JP2009237420A - Colored curable composition, color filter, method for manufacturing color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition that can form a colored pattern of high definition with forward tapered cross-sectional shape and excellent film strength by exposure, development and heat treatment. <P>SOLUTION: The colored curable composition contains: (a) a polymerizable monomer or oligomer having two ethylenic unsaturated bonds in a molecule; (b) a photopolymerization initiator; (c) a thermal cross-linking agent; and (d) a colorant. The polymerizable monomer or oligomer having two ethylenic unsaturated bonds in the molecule (a) has an I/O value of 0.65 or less and a distance between the ethylenic unsaturated bonds in the molecule being 60 atoms or less, and further has two or more ring structures in the molecule. The content of the colorant (d) is 30 to 60 mass% to the total solid content of the colored curable composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a color filter having a colored pattern formed using the colored curable composition, a method for producing the same, and a liquid crystal display device.

Conventionally, colored curable compositions have been applied to various uses.
For example, a permanent pattern forming method using a photosensitive composition containing a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a colorant is known (see, for example, Patent Document 1). .
In addition to this application, for example, a colored curable composition is used to form a pixel (colored pattern) of a color filter.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. In addition, color filters for image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction of color unevenness and improvement of color resolution, and high definition is also desired. ing.

  As described above, in recent years, the demand for high color reproducibility of color filters is increasing, and colored curable compositions tend to have high pigment concentrations. However, when a colored pattern is formed by a photolithographic method using a colored curable composition with a high pigment concentration, the pigment is not sufficiently exposed because it prevents or absorbs the transmission of ultraviolet rays. There is a tendency that the deep part curability is not obtained. As a result, there is a problem that an undercut is likely to occur in the development process, and a colored pattern having a cross-sectional shape of an inverse taper is formed, resulting in poor adhesion to the substrate.

Several techniques for suppressing the occurrence of such an undercut shape have been proposed. For example, a technique for forming a rectangular or forward taper after development by adding a chain transfer agent to the photosensitive composition is disclosed (for example, see Patent Document 2).
As another proposal, a technique for forming a forward taper by including a copolymer having an imide group and an epoxy group in the photosensitive composition is disclosed. (For example, refer to Patent Document 3.)

However, with the two techniques described above, for example, when the pigment concentration is 30% or more, it is difficult to form a high-definition, forward-tapered colored pattern after development and heat treatment.
In addition, Patent Document 4 discloses a technique for forming a square-shaped or reverse-tapered partition using a composition having a very high colorant concentration. A technique for forming a fine, forward-tapered colored pattern is not described.
JP 2006-243543 A JP 2002-167404 A JP 2004-341245 A JP 2006-349895 A

That is, this invention is made | formed in view of said background art, and makes it a subject to achieve the objective shown below.
An object of the present invention is to provide a colored curable composition having a high-definition, forward-tapered cross-sectional shape and capable of forming a colored pattern with excellent film strength by exposure, development, and heat treatment. There is to do.
Another object of the present invention is to provide a color filter having a high-definition, forward-tapered cross-sectional shape and a colored pattern having excellent film strength, a method for producing the same, and the color filter. The object is to provide a liquid crystal display element.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
That is, the colored curable composition of the present invention comprises (a) a polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule, (b) a photopolymerization initiator, (c) a thermal crosslinking agent, and ( d) A polymerizable monomer or oligomer containing a colorant and having (a) two ethylenically unsaturated bonds in the molecule has an I / O value of 0.65 or less, and an ethylenically unsaturated bond in the molecule. The distance between them is 60 atoms or less, and the molecule has two or more ring structures, and the content of the colorant (d) is based on the total solid content of the colored curable composition. 30 mass% or more and 60 mass% or less.

In the colored curable composition of this invention, it is preferable that the softening point of (c) thermal crosslinking agent is -100 degreeC or more and 130 degrees C or less.
In addition, it is preferable from the viewpoint of film strength that (c) the thermal crosslinking agent has one or more ring structures in the molecule.
Furthermore, it is preferable from the viewpoint of film strength that (c) the heat crosslinkable group equivalent of the heat crosslinker is 100 or more and 1000 or less.
Furthermore, the colored curable composition of the present invention is preferably used for forming a colored pattern in a color filter.

The color filter of the present invention is characterized by having a colored pattern formed on the substrate using the colored curable composition of the present invention.
Moreover, the manufacturing method of the color filter of this invention forms arbitrary coloring patterns by repeating application | coating, prebaking, exposure, image development, and heat processing on the board | substrate using the colored curable composition of this invention. It is characterized by.
The liquid crystal display device of the present invention is equipped with the color filter of the present invention.

According to the present invention, a colored curable composition having a high-definition, rectangular or forward-tapered cross-sectional shape by exposure, development, and heat treatment, and capable of forming a colored pattern with excellent film strength. Can be provided.
In addition, according to the present invention, a color filter having a high-definition, rectangular or forward-tapered cross-sectional shape and further having a colored pattern with excellent film strength, a method for manufacturing the same, and the color filter are provided. A liquid crystal display element can be provided.

Hereinafter, the present invention will be described in detail.
<Colored curable composition>
The colored curable composition of the present invention comprises (a) a polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule, (b) a photopolymerization initiator, (c) a thermal crosslinking agent, and (d). A polymerizable monomer or oligomer containing a colorant and having (a) two ethylenically unsaturated bonds in the molecule has an I / O value of 0.65 or less, and the distance between the ethylenically unsaturated bonds in the molecule Is 60 atoms or less, and further has two or more ring structures in the molecule, and the content of the colorant (d) is 30 masses based on the total solid content of the colored curable composition. % Or more and 60% by mass or less.
Hereinafter, the components (a) to (d) will be described.

[(A) Polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule]
In the present invention, (a) a polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule has a zero I / O value for a polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule. .65 or less, the distance between ethylenically unsaturated bonds in the molecule is 60 atoms or less, and the molecule has two or more ring structures. Hereinafter, these compounds will be referred to as “specific bifunctional monomers” as appropriate.

The specific bifunctional monomer in the present invention requires an I / O value of 0.65 or less, preferably 0.63 or less, and more preferably 0.6 or less. The lower limit of the I / O value of the specific bifunctional monomer is 0.4.
When the I / O value falls within this range, the developability of the colored curable composition is good, and the shape of the colored pattern can be made excellent.

The specific bifunctional monomer in the present invention requires that the distance between ethylenically unsaturated bonds in the molecule is 60 atoms or less, preferably 8 atoms or more and 55 atoms or less, more preferably 10 atoms or more. 50 atoms or less.
If it is this range, the developability of a colored curable composition will be excellent, and the shape of a colored pattern can be made excellent.

  In the specific bifunctional monomer, the divalent group that links the ethylenically unsaturated bond in the molecule includes bisphenol A, bisphenol F, bisphenol AP, bisphenol C, bisphenol E, bisphenol S, bisphenol Z, and dihydroxybiphenyls. A divalent linking group containing a skeleton having two or more ring structures, such as dihydroxynaphthalene, and the divalent linking group has a ring structure such as an alkylene group, an ethyleneoxy group, or a propyleneoxy group. It may be combined with a divalent linking group that does not have.

  Specific examples of the specific bifunctional monomer in the present invention (Exemplary Compounds A-1 to A-6) are shown below, but the present invention is not limited thereto.

In the present invention, the specific bifunctional monomer may be used alone or in combination of two or more.
As content in the coloring curable composition of a specific bifunctional monomer, 1.0 mass%-40.0 mass% are preferable with respect to the total solid of this composition, More preferably, 1.5 mass% It is -35.0 mass%, More preferably, it is 2.0 mass%-30.0 mass%. When the content of the specific bifunctional monomer is within the above range, the curing reaction is sufficiently performed, and thermal deformation during the heat treatment is easily and sufficiently generated, and a colored pattern having a desired cross-sectional shape is obtained. be able to.

[(B) Photopolymerization initiator]
The colored curable composition of the present invention contains (b) a photopolymerization initiator.
The photopolymerization initiator used in the colored curable composition of the present invention is not particularly limited as long as it can be decomposed by energy by light irradiation to generate an initiating species, but is a known photopolymerization initiator. Etc. are preferred.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent No. 88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic ketone compounds such as, (thio) xanthone-based or acridine-based compounds described in French Patent 2,456,741, and biimidazole-based compounds including coumarin-based or lophine dimers described in JP-A-10-62986. Compound, sulfonium such as JP-A-8-015521 Machine boron complex, etc., etc. can be mentioned.

  As photopolymerization initiators, (1) acetophenone series, (2) ketal series, (3) benzophenone series, (4) benzoin series / benzoyl series, (5) xanthone series, (6) active halogen compounds [(6- 1) triazine, (6-2) halomethyloxadiazole, (6-3) coumarins], (7) acridines, (8) biimidazoles, (9) oxime esters, etc. A polymerization initiator is preferred.

  (1) As the acetophenone photopolymerization initiator, for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino Acetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. are preferred Can be listed.

  (2) Preferred examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  (3) Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy. -Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  (4) Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  (5) Preferred examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  (6) Examples of (6-1) triazine photopolymerization initiators that are active halogen compounds include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis. (Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2, 4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2 6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) ) -Phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s- A triazine etc. can be mentioned suitably.

(6-2) Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl). -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl- Preferable examples include 1,3,4-oxodiazole.
Examples of (6-3) coumarin-based photopolymerization initiators include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin and 3-chloro-5-diethylamino. Preferred examples include-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. be able to.

  (7) Preferred examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  (8) Examples of biimidazole photopolymerization initiators known as lophine dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5. Preferred examples include -diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like. be able to.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples thereof include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

  (B) As content in the colored curable composition of a photoinitiator, 0.1 mass%-15.0 mass% are preferable with respect to the total solid of this composition, More preferably, it is 0.8. It is 5 mass%-12.0 mass%, More preferably, it is 1.0 mass%-10.0 mass%. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

[(C) Thermal crosslinking agent]
The colored curable composition of the present invention contains (c) a thermal crosslinking agent.
By containing this (c) thermal crosslinking agent, the thermosetting property by the heat treatment after exposure and development is increased, and the strength of the film can be improved.
Here, the thermal crosslinking agent in the present invention is preferably a compound having one or more ring structures in the molecule from the viewpoint of pattern formability and pattern hardness. Examples of this ring structure include benzene, furan, thiophene, pyrrole, imidazole, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like.
Moreover, it is preferable that 1-150 pieces exist in a molecule | numerator from the point of pattern formation property and pattern hardness, and, as for these ring structures, it is more preferable that 1-100 pieces exist.

Examples of the heat crosslinkable group in the heat crosslinker include glycidyl (epoxy) group, oxetanyl group, isocyanate group, allyl group and the like.
These thermally crosslinkable groups are preferably compounds having a thermal crosslinkable group equivalent of 50 or more and 1000 or less from the viewpoint of the cross-sectional shape and pattern hardness. More preferably, the heat crosslinkable group equivalent is 80 to 900, and the range of 100 to 800 is more preferable.

As the thermal crosslinking agent, an epoxy compound is preferably used.
This epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, phenol novolak type, cresol novolak type, naphthalene type, dicyclopentadiene type, biphenyl type, fluorene type, and alicyclic epoxy type. is there.

  Specifically, for example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above, manufactured by Toto Kasei), Denacol EX-1101, EX-1102, EX-1103 etc. (above, produced by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (above, Daicel Chemical) In addition to these, these similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  Examples of the phenol novolac type include EPICLON N-740, N-770, N-775, N-885 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like.

  Cresol novolak types include EPICLON N-660, N-665, N-670, N-680, N-695 (above, manufactured by Dainippon Ink & Chemicals), Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), and naphthalene types such as EPICLON HP-4032, HP-4032D, HXA-4700 (above, Dainippon Ink Chemical Industries, Ltd.) and the like, and examples of the dicyclopentadiene type include HP-7200L, HP-7200, HP-7200H (above, Dainippon Ink & Chemicals).

  Examples of the biphenyl type include 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, and examples of the fluorene type include Ogsol PG100, EG100 (above, manufactured by Osaka Gas Chemical) and the like. Examples of cyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE3150 (above, manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000. ST-5080, ST-5100, etc. (above, manufactured by Toto Kasei). 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid In addition to diglycidyl ester, amine-type epoxy resins such as Epototo YH-434 and YH-434L, glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resin, and the like can also be used.

Among these, it is preferable to use those having a softening point of −100 ° C. or higher and 130 ° C. or lower, more preferably from 0 ° C. to 120 ° C., from the viewpoint of easy thermal deformation and thermosetting. It is more preferable to use a 20 to 110 degreeC thing, and it is especially preferable to use a 40 to 100 degreeC thing.
Specifically, among the above compounds, a phenol novolak type, a cresol novolak type, a naphthalene type, and an alicyclic epoxy type structure are preferable, and a cresol novolak type and an alicyclic epoxy type are more preferable.
In addition, said softening point can be measured by TMA (made by Rigaku).

  (C) As content in the colored curable composition of a thermal crosslinking agent, 0.1 mass%-20 mass% are preferable with respect to the total solid of this composition, More preferably, it is 0.5 mass%. It is -15 mass%, More preferably, it is 1 mass%-10 mass%. When the content of the thermal crosslinking agent is within the above range, the thermosetting property can be improved without impairing the photocuring property.

[(D) Colorant]
The colored curable composition of the present invention contains (d) a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the colored curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of light resistance.

-Pigment-
As the pigment that can be used in the colored curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. The pigment particle size is preferably an organic pigment considering that the color filter in which the colored curable composition of the present invention is suitably used preferably has a high transmittance, and the particle size is as small as possible. It is preferable to use one. Considering the handling property of the colored curable composition of the present invention, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 nm to 25 nm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1, 7

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of the above combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, and a diketopyrrolopyrrole pigment may be used alone, but at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone pigment A yellow pigment, or a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment may be mixed. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139, or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other pigments is preferably 100: 5 to 100: 80 from the viewpoints of light transmittance, color purity, and coloring power. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone, but a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. May be performed. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoints of light transmittance, color purity, and NTSC target hue. Moreover, as mass ratio, the range of 100: 20-100: 150 is especially preferable.

As the blue pigment, a phthalocyanine pigment may be used alone, but it may be mixed with a dioxazine purple pigment. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Further, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide can be used alone or in combination, and a combination of carbon black and titanium black is preferable. .
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60 from the viewpoint of dispersion stability.

In the present invention, if necessary, a pigment obtained by finely pulverizing the organic pigment as described above may be used.
In order to refine the organic pigment, it is preferable to use a method including a step of grinding the pigment as a highly viscous liquid composition together with the water-soluble organic solvent and the water-soluble inorganic salts.
In the present invention, it is more preferable to use the following method for refining the organic pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single The organic pigment in the mixture is ground by applying a strong shearing force using a kneader such as a twin or twin screw extruder, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a refined organic pigment.

Examples of the water-soluble organic solvent used for the above-mentioned miniaturization include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol, propylene glycolic monomethyl ether acetate and the like.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the organic pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The amount of the water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and the larger the amount, the more effective the grinding effect is. is there.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when a liquid composition containing an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is ground, a wet grinding device such as the kneader described above may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, Organic pigments can be obtained.

In addition, when the above-described organic pigment is refined, by using a resin that is at least partially soluble in a water-soluble organic solvent in the liquid composition, the surface is coated with the resin. A processed pigment with little aggregation of the pigment is obtained.
You may use this processed pigment for the colored curable composition of this invention.
Here, as the resin which is used when obtaining the processed pigment and is at least partially soluble in the water-soluble organic solvent, a known resin used as a pigment dispersant can be used.

-Dye-
In the present invention, when a dye is used as the colorant, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the colored curable composition of the present invention 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 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder polymer and / or the dye in the non-irradiated part by development. .
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto.
For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83 , 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3 , 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17 , 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; 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, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 , 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and the like and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

  Among them, as colorants, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo A colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferred.

The colorant that can be used in the present invention is a dye or a pigment having an average particle diameter r (unit: nm) satisfying 5 ≦ r ≦ 250, preferably 10 ≦ r ≦ 200, particularly preferably 15 ≦ r ≦ 150. desirable. By using a pigment having such an average particle diameter r, a colored pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture liquid prepared can be prepared, for example, by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

-Pigment dispersion-
The pigment dispersion containing the above pigment is obtained by dispersing (d) a pigment as a colorant in a solvent together with a dispersant and a pigment derivative.
The dispersant used here is used for improving the dispersibility of the pigment. For example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Nippon Lubrizol Corp.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content in the pigment dispersion liquid of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the mass of the above-mentioned pigment, and 3 mass%-70 mass% are more preferable.

In addition, a pigment derivative is added to the pigment dispersion in the present invention as necessary.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is dispersed as fine particles. It can be dispersed in the liquid, and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the dispersant by modifying the pigment surface.

  Specifically, the pigment derivative used in the present invention is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, Examples include imidazolone pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion liquid of the pigment derivative based on this invention, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

Examples of the solvent constituting the pigment dispersion in the present invention include those similar to the solvent (f) described later.
The pigment concentration in the pigment dispersion is preferably 30% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass.

The pigment dispersion in the present invention can be prepared through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, for example, a bead disperser using zirconia beads or the like (for example, manufactured by GETZMANN Co., Ltd.) is prepared by previously mixing a pigment and a dispersant as necessary, and further dispersing in advance with a homogenizer or the like. The pigment dispersion liquid can be prepared by finely dispersing using a disperse mat).
The dispersion time is preferably about 3 to 6 hours.
The fine dispersion treatment with beads is mainly made of vertical or horizontal sand grinders, pin mills, slit mills, ultrasonic dispersers, etc., and beads made of glass having a particle diameter of 0.01 mm to 1 mm, zirconia, etc. Can be used.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

The content (pigment concentration) of the colorant (d) is required to be 30% by mass to 60% by mass, preferably 35% by mass to 60% by mass with respect to the total solid content of the colored curable composition. It is 40 mass%, More preferably, it is 40 mass%.
When the concentration of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.
In the present invention, when a pigment derivative is used, the pigment concentration of the colored curable composition in the present invention is a value obtained by dividing the total mass of the pigment and the pigment derivative by the total solid content of the colored curable composition. Is used.

[(E) Binder polymer]
The colored curable composition of the present invention preferably contains (e) a binder polymer.
The binder polymer is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ² = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  As content in the colored curable composition of alkali-soluble resin which is a binder polymer, 1 mass%-15 mass% are preferable with respect to the total solid of this composition, More preferably, 2 mass%-12 It is mass%, Most preferably, it is 3 mass%-10 mass%.

[(F) Solvent]
The colored curable composition of the present invention can be suitably prepared using (f) a solvent, if necessary, together with the above components.
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, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropio Acid ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2 -Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of 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 acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

[Other ingredients]
In the colored curable composition of the present invention, if necessary, a sensitizing dye, a hydrogen donating compound, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization inhibitor, other fillers, the above-mentioned alkali-soluble resin Various additives such as a polymer compound other than (binder polymer), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

-Sensitizing dye-
A sensitizing dye may be added to the colored curable composition of the present invention as necessary. The sensitizing dye can promote the radical generation reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 nm to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 nm to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or —NR ⁶⁰ —, R ⁶⁰ represents an alkyl group or an aryl group, and L ⁰¹ represents the basicity of the dye in combination with adjacent A ¹ and the carbon atom. Represents a non-metallic atomic group forming a nucleus, R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶¹ and R ⁶² are bonded to each other to form an acidic nucleus of a dye. W may represent an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, ^{-L 02} - are connected via a bond by wherein ^{-L 02} -. Is -O- or -S- In addition, W is synonymous with that shown in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or —NR ⁶⁹ —, L ⁰³ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ each independently represent a monovalent non-metallic atomic group, and R ⁶⁹ represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁷³ —, and R ⁷³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. , L ⁰⁴ and L ⁰⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and a carbon atom, and R ⁷¹ and R ⁷² each independently represent 1 A non-metallic atomic group which can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A ⁵ represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —, and Y represents An oxygen atom, a sulfur atom, or ═N (R ⁷⁴ ), each of R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ independently represents a hydrogen atom or a monovalent non-metallic atomic group, A ⁵ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ represent a monovalent non-metallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ⁷⁴ , R ⁷⁵ and R ⁷⁶ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and examples of the heteroaryl ring in the particularly preferred heteroaryl group include Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ obtained by combining the above substituents with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, Xoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N- Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N -Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group , Methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl Group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl Group, etc. can be mentioned.

Specific examples of preferred aryl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferable substituted aryl group as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ⁷⁵ and R ⁷⁶ include a substituted or unsubstituted alkyl group. A more preferred example of R ⁷⁴ includes a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, ^{A 5} will be described in the general formula (XVIII). A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent, and specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ⁷⁴ in formula (XVIII). , R ⁷⁵ , or R ⁷⁶ may be the same as those exemplified in the above description.
Among them, preferable A ⁵ includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A ⁵ includes an aryl group having an amino group.

Next, Y in the general formula (XVIII) will be described. Y is a nonmetallic atom or a nonmetallic atomic group directly bonded to the nitrogen-containing heterocycle in the general formula (XVIII) via a double bond, and represents an oxygen atom, a sulfur atom, or = N (R ⁷⁴ ).
Moreover, X in general formula (XVIII) represents an oxygen atom, a sulfur atom, or -N ( ^R74 )-.

  Next, the compound represented by the general formula (XVIII-1), which is a preferred embodiment of the compound represented by the general formula (XVIII) used in the present invention, will be described.

In General Formula (XVIII-1), A ⁵ represents an aromatic ring or a hetero ring that may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —. R ⁷⁴ , R ⁷⁷ , and R ⁷⁸ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁷ , and R ⁷⁸ are each aliphatic or aromatic. Can be linked to form a sex ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In general formula (XVIII-1), A ⁵ and R ⁷⁴ have the same meanings as in general formula (XVIII), R ⁷⁷ is R ⁷⁵ in general formula (XVIII), and R ⁷⁸ is R in general formula (XVIII). ^It is synonymous with ⁷⁶ . Ar represents an aromatic ring or a hetero ring having a substituent, and has the same meaning as A ⁵ in formula (XVIII).
However, as a substituent that can be introduced into Ar in the general formula (XVIII-1), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary Compound (F1) to Illustrative Compound (F56)] are shown below, but the present invention is not limited to these. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep curability.

  The above sensitizing dye can be subjected to various chemical modifications as follows for the purpose of improving the characteristics of the colored curable composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and still more preferably based on the total solid content of the colored curable composition. Is 0.1% by mass to 5% by mass.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

-Hydrogen donating compound-
The colored curable composition of the present invention preferably contains a hydrogen donating compound. In the present invention, the hydrogen-donating compound has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such hydrogen donating compounds include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of the hydrogen donating compound include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142277, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Further examples of the hydrogen donating compound include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B-55. -34414, a hydrogen donor described in JP-A-6-308727, and a sulfur compound (eg, trithiane).

  The content of these hydrogen-donating compounds is 0.1% by mass to 30% by mass with respect to the mass of the total solid content of the colored curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 1 mass%-25 mass% is more preferable, and the range of 0.5 mass%-20 mass% is still more preferable.

-Fluorine organic compounds-
The colored curable composition of the present invention can also contain a fluorine-based organic compound.
By containing this fluorinated organic compound, the liquid properties (particularly fluidity) when the colored curable composition of the present invention is used as a coating liquid can be improved, and the uniformity of coating thickness and liquid-saving properties can be improved. Can be improved. That is, since the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coating property to the surface to be coated is improved. Even when a thin film is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content in the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorine-based organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, manufactured by Dainippon Ink and Chemicals), Fluorard FC430, FC431, FC171 (Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.

  As described above, the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Furthermore, it is also effective when applied to slit coating that easily causes liquid breakage.

  The addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored curable composition. is there.

-Thermal polymerization initiator-
It is also effective to contain a thermal polymerization initiator in the colored curable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

-Surfactant-
The colored curable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coating properties, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include the Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, and the Fluorad (registered trademark) series manufactured by 3M.

  Moreover, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, Nonionic surfactants such as 150R1 and anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) can also be used.

-Other additives-
In addition to the above, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, Alkali-soluble resins such as those obtained by adding an acid anhydride to a polymer having a hydroxyl group, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA High polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Molecular dispersant; Solsperse 3000 Various Solsperse dispersants such as 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95 , F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.); 2- (3-t- UV absorbers such as butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

Further, when the alkali solubility of the uncured part is promoted and the developability of the colored curable composition is further improved, the colored curable composition may have an organic carboxylic acid, preferably a low molecular weight of 1000 or less. It is preferable to add an organic carboxylic acid.
Specific examples of the organic carboxylic acid include 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, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, Aromatic polymers such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid Rubonic acid; Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

-Thermal polymerization inhibitor-
In addition to the above, a thermal polymerization inhibitor can also be added to the colored curable composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

(Preparation of colored curable composition)
The colored curable composition of the present invention contains the aforementioned (a) to (d), and can be further prepared by mixing additives such as a solvent and a surfactant as necessary. it can.
In the case where (d) the colorant is a pigment, first, after preparing a pigment dispersion as described above, the colored curable composition of the present invention may be obtained using this pigment dispersion.
When the pigment dispersion is used for the preparation of the colored curable composition of the present invention, the content thereof is 30% by mass or more and 60% by mass with respect to the total solid content (mass) of the colored curable composition. An amount that is in the range of mass% or less is preferable, an amount in which the pigment content is in the range of 35 mass% to 60 mass% is more preferable, and a pigment content is in the range of 40 mass% to 60 mass%. A more preferred amount.
When the content of the pigment dispersion is within this range, the color density is sufficient and effective in securing excellent color characteristics.

<Color filter and manufacturing method thereof>
The color filter of the present invention has a colored pattern formed on the substrate by the above-described colored curable composition of the present invention.
Moreover, the manufacturing method of the color filter of this invention uses the above-mentioned colored curable composition of this invention, and forms arbitrary colored patterns by repeating application | coating, prebaking, exposure, and image development.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

As described above, the method for producing a color filter of the present invention includes the steps of coating, pre-baking, exposure, and development. By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. In addition, a color filter formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the colored curable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Further, the solid content of the colored curable composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.

When forming the coating film by the coloring curable composition of this invention on a board | substrate, as thickness (after prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 μm to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. High frequency processing can be used alone.

[Exposure process]
In the exposure step, the coating film made of the colored curable composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

[Development process]
In the development step, the uncured portion of the coated film after exposure is eluted into the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the colored curable composition in the uncured part while not dissolving the cured part.
Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen 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, in a concentration of 0.001% by mass to 10% by mass, preferably 0 An alkaline aqueous solution dissolved so as to be 0.01 mass% to 1 mass% can be mentioned.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development processing, the substrate is dried through a rinsing process for washing and removing excess developer.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

[Heat treatment]
After drying as described above, heat treatment at 100 ° C. to 250 ° C. is usually performed.
In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.
Such post-baking is a process for the purpose of complete curing and for the purpose of forward-tapering the pattern shape after development by thermal deformation, and heating (hard baking) at 200 ° C. to 250 ° C. It is common to do.

  Since the colored curable composition of the present invention contains the components (a) to (d), in the heating step, the pattern shape after development is forward-tapered by thermal deformation, and then thermally cured. As a result, it is possible to form a fine colored pattern having a fine cross section and a high hardness.

  By repeating the above steps in order for each color according to the desired number of hues, a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed can be produced.

As the application of the colored curable composition of the present invention, the description has mainly focused on the application to the color pattern of the color filter, but also for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

<Liquid crystal display device>
The liquid crystal display device of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter of the present invention, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display device of the present invention. It is done.

  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
<Preparation of colored curable composition 1>
Ingredients having the following composition were mixed, and a rotational speed of 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
〔composition〕
Pigment Green 36 (average primary particle diameter 25 nm) 70 parts Pigment Yellow 150 (average primary particle diameter 25 nm) 30 parts Phthalocyanine derivative 10 parts (Solsperse 3000, manufactured by Avicia Co., Ltd.)
A solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw 5,000) in propylene glycol monomethyl ether acetate (solid content 40%)
75 parts Dispersant (BYK-161, manufactured by BYK) 35 parts Propylene glycol monomethyl ether acetate 495 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours by a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a green pigment dispersion composition.
Components of the following composition were further added to the obtained green pigment dispersion composition and mixed by stirring to prepare a colored curable composition 1 (color resist solution) of the present invention. The pigment concentration in the total solid content of the obtained colored curable composition 1 was 48%.

〔composition〕
-30 parts of exemplary compound A-1 of said Table 1 (Shin-Nakamura Chemical Co., Ltd. A-BPE-4, specific bifunctional monomer)
・ 10 parts of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator)
・ 5 parts of 4,4′-bis (diethylamino) benzophenone (sensitizing dye) ・ 5 parts of 2-mercaptobenzothiazole (hydrogen donating compound) 5 parts of EHPE3150 (manufactured by Daicel Chemical Industries, Ltd. Point: 60-90 ° C., epoxy equivalent: 180, molecular weight: 3100)
・ 230 parts of propylene glycol monomethyl ether acetate

The pigment concentration in the colored curable composition 1 was calculated as follows.
Pigment (PG36 + PY150 + phthalocyanine derivative) = 110 parts Solid content = Pigment (110 parts) + Benzyl methacrylate / methacrylic acid copolymer (75 × 0.4 = 30 parts) + Dispersant (35 parts) +55 parts (specific bifunctional monomer) + Photopolymerization initiator + sensitizing dye + hydrogen donating compound + thermal crosslinking agent) = 230 parts Pigment concentration = 110/230 × 100 = 48%

(Example 2)
The colored curable composition 2 was the same as Example 1 except that the exemplified compound A-1 which was the specific bifunctional monomer used in Example 1 was replaced with the exemplified compound A-2 shown in Table 1 above. Was made.

(Example 3)
A colored curable composition 3 was prepared in the same manner as in Example 1 except that Exemplified Compound A-1 as the specific bifunctional monomer used in Example 1 was replaced with Exemplified Compound A-3 described in Table 1 above. Was made.

Example 4
The colored curable composition 4 was used in the same manner as in Example 1 except that Exemplified Compound A-1 as the specific bifunctional monomer used in Example 1 was replaced with Exemplified Compound A-4 shown in Table 1 above. Was made.

(Example 5)
The colored curable composition 5 was used in the same manner as in Example 1 except that Exemplified Compound A-1 as the specific bifunctional monomer used in Example 1 was replaced with Exemplified Compound A-5 shown in Table 1 above. Was made.

(Example 6)
The colored curable composition 6 was the same as Example 1 except that the exemplified compound A-1 that was the specific bifunctional monomer used in Example 1 was replaced with the exemplified compound A-6 shown in Table 1 above. Was made.

(Example 7)
EHPE3150 which is a thermal cross-linking agent used in Example 1 is replaced with EPICLON N-660 (softening point: 60 to 90 ° C., epoxy equivalent: 190 to 250, molecular weight: 3400) manufactured by Dainippon Ink & Chemicals, Inc. having the following structure. A colored curable composition 7 was prepared in the same manner as in Example 1 except for the above.

(Example 8)
Except that EHPE3150 which is a thermal crosslinking agent used in Example 1 was replaced with HXA-4700 (softening point: 85 to 98 ° C., epoxy equivalent: 155 to 170) manufactured by Dainippon Ink & Chemicals Co., Ltd. having the following structure. In the same manner as in Example 1, a colored curable composition 8 was produced.

(Comparative Example 1)
<Preparation of colored curable composition R1>
Based on the following composition, colored curable composition R1 was prepared.

[Composition of colored curable composition R1]
-Barium sulfate dispersion ⁽¹⁾ 66.7 parts-PR300 36.38 parts (Propylene glycol monomethyl ether acetate solution containing 3% Solvesso 150 having an epoxy acrylate solid content of 68%, Showa Polymer Co., Ltd.)
・ 76% propylene glycol monomethyl ether acetate solution of dipentaerythritol hexaacrylate 20.96 parts ・ IRGACURE 819 (manufactured by Ciba Specialty Chemicals) 5.07 parts ・ Epicron EXA850S (manufactured by Dainippon Ink & Co.) 7.36 parts ・ DICY7 (Manufactured by Shikoku Kasei Co., Ltd.) 1.45 parts · 2 MAOK (manufactured by Shikoku Kasei Co., Ltd.) 0.41 parts · 30% methyl ethyl ketone solution of F780F (manufactured by Dainippon Ink & Co.) 0.17 parts blue pigment dispersion ⁽²⁾ 0 parts, methyl ethyl ketone 40 parts

(1): 30 parts of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), styrene / maleic anhydride / butyl acrylate copolymer (molar ratio: 40/32/28) and benzylamine (anhydrous of the copolymer) After adding 34.29 parts of 35% methyl ethyl ketone solution of the addition reaction product and 1.05 equivalents of the product group in advance to 35.71 parts of 1-methoxy-2-propyl acetate, the motor mill M-200 (Manufactured by Eiger Corp.) and using zirconia beads having a diameter of 1.0 mm and dispersing at a peripheral speed of 9 m / s for 3.5 hours.
(2): 14 parts of a blue pigment (HELIOGEN BLUE L6700F; CI Pigment Blue 15: 6), 13.79 parts of the PR300 (68% solid content solution), and 112.21 parts of propylene glycol monomethyl ether acetate Were mixed in advance, and then dispersed with a motor mill (M-200, manufactured by Eiger) using zirconia beads having a diameter of 0.3 mm for 180 minutes at a peripheral speed of 9 m / s.

The pigment concentration in the colored curable composition R1 was calculated as follows.
Pigment (PB15: 1) = 0.1 part Solid content = Pigment (0.1 part) + Barium sulfate (20 parts) + Binder (8 parts) + Heat-crosslinking agent (24.8 parts) + Others (30.3) Part) = 83.2 parts Pigment concentration = 0.1 / 83.2 × 100 = 0.12%

(Comparative Example 2)
<Preparation of colored curable composition R2>
A colored curable composition R2 was prepared as follows.

(Synthesis of Resin A including a structure having a radical polymerizable group)
-Cresol-novolak resin "EP4050G" (Asahi Organic Materials Co., Ltd.) 20 parts-Cyclohexanone 100 parts The above materials are mixed,
(Meth) acryloyloxyalkyl isocyanate (manufactured by Showa Denko KK, trade name: “Karenz MOI”) was added at 20 mol% with respect to the hydroxyl group of the cresol novolak resin, and 0.1 part of (catalyst (triethylamine) was added at 60 ° C. The reaction was performed for 6 hours.

  The obtained compound was purified by reprecipitation with a chloroform solvent to obtain a resin A containing a structure having a radical polymerizable group. Determination of the introduction rate of the compound having radical polymerizability was measured by 1H-NMR, and it was found from the area ratio that it was 20% with respect to the hydroxyl group of the cresol novolak resin. Subsequently, using the resin A including a structure having a radical polymerizable group, each material was mixed at the following composition ratio and sufficiently kneaded with three rollers to prepare a colored curable composition R2.

(Composition of colored curable composition R2)
Resin A containing a structure having a radical polymerizable group 20 parts Cyclohexanone (Wako Pure Chemical Industries, Ltd.) 400 parts Photopolymerization monomer 20 parts (Pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name “V # 300”) ))
・ Photopolymerization initiator 0.6 parts (product name “Irgacure 369” manufactured by Ciba Specialty Chemicals)
・ 90 parts of carbon pigment “MA-8” (manufactured by Mitsubishi Materials) ・ 0.9 part of dispersant “Solsperth # 5000” (manufactured by Zeneca) ・ Fluorine-containing compound (product name “F179”, manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts

The pigment concentration in the colored curable composition R2 was calculated as follows.
Carbon pigment = 90 parts Solid content = carbon pigment (90 parts) + resin A (20 parts) containing a structure having a radical polymerizable group + dispersant (0.9 parts) + monomer, initiating system, surfactant (21 .1 part) = 132 parts Pigment concentration = 90/132 × 100 = 68%

(Comparative Example 3)
<Preparation of colored curable composition R3>
Ingredients having the following composition were mixed, and a rotational speed of 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
〔composition〕
Pigment Green 36 (average primary particle diameter 25 nm) 70 parts Pigment Yellow 150 (average primary particle diameter 25 nm) 30 parts Phthalocyanine derivative 10 parts (Solsperse 3000, manufactured by Avicia Co., Ltd.)
A solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw 5,000) in propylene glycol monomethyl ether acetate (solid content 40%)
75 parts Dispersant (BYK-161, manufactured by BYK) 35 parts Propylene glycol monomethyl ether acetate 495 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours by a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a green pigment dispersion composition.
Components of the following composition were further added to the obtained green pigment dispersion composition, and mixed by stirring to prepare a colored curable composition R3 (color resist solution) of the present invention. In addition, the pigment density | concentration in the total solid of obtained colored curable composition R3 was 48%.

〔composition〕
-30 parts of exemplary compound A-1 of said Table 1 (Shin-Nakamura Chemical Co., Ltd. A-BPE-4, specific bifunctional monomer)
2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 13 parts (photopolymerization initiator)
・ 6 parts of 4,4′-bis (diethylamino) benzophenone (sensitizing dye) ・ 6 parts of 2-mercaptobenzothiazole (hydrogen-donating compound) 230 parts of propylene glycol monomethyl ether acetate

The pigment concentration in the colored curable composition R3 was calculated as follows.
Pigment (PG36 + PY150 + phthalocyanine derivative) = 110 parts Solid content = Pigment (110 parts) + Benzyl methacrylate / methacrylic acid copolymer (75 × 0.4 = 30 parts) + Dispersant (35 parts) +55 parts (specific bifunctional monomer) + Photopolymerization initiator + sensitizing dye + hydrogen-donating compound) = 230 parts Pigment concentration = 110/230 × 100 = 48%

(Comparative Example 4)
<Preparation of green pigment dispersion composition>
Ingredients having the following composition were mixed, and a rotational speed of 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
〔composition〕
Pigment Green 36 (average primary particle diameter 25 nm) 70 parts Pigment Yellow 150 (average primary particle diameter 25 nm) 30 parts Phthalocyanine derivative 10 parts (Solsperse 3000, manufactured by Avicia Co., Ltd.)
A solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw 5,000) in propylene glycol monomethyl ether acetate (solid content 40%)
75 parts Dispersant (BYK-161, manufactured by BYK) 35 parts Propylene glycol monomethyl ether acetate 495 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours by a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a green pigment dispersion composition.
Components of the following composition were further added to the obtained green pigment dispersion composition, and mixed by stirring to prepare a colored curable composition R4 (color resist solution) of the present invention. The pigment concentration in the total solid content of the obtained colored curable composition R4 was 48%.

〔composition〕
・ Tetramethylol methane tetraacrylate 30 parts (Shin Nakamura Chemical Co., Ltd. A-TMMT, tetrafunctional acrylate)
・ 10 parts of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator)
・ 5 parts of 4,4′-bis (diethylamino) benzophenone (sensitizing dye) 5 parts of 2-mercaptobenzothiazole (hydrogen donating compound) 5 parts of EHPE-3150 (manufactured by Daicel Chemical Industries) (thermal crosslinking agent) 230 parts of propylene glycol monomethyl ether acetate

The pigment concentration in the colored curable composition R4 was calculated as follows.
Pigment (PG36 + PY150 + phthalocyanine derivative) = 110 parts Solid content = Pigment (110 parts) + Benzyl methacrylate / methacrylic acid copolymer (75 × 0.4 = 30 parts) + Dispersant (35 parts) +55 parts (tetrafunctional monomer + Photopolymerization initiator + sensitizing dye + hydrogen donating compound + thermal crosslinking agent) = 230 parts Pigment concentration = 110/230 × 100 = 48%

(Comparative Example 5)
A colored curable composition was prepared in the same manner as in Example 1 except that the exemplified compound A-1 which was the specific bifunctional monomer used in Example 1 was replaced with the comparative monomer C-1 shown in Table 2 below. R5 was produced.

(Comparative Example 6)
A colored curable composition was prepared in the same manner as in Example 1 except that Example Compound A-1 which was a specific bifunctional monomer used in Example 1 was replaced with Comparative Monomer C-2 described in Table 2 below. R6 was produced.

<Formation of colored curable composition layer>
-Application-
The colored curable composition obtained as described above was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions. Thereafter, vacuum drying and pre-baking (100 ° C., 80 seconds) were performed to form a colored curable composition layer.

(Slit application conditions)
Gap at the opening of the coating head tip: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry film thickness): 2.0 μm
Application temperature: 23 ° C

-Exposure and development-
Thereafter, an ultra high pressure mercury lamp with an energy of 20 mW / cm ² is used as a light source, and an exposure amount of 50 mJ / cm ² is irradiated in a pattern form to the colored curable composition layer through a mask (width 20 um). The entire surface of the colored curable composition layer was shower-developed with a 1.0% aqueous solution of KOH developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) and washed with pure water.

  The colored curable composition layer subjected to the development treatment was heated in an oven at 230 ° C. for 0.5 hour (post-baking). As a result, a colored pattern was formed on the glass substrate to obtain a color filter.

-Evaluation-
The line width, cross-sectional shape and film strength of the colored pattern formed on the glass substrate, and the ITO sputtering suitability were evaluated as follows. The results are summarized in Table 3.

<Line width of coloring pattern>
The line width of the colored pattern after exposure, development, and heat treatment (post-bake) was measured.
○: A high-definition coloring pattern having a width of 19 to 21 μm was obtained.
X: A high-definition coloring pattern was not obtained with a width of 21 μm or more.

<Cross-sectional shape of the colored pattern>
The cross-sectional shape of the formed colored pattern was observed with a field emission scanning electron microscope S-4800 (manufactured by HITACHI) and evaluated.
○: Tapered angle in the range of 30 to less than 85 degrees (forward taper)
X: The taper angle exceeds 85 degrees (rectangular or reverse taper)

<Colored pattern film hardness, ITO sputtering suitability>
The micro hardness of the formed colored pattern was evaluated according to the following criteria using a nanoindenter (Nanoindenter SA2, manufactured by MTS SYSTEM).
○: Coloring pattern hardness (H) is 0.25 GPa or more, and has sufficient pattern hardness.
X: Coloring pattern hardness (H) is less than 0.25 GPa, and pattern hardness is insufficient.

In addition, an ITO transparent electrode was sputtered on the color filter on which the colored pattern was formed, using MH90-1117 (manufactured by ULVAC).
When the color pattern hardness (H) was 0.25 GPa or more, no wrinkles were observed on the surface of the color pattern after the ITO transparent electrode was formed by sputtering. However, when the pattern hardness (H) is less than 0.25 GPa, wrinkles were observed on the surface of the colored pattern after the ITO transparent electrode was formed by sputtering. As a result, it is presumed that a liquid crystal display element using this color filter causes a liquid crystal display defect.

  As can be seen from the results in Table 3, it can be seen that the colored curable compositions of the examples have a small line width, excellent cross-sectional shape of the colored pattern, and high film strength.

Claims (8)

(A) a polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule, (b) a photopolymerization initiator, (c) a thermal crosslinking agent, and (d) a colorant,
(A) The polymerizable monomer or oligomer having two ethylenically unsaturated bonds in the molecule has an I / O value of 0.65 or less, and the distance between ethylenically unsaturated bonds in the molecule is 60 atoms or less. And further having two or more ring structures in the molecule, and
The colored curable composition, wherein the content of the colorant (d) is 30% by mass or more and 60% by mass or less with respect to the total solid content of the colored curable composition.   The colored curable composition according to claim 1, wherein the softening point of the thermal crosslinking agent (c) is -100 ° C or higher and 130 ° C or lower.   The colored curable composition according to claim 1, wherein the thermal crosslinking agent (c) has one or more ring structures in the molecule.   The colored curable composition according to any one of claims 1 to 3, wherein the thermal crosslinkable group equivalent of the (c) thermal crosslinking agent is 50 or more and 1000 or less.   The colored curable composition according to any one of claims 1 to 4, wherein the colored curable composition is used for forming a colored pattern in a color filter.   A color filter comprising a colored pattern formed using the colored curable composition according to any one of claims 1 to 5 on a substrate.   Using the colored curable composition according to any one of claims 1 to 5, an arbitrary colored pattern is formed on a substrate by repeating coating, prebaking, exposure, development, and heat treatment. A method for producing a color filter characterized by the above.   A liquid crystal display device comprising the color filter according to claim 6.