈ represent a hydrogen atom or a substituent.

In General Formula (3), when R ₅ and R ₈ represent a substituent, examples of the substituent include the same groups as the substituent that the alkyl group represented by R ₁ and R ₂ may have. Among them, an alkyl group, an amino group, an anilino group, an alkoxy group, an acylamino group, a sulfonamide group, a ureido group, and an alkoxycarbonylamino group are preferable, and a methyl group is particularly preferable.

  The dye represented by the general formula (1) is preferably represented by the general formula (4).

In the general formula _{(4), R 1, R} 2, R 3, Z 1 and Z ₂ have the same meanings as _{R 1, R 2, R 3} , Z 1 and Z ₂ in the general formula (1).

In the general formula (4), R ₉ represents a hydrogen atom or a substituent. When R ₉ represents a substituent, examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ and R ₂ may have.

  Next, specific examples of the dyes represented by the general formulas (1) to (4) in the present invention are shown, but the present invention is not limited to the following specific examples.

  Next, although the synthesis example of the exemplary dye in this invention is shown in the following reaction schemes, it is not limited to this.

Synthesis of Exemplified Dye 1-1 (1) Synthesis of Intermediate (A)

  10.6 g of 5-t-butyl-2-hydrazinothiadiazine was added to 100 ml of acetonitrile, 10 g of trifluoroacetic anhydride was added with further stirring, and the mixture was stirred for 1 hour. Thereafter, acetonitrile was distilled off, ethyl acetate was added, and the ethyl acetate solution was washed with water and an aqueous sodium carbonate solution. Then, the ethyl acetate solution was extracted and dried, and then ethyl acetate was distilled off to give intermediate (A) 12 .4 g was obtained.

  (2) Synthesis of intermediate (B)

  12 g of intermediate (A) was mixed with 50 ml of acetic anhydride and stirred for 30 hours. Thereafter, the solvent was distilled off, 100 ml of methanol and 10 ml of concentrated hydrochloric acid were added and stirred for 2 hours, followed by suction filtration. Ethyl acetate and saturated brine were added to the filtrate, and the ethyl acetate solution was separated. The ethyl acetate solution was further washed with a sodium hydrogen carbonate solution and saturated brine and dried, and then ethyl acetate was distilled off to obtain 7.2 g of intermediate (B).

(3) Synthesis of Exemplified Dye 1-1 Intermediate (B) (4.0 g) and methanol (200 ml) are mixed, 2-methyl-3-amino-6-N, N-diethylaminopyridine (3.1 g) is added, and the mixture is further stirred. Then, a solution in which 9.1 g of sodium carbonate was dissolved in 20 ml of water was added. Next, 20 ml of water containing 4.3 g of ammonium persulfate was added dropwise and stirred for 2 hours. Thereafter, water was further added and the precipitated crystals were filtered off and recrystallized from acetonitrile to obtain 3.5 g of dye 1-1. NMR and MASS spectrum confirmed the target product. The melting point was 143 to 145 ° C.

  Next, a metal chelate dye having a dye selected from the general formulas (1) to (4) as a ligand will be described in detail.

  The metal chelate dye having a dye selected from the general formulas (1) to (4) as a ligand is at least one nitrogen atom and metal atom of the dye selected from the general formulas (1) to (4). It means a dye forming a coordination bond.

  The metal chelate dye having a dye selected from the general formulas (1) to (4) as a ligand is preferably represented by the following general formulas (5) to (8), respectively.

In the formula, M represents a metal ion, L represents an anion, n ₁ represents an integer of ₁ to 3, and n ₂ represents an integer of 0 to 3. R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , A and m are R in the general formulas (1) to (4). ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , A and m are synonymous.

  In the general formulas (5) to (8), the metal ion represented by M is selected from metal atoms of Group VIII, Group Ib, Group IIb, Group IIIa, Group IVa, Group Va, Group VIa, and Group VIIa Preferably, it is a divalent transition metal ion. Specific examples include divalent metal ions of Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, and more preferable examples include divalent metal ions of Ni, Cu, Co, and Zn. Ni or Cu divalent metal ions are preferred.

In the general formulas (5) to (8), examples of the anion represented by L include enolate (acetylacetonate, hexafluoroacetylacetonate), halogen ion (fluoride, chloride, bromide, iodide, etc.), water, and the like. Acid ion, sulfite ion, sulfate ion, alkylsulfonate ion, arylsulfonate ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkylcarboxylate ion, arylcarboxylate ion, tetraalkylborate, salicinate, Examples include benzoate, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ^{− and the} like.

  Next, although the specific example of the metal chelate dye in this invention is shown, this invention is not limited by the following specific examples.

  As a method for producing a metal chelate dye, for example, it can be synthesized according to the method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method (I) (Edited by Nanedo)”. When using the obtained metal chelate dye, one isolated as a crystal may be used, and when isolation is difficult, the solvent may be distilled off and the residue may be used. May be used after organically dissolved in another solvent.

  The metal chelate dyes represented by the general formulas (5) to (8) may have a neutral ligand depending on the central metal, and typical ligands include water, alcohols, and amines. Kind.

  Next, although the synthesis example of the exemplary metal chelate dye in this invention is shown in the following reaction schemes, it is not limited to this.

  Synthesis of exemplary metal chelate dye 5-2

(1) Synthesis of intermediate (D) 8.5 g of intermediate (C), 10.1 g of 3-amino-6-N, N-diethylamino-2-methylpyridine dihydrochloride and 25 g of triethylamine were placed in 275 ml of methanol. And dissolved at room temperature. 11.0 g of ammonium persulfate dissolved in 90 ml of distilled water was added dropwise in about 30 minutes. After stirring for 30 minutes after the dropping, 300 ml of distilled water was added little by little and stirred, and the precipitated crystals were collected by filtration and washed with water. The crystals were placed in 250 ml of methanol and boiled, allowed to cool, and the precipitated crystals were collected by filtration, washed with methanol and dried to obtain 10.2 g of dark reddish brown crystals (intermediate (D)). NMR and MASS spectrum confirmed the target product.

(2) Synthesis of Exemplary Metal Chelate Dye 5-2 4.3 g of intermediate (D) was dissolved in 50 ml of methanol, and 1.1 g of nickel chloride hexahydrate was added thereto. After distilling off the solvent, acetonitrile was added, and the crystals were collected by filtration, washed and dried to obtain 2.8 g of the target metal complex dye (Exemplary Metal Chelate Dye 5-2). The absorption maximum of this metal complex dye in an acetone solution was 534 nm.

  As the dye in the colored curable composition of the present invention, only one dye selected from the dyes represented by the general formulas (1) to (4) or a metal chelate dye having the dye as a ligand was used. Or a combination of two or more dyes, or a combination of dyes outside the present invention.

  The concentration of the dye in the colored curable composition of the present invention varies depending on the molecular weight and molar extinction coefficient, but is preferably 0.5 to 80% by mass relative to the total solid components of the composition, 0.5 to 60 % Mass% is more preferable, and 0.5 to 50% mass% is particularly preferable.

(binder)
The colored curable composition of the present invention preferably contains at least one binder. The 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.

  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 a linear organic high molecular polymer include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-A-58-12777, JP-A-54-25957, Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid as described in JP-A-59-53836 and 59-71048 There are copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful.

  In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized. Examples of this monomer include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N- Methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl ( Examples include meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

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

  Moreover, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, the polymer etc. which contained the allyl group, the (meth) acryl group, the allyloxyalkyl group, etc. in the side chain are useful. Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

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

  Moreover, an alkali-soluble phenol resin can be used as a binder used for this invention. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.

  Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

  Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like. Phenols and aldehydes can be used alone or in combination of two or more.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin. The molecular weight distribution of the novolak resin may be adjusted using a means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.

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

(Crosslinking agent)
In the present invention, by using the dye represented by the general formulas (1) to (4) or the metal chelate dye having the dye as a ligand, the curing reaction of the film is advanced to a higher degree than before. Thus, a film having good curability can be obtained. However, it is possible to obtain a film that is further highly cured by using a cross-linking agent.

  The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one selected substituent, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group; A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted by Among these, a polyfunctional epoxy resin is particularly preferable.

  The epoxy resin as component (a) may be any epoxy resin as long as it has an epoxy group and crosslinkability. Examples of these compounds include bisphenol A-glycidyl ether, ethylene glycol diester. Low divalent glycidyl group content such as glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline Molecular compounds, trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether, trivalent glycidyl group-containing low molecular weight compounds represented by TrisP-PA triglycidyl ether, etc. Tetravalent glycidyl group-containing low molecular weight compounds typified by, for example, lysitol tetraglycidyl ether, tetramethylol bisphenol-A-tetraglycidyl ether, as well as polyvalent compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, etc. Glycidyl group-containing low molecular weight compounds, polyglycidyl (meth) acrylate, glycidyl represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like And group-containing polymer compounds.

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the component (b) is 2 to 6 in the case of melamine compounds, 2 to 2 in the case of glycoluril compounds, guanamine compounds, and urea compounds. 4, preferably 5 to 6 in the case of a melamine compound, and 3 to 4 in the case of a glycoluril compound, a guanamine compound, and a urea compound. These methylol group-containing compounds can be obtained by heating the alkoxymethyl group-containing compound in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound is obtained by mixing and stirring a methylol group-containing compound with acyl chloride in the presence of a basic catalyst.

  Hereinafter, specific examples of the compound in (b) having the above substituent are given.

  Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine And a compound in which 1 to 5 of the methylol groups are acyloxymethylated or a mixture 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 guanamine. Or a compound obtained by acyloxymethylating 1 to 3 methylol groups, or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, and a compound obtained by methoxymethylating one to three methylol groups of tetramethylolglycoluril, or a mixture thereof, or the 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.

  The compounds according to (b) may be used alone or in combination.

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

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

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

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

  Specific examples of the component (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol-A, Tetramethoxymethyl bisphenol-A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol-A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4'-bishydroxy Bifeni , Hexamethylol of Tris P-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, there is bishydroxymethyl naphthalene diol.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.

  Examples of the acyloxymethyl group-containing compound include compounds in which the methylol group of the methylol group-containing compound is partially or fully acyloxymethylated.

  Among these compounds, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, hexamethylol body of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxy. It is a phenol compound substituted with both a methyl group and a methylol group and an alkoxymethyl group.

  These compounds according to component (c) may be used alone or in combination.

  The colored curable composition of the present invention does not necessarily contain a cross-linking agent, but in the case where it is contained, the total content of the components (a) to (c) varies depending on the material. 1-70 mass% is preferable with respect to solid content of this, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

(Polymerizable monomer)
The colored curable composition of the present invention can be suitably constituted by containing at least one polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is configured as a negative type.

  In addition, it can further contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more. Hereinafter, the polymerizable monomer will be described.

  The polymerizable monomer is preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of 100 ° C. or higher under normal pressure. Monofunctional acrylates and methacrylates such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Ethylene oxide and propylene oxide were added to polyfunctional alcohols such as acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Later (meth) acrylates, urethane acrylates as described in JP-B-48-41708, JP-A-50-6034, JP-A-51-37193, JP-A-48-64183 Polyfunctional acrylates such as polyester acrylates described in JP-B Nos. 49-43191 and 52-30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and the like. Meta-acrylic Over preparative and can mixtures thereof.

  Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  As content in the colored curable composition of the said polymerizable monomer, 0.1-90 mass% is preferable with respect to solid content, 1.0-80 mass% is still more preferable, 2.0-70 mass% Is particularly preferred.

(Radiosensitive compounds)
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing a chemical reaction such as generation of a radical, generation of an acid, generation of a base, etc. with respect to radiation such as UV, Deep UV, visible light, infrared light, and electron beam. The coating film is made insensitive to an alkaline developer by insolubilizing the binder of the resin 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. Used for insolubilization.

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

(Photopolymerization initiator)
Next, the photopolymerization initiator contained when the colored curable composition of the present invention is a negative composition will be described.

  The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  In addition, you may further contain in the positive type system containing said naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be accelerated | stimulated more.

  As the photopolymerization initiator, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds.

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

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

  Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-) ) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho- -Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7 -Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 − [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophen L] -2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri 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-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[M-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonyl) Methylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (O-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine and the like.

  Others, TAZ series made by Midori Chemical, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ-104, T series made by PANCHIM, T -OMS, T-BMP, TR, T-B, Ciba Geigy's Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocur Series, Darocur 1173, 4,4'-bis (diethylamino) -benzophenone, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2 Dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5 -Diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p- Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenyl Imidazolyl dimer, benzoin isopropyl ether and the like are also usefully used.

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

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass with respect to the polymerizable monomer solid content. Is particularly preferred. When the content is less than 0.01% by mass, the polymerization is difficult to proceed, and when it exceeds 50% by mass, the polymerization rate increases, but the molecular weight may be lowered and the film strength may be weakened.

  A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.

  Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, and tinuvin 1130, 400. It is done.

  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.

(Naphthoquinonediazide compound)
Next, the naphthoquinone diazide compound contained when the colored curable composition of the present invention is a positive composition will be described.

  The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group. For example, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4- Examples thereof include sulfonic acid esters and o-naphthoquinonediazide-4-sulfonic acid amide. These esters and amide compounds can be produced by a known method using, for example, the phenol compounds described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. it can.

  When the colored curable composition is constituted as a positive type, the alkali-soluble phenol resin and the cross-linking agent are usually in a ratio of about 2 to 50% by mass and about 2 to 30% by mass in the organic solvent, respectively. Is preferably dissolved. The contents of the naphthoquinone diazide compound and the dye are usually preferably added at a ratio of about 2 to 30% by mass and 2 to 50% by mass, respectively, with respect to the solution in which the binder and the crosslinking agent are dissolved.

(solvent)
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent to be used is not particularly limited as long as the solubility of each component of the composition and the coating property of the colored curable composition are satisfied, but particularly considering the solubility, coating property and safety of the binder. Are preferably selected.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid Alkyl esters of 3-oxypropionic acid such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropyl Ethyl pionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene are preferable.

  Among 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 colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents Etc. can be blended.

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

  Further, when the alkali solubility of the non-irradiated part (non-image part) is promoted and the developability of the colored curable composition of the present invention is further improved, an organic carboxylic acid, preferably Addition of a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be performed.

  Specifically, 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 colored curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display device (LCD), a solid-state imaging device (for example, CCD, CMOS, etc.), printing ink, inkjet ink, In addition, it can be suitably used as a production application for paints and the like.

(Color filter and manufacturing method thereof)
The color filter of the present invention will be described in detail through its manufacturing method.

  In the method for producing a color filter of the present invention, the above-described colored curable composition of the present invention is used. The color filter of the present invention forms a radiation-sensitive composition layer by applying the colored curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, etc. By exposing through a pattern and developing with a developer, a negative or positive colored pattern (resist pattern) can be formed (image forming step). At this time, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure can be provided. As light or radiation used in this case, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used.

  In addition, when the colored curable composition is configured as a positive type, a step of post-baking the colored pattern after image formation can be provided.

  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 according to the desired number of hues, and in the case of the positive type, the image forming step and the post-bake step are desired. By repeating according to the number of hues, a color filter having a desired number of hues can be produced.

  Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached to these, and a photoelectric conversion element substrate used for an imaging element and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These supports may be formed with black stripes that separate pixels.

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

  The developer used in the method for producing the color filter of the present invention may be any developer as long as it has a composition that dissolves the uncured portion of the colored curable composition of the present invention but does not dissolve the radiation irradiated portion (cured portion). Things can also be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.

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

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

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

Example 1
1) Preparation of resist solution Propylene glycol monomethyl ether acetate (PGMEA) 5.20 parts Ethyl lactate (EL) 52.6 parts Binder [benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60:20:20) 41% EL solution] 30.5 parts Dipentaerythritol hexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant (F-475 Dainippon Ink) 0.80 part, photopolymerization initiator TAZ-107 (manufactured by Midori Kagaku) 0.58 part The above was mixed and dissolved to prepare a resist solution.

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C./20 minutes).

  Next, the resist solution obtained in 1) above was applied onto a glass substrate washed with 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 dye resist solution (colored curable composition [negative type]) 9.4 g of the resist solution obtained in 1) above and 0.75 g of Exemplified Dye 1-1 according to the present invention were mixed and dissolved. Thus, a dye resist solution (colored curable composition [negative type] solution) was prepared.

4) Exposure and development of dye resist solution (image formation)
The dye resist solution obtained in 3) above was applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1.0 μm. For 120 seconds.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm. After the exposure, development was performed using an organic alkaline developer (tetramethylammonium hydroxide aqueous solution) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.

  As described above, a pattern suitable for a magenta color filter was obtained.

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

(1) Storage stability The degree of foreign matter precipitation after the dye resist solution was stored at room temperature for 2 months was visually evaluated according to the following criteria.

◯: No precipitation was observed Δ: Slight precipitation was observed ×: Precipitation was observed

(2) Heat resistance After heating the glass substrate coated with the dye resist solution at 200 ° C. for 2 hours with a hot plate, the ΔEab value of the color difference before and after the heat test is measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). Measured and evaluated according to the following criteria. A smaller ΔEab value indicates better heat resistance.

○: ΔEab value <5
Δ: 5 ≦ ΔEab value ≦ 10
X: 10 <ΔEab value.

(3) Light resistance The glass substrate coated with the dye resist solution was irradiated with a xenon lamp at 70,000 lux for 20 hours, and then the ΔEab value of the color difference before and after the light resistance test was measured. A smaller ΔEab value indicates better light resistance.

○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
X: 10 <ΔEab value.

Examples 2 to 15 and Comparative Examples 1 to 10
The same procedure as in Example 1 was performed except that in the preparation of the dye resist solution 3) of Example 1, the dye was replaced with an equimolar amount of the dye shown in Table 1 below. The results are shown in Table 1.

  From the results of Table 1, the colored curable compositions of the examples using the dyes according to the present invention are superior in storage stability in the solution state to the comparative examples using other dyes, and further this coloring. It can be seen that the image pattern formed using the curable composition is both excellent in heat resistance and light resistance. Moreover, when the obtained pattern image was observed by optical microscope and SEM photograph observation, the resolution and the transmittance | permeability were high for this invention, but the resolution and the transmittance | permeability were low for the comparative example.

Example 16
1) Preparation of colored curable composition [positive type] Ethyl lactate (EL) 30 parts Resin P-1 (below) 3.0 parts Naphthoquinonediazide compound N-1 (below) 1.8 parts Crosslinker: Hexamethoxymethylol 0.6 parts of photoacid generator: TAZ-107 (manufactured by Midori Chemical) 1.2 parts Fluorosurfactant (F-475, Dainippon Ink and Chemicals, Inc.) 0.0005 parts Exemplary Dye 1-1 5 parts or more were mixed and dissolved to obtain a colored curable composition [positive type].

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

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

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

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

  When the storage stability of the colored curable composition using the dye in the present invention, the heat resistance, light resistance, resolution and transmittance of the coated composition were evaluated in the same manner as in Example 1, it was excellent in storage stability and light resistance. The heat resistance, heat resistance, resolution and transmittance were found to be good.

Example 17
Except that the glass substrate of Example 1 was changed to a silicon wafer substrate, the same operation as in Example 1 was performed to obtain a coated substrate of a silicon wafer with an undercoat layer.

Next, the 2 μm square pattern is exposed at an exposure amount of 500 mJ / cm ² using an i-line reduction projection exposure apparatus, and an organic alkaline developer (tetramethylammonium hydroxide aqueous solution) is used at 23 ° C. Developed for 60 seconds.

  Next, after rinsing with running water for 30 seconds, spray drying was performed. A pattern suitable for a color filter for a CCD having a square cross section was rectangular.

Examples 18-25
According to the method of Example 1 described in JP-A-2002-14222, C.I. I. Acid Blue 83 is added to equimolar amounts of the dyes according to the present invention (Exemplary dyes 1-1, 1-2, 1-30, 5-1, 5-2, 5-8, 5-9, 5-10). Except for the replacement, a positive colored curable composition was obtained according to the method of Example 1 described in JP-A-2002-14222. Using the obtained composition, a magenta filter layer was formed in the same manner as in Example 1 described in the publication.

  As a result of evaluating storage stability, heat resistance, light resistance, resolution and transmittance of the colored curable composition according to the method of Example 1 of the present invention, Examples 18 to 25 were the same as the results in Table 1 above. A good trend was observed.

Claims (7)

A colored curable composition comprising a dye represented by the following general formula (1).

(Wherein R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, R ₃ represents a hydrogen atom or a substituent, Z ₁ represents —N═ or —CR ₄ ═, and Z ₂ represents —N = Or -CR ₅ =, R ₄ and R ₅ represent a hydrogen atom or a substituent, and A represents a 5-membered or 6-membered aromatic heterocyclic ring. The colored curable composition according to claim 1, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (2).

_{(Wherein, R 1, R 2, R} 3, Z 1 and Z ₂ R ₁ in the general formula _{(1), R 2, R} 3, the same meaning as Z ₁ and Z ₂ .R ₆ substituent Z ₃ represents —N═ or —CR ₇ ═, Z ₄ represents —N═ or —CR ₈ ═, and at least one of Z ₃ and Z ₄ represents —N═, R ₇ And R ₈ represents a hydrogen atom or a substituent, and m represents an integer of 0 to 3.) The colored curable composition according to claim 2, wherein the dye represented by the general formula (2) is a dye represented by the following general formula (3).

(Wherein, R _1, R ₂ and R ₃ R _1, R ₂ and R ₃ as synonymous .R ₅ and R ₈ in the general formula (1) represents a hydrogen atom or a substituent.) The colored curable composition according to claim 1, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (4).

_{(Wherein, R 1, R 2, R} 3, Z 1 and Z ₂ R ₁ in the general formula _{(1), R 2, R} 3, Z 1 and Z ₂ as synonymous .R ₉ is hydrogen Or represents a substituent.) A colored curable composition comprising at least one metal chelate dye having a dye selected from the general formulas (1) to (4) as a ligand. A color filter comprising the colored curable composition according to any one of claims 1 to 5. 6. A color filter comprising a step of applying a colored curable composition according to any one of claims 1 to 5 on a support, exposing the film through a mask, and developing to form a pattern. Method.