JPH1172615A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter whose spectral transmissivity is made optimum in accordance with the spectrum of ambient light by forming a colorant from a mixture of specified copper phthalocyanine blue and a specified green pigment. SOLUTION: This radiation sensitive compsn. is a subtractive color mixture type radiation sensitive compsn. contg. a colorant, an alkali-soluble resin, a multifunctional monomer and a photopolymn. initiator. The colorant is a mixture of copper phthalocyanine blue represented by formula I and a green pigment represented by formula II, etc. The amt. of the green pigment is <=50 wt.%, preferably 10-50 wt.%, especially preferably 25-50 wt.% of the total amt. of the pigments and the green pigment is used for regulating the hue of the resultant picture elements. The copper phthalocyanine blue is preferably β-crystalline copper phthalocyanine blue or non-crystalline and non-aggregable copper phthalocyanine blue. The green pigment represented by the formula II corresponds to C.I. Pigment Green 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition for a color filter used for producing a subtractive color filter used in a reflection type color liquid crystal display device.

[0002]

2. Description of the Related Art A color filter used in a color liquid crystal display device has two or more kinds of pixels having different color tones arranged on a transparent substrate such as a glass substrate in parallel or crosswise in a striped pixel. The rectangular pixels are arranged vertically and horizontally, and the pixel size is as fine as several tens μm to several hundred μm. Conventionally, when manufacturing a color filter in which such fine pixels are regularly arranged, a photosensitive resin is applied on a substrate, and the formed coating film is irradiated with radiation through a photomask to irradiate the radiation with a radiation irradiation unit. Is cured and then developed to remove the unirradiated portion of the coating film and pattern it. After that, a dyeing method of dyeing or a composition in which a coloring agent (dye or pigment) is dissolved or dispersed in a photosensitive resin is used. A method such as a photolithography method in which an object is used to form a pattern by performing coating film formation, radiation irradiation, and development processing in the same manner as described above, is employed. In addition, the color liquid crystal display device includes:
Generally, in order to drive the liquid crystal, a transparent electrode made of indium oxide, tin oxide, or the like is formed on the color filter by, for example, vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. In order to obtain a high-performance transparent electrode and an alignment film, a high temperature of generally 200 ° C. or higher, preferably 250 ° C. or higher is required at the time of forming them. Among the color filters manufactured by the above method, a color filter using a dye has high transparency to radiation, but has insufficient heat resistance. Therefore, formation of a transparent electrode and an alignment film is performed at a temperature of less than 200 ° C. Inevitably, the performance of the transparent electrode and the alignment film cannot be sufficiently ensured. In addition, color filters using dyes also have poor light resistance, and are not suitable for outdoor use. Therefore, instead of dyes, pigments having excellent heat resistance and light resistance have come to be used, and most of currently manufactured color filters use organic pigments. By the way, a color liquid crystal display device is roughly divided into a light source (backlight) provided on the back surface of the device, and a transmission type color liquid crystal display device for displaying by the transmitted light and a light reflection plate such as an aluminum foil provided on the back surface of the device. There is a reflective color liquid crystal display device that is attached to the back of the transparent substrate and reflects and reflects the incident light from the front of the device.The reflective color liquid crystal display device has the advantage of low power consumption without requiring a separate light source. Has become widely adopted. Today, as a color filter used in a color liquid crystal display device, an additive color mixture type of three primary colors of red (R), green (G) and blue (B) is generally used. A reflective color liquid crystal display device using a subtractive color filter of three colors of C), magenta (M) and yellow (Y) has also been announced (see “Electronic Display Forum 97”). However, the additive color mixture type color filter used in the transmission type color liquid crystal display device is optimized for the spectrum of the three wavelength tube of the backlight which is the light source, and is not necessarily suitable for the reflection type color liquid crystal display device. I couldn't say. Therefore, the subtractive color filter used in the reflection type color liquid crystal display device has the spectral transmittance of ambient light (for example, sunlight,
There has been a strong demand for the development of a color filter that is optimized according to the spectrum of fluorescent light or the like.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a subtractive color liquid crystal display device which is excellent in heat resistance and light resistance and has a spectral transmittance optimized in accordance with the spectrum of ambient light. An object of the present invention is to provide a radiation-sensitive composition used for producing a color mixture type color filter.

[0004]

The present invention is directed to a subtractive color mixing type comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator. In the radiation-sensitive composition for a color filter, the colorant (A) is represented by the following structural formula (2) in which the colorant is copper phthalocyanine blue represented by the following structural formula (1) and 50% by weight or less of the total pigment. A radiation-sensitive composition for a subtractive color filter used in a reflective color liquid crystal display device, comprising a mixture of a green pigment and / or a green pigment represented by the following structural formula (3):

[0005]

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[0006]

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[0007]

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[0008] "Radiation" in the present invention is
It includes visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams and the like. Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention is a copper phthalocyanine blue represented by the structural formula (1), a green pigment represented by the structural formula (2) at 50% by weight or less of the total pigment, and / or It is composed of a mixture with the green pigment represented by the structural formula (3). In the present invention, the green pigment is used for the purpose of adjusting the hue of the obtained pixel. As the copper phthalocyanine blue represented by the structural formula (1), β-type copper phthalocyanine blue and non-crystalline / non-aggregated copper phthalocyanine blue are preferable. The β-type crystal copper phthalocyanine blue has a color index (CI; The Society of Dyers and Color).
(issued by companies) The number is "CI Pigment Blue 15:
The non-crystalline / non-aggregated copper phthalocyanine blue corresponds to “CI Pigment Blue 15: 4” in color index (CI) number, and among them, especially CI pigment Blue 15: 4
Is preferred.

The green pigment represented by the structural formula (2) corresponds to “CI Pigment Green 7” in a color index (CI) number, and the green pigment represented by the structural formula (3) is a color pigment. The index (CI) number corresponds to “CI Pigment Green 36”, and among them, CI Pigment Green 36 is particularly preferable. The use ratio of the green pigment in the present invention is 50% by weight or less of the total pigment, preferably 50 to 50% by weight.
It is 10% by weight, more preferably 50 to 25% by weight.

In the present invention, the surface of each of the pigments can be modified with a polymer for use. Examples of the polymer for modifying the pigment surface include, for example, JP-A-8-2598.
Examples of the polymer include a polymer described in JP-A-76-176 and various commercially available polymers or oligomers for dispersing a pigment. Further, each pigment in the present invention, if desired,
It can be used with dispersants. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants. As a specific example of the surfactant,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether;
Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters;
Tertiary amine-modified polyurethanes; polyethyleneimines, etc., and KP (Shin-Etsu Chemical Co., Ltd.)
), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink & Chemicals, Inc.), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant to be used is generally 50 parts by weight or less, preferably 0 to 30 parts by weight, based on 100 parts by weight of the total pigment.

(B) Alkali-Soluble Resin Next, as the alkali-soluble resin in the present invention,
(A) When it acts as a binder for a colorant and is soluble in a developing solution used in the developing step, particularly preferably an alkali developing solution, in producing a color filter, Although not limited, a polymer containing a carboxyl group, in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, simply referred to as “carboxyl group-containing unsaturated monomer”). Other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “copolymerizable unsaturated monomers”)
(Hereinafter, simply referred to as “carboxyl group-containing copolymer”). Examples of the carboxyl group-containing unsaturated monomer include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, Unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof; succinic acid mono (2- Divalent or higher polyvalent carboxylic acids such as acryloyloxyethyl), mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate Mono [(meth) acryloyloxyalkyl] esters of acids; ω-carboxypolycaprolactone monoacrylate, ω-carbo Shi polycaprolactone both ends dicarboxylate polymers monomethacrylate such as mono (meth) may be mentioned acrylates, and the like. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene and o-methoxystyrene. , M-
Methoxystyrene, p-methoxystyrene, indene,
aromatic vinyl compounds such as o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; methyl acrylate , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate DOO, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-
Hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl Methacrylate, 2-methoxyethyl acrylate, 2
-Methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxy Propylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-
Unsaturated carboxylic acid esters such as 3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate; 2-aminoethyl acrylate,
2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3
-Unsaturated carboxylic acid aminoalkyl esters such as -aminopropyl acrylate and 3-aminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and the like Carboxylic acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide Acrylamide, methacrylamide,
unsaturated amides or unsaturated imides such as α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethyl methacrylamide, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 1,3-butadiene; Aliphatic conjugated dienes such as isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n
And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain, such as -butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer in the present invention, acrylic acid and / or methacrylic acid are essential, and in some cases, mono (2-acryloyloxyethyl) succinate and / or mono (2-methacrylic acid) are used. Carboxyl group-containing unsaturated monomer component further containing styrene, methyl methacrylate, 2-hydroxyethyl acrylate,
A copolymer with at least one selected from the group consisting of hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “carboxyl group containing Copolymer (I) ").

Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (meth) ) Acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) ) Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth)
Acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acryl Acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / 2-acryloyloxy Ethyl succinic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / 2-acryloyloxyethylsuccinic acid / styrene / allyl methacrylate / N-phenylmaleimide copolymer It can be mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
５０50% by weight, preferably 10-40% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developer tends to decrease, while if it exceeds 50% by weight, the solubility in an alkali developer becomes poor. When developed with an alkali developing solution, the pixel tends to easily fall off from the substrate or become rough on the pixel surface. Gel permeation chromatography of the alkali-soluble resin in the present invention (GPC, elution solvent: tetrahydrofuran)
Weight average molecular weight in terms of polystyrene (hereinafter, referred to as
It is called "Mw". ) Is usually 3,000 to 300,0
00, preferably 5,000 to 100,000.
By using such an alkali-soluble resin having a specific Mw, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, and Occasionally background dirt in areas other than the areas where pixels are formed on the substrate,
Film residue and the like hardly occur. In the present invention, the alkali-soluble resins can be used alone or in combination of two or more. The amount of the alkali-soluble resin used in the present invention is usually based on 100 parts by weight of the colorant (A).
It is 10 to 1000 parts by weight, preferably 20 to 500 parts by weight. In this case, the amount of the alkali-soluble resin used is 10
If the amount is less than 10 parts by weight, for example, the alkali developability may be reduced, or background contamination or film residue may occur in a region other than the portion where the pixels are formed on the substrate. Since the pigment concentration decreases, it may be difficult to achieve the color concentration required for the color filter.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds, and examples thereof include ethylene glycol and propylene glycol. Diacrylates or dimethacrylates of alkylene glycols such as polyglycols; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; trivalent or higher polyvalent such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Polyacrylates or polymethacrylates of alcohols and their dicarboxylic acid modified products; oligoacrylates or oligomethacrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin Classes; diacrylate or dimethacrylates of hydroxyl-terminated polymers such as hydroxypolybutadiene, hydroxypolyisoprene, hydroxypolycaprolactone at both ends, trisacryloyloxyethyl phosphate, and trismethacryloyloxyethyl phosphate And the like.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof, specifically, trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, a compound represented by the following formula (4), and the like, are particularly preferable. Trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate have higher pixel strength Excellent smoothness of the pixel surface, and are unlikely to generate scumming and film remaining in the region other than a portion where pixels are formed.

[0018]

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The polyfunctional monomers can be used alone or in combination of two or more. In the present invention, if necessary, a monofunctional monomer may be used together with the polyfunctional monomer. Specific examples of such a monofunctional monomer include carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the carboxyl group-containing copolymer, and commercially available M -5300 (trade name, manufactured by Toagosei Co., Ltd.). These monofunctional monomers can be used alone or in combination of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 0 to 50% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, if the use ratio exceeds 90% by weight, the strength and surface smoothness of the obtained pixels may be insufficient. The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is,
(B) The amount is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin. In this case, if the used amount is less than 5 parts by weight, the strength and surface smoothness of the obtained pixels tend to decrease,
On the other hand, when the amount exceeds 500 parts by weight, for example, alkali developability tends to decrease, and background dirt or film residue tends to easily occur in a region other than the portion where pixels are formed on the substrate.

(D) Photopolymerization initiator The photopolymerization initiator in the present invention includes visible light, ultraviolet light,
Irradiation of radiation such as far ultraviolet rays, electron beams and X-rays (hereinafter referred to as "exposure") causes decomposition or cleavage of bonds, and polymerization of the (C) polyfunctional monomers such as radicals, cations and anions. Means a compound that generates an active species capable of initiating Examples of such a photopolymerization initiator include imidazole compounds having at least one main skeleton represented by the following formula (5), formula (6) or formula (7), benzoin compounds, acetophenone compounds, Benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds,
Triazine compounds and the like can be mentioned.

[0021]

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Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5 ′ {tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-
Bis (2-chlorophenyl) -4,4 ', 5,5'
Tetrakis (4-ethoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2,4-dichlorophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2,4
-Dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-
Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4
-Methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl)- 1,2′-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,
2'-bis (2-cyanophenyl) -4,4 ', 5.
5'-tetrakis (4-methoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4
-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-cyanophenyl) -4,
4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-
Bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-methylphenyl) -4,
4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-
Bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-ethylphenyl) -4,
4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-
Bis (2-phenylphenyl) -4,4 ', 5,5'-
Tetrakis (4-methoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-phenylphenyl) -4,
4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5 ′ {tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1 ,
2′-biimidazole, 2,2′-bis (2,4,6-
Trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-
Tetraphenyl-1,2'-biimidazole, 2,2 '
-Bis (2,4,6-tribromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-cyanophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dicyanophenyl)
-4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'- Tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4-
Dimethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-ethylphenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-diethylphenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triethylphenyl) -4,4', 5,5'-tetraphenyl −
1,2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4
-Diphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4',
5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.

Of these biimidazole compounds,
In particular, 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4-
Dibromophenyl) -4,4 ′, 5,5′-tetraphenylbi-1,2′-imidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5
5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl)
-4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole is preferred. The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, and has high sensitivity. Since the curing reaction is high and no curing reaction occurs in the unexposed area, the coated film after exposure is clearly divided into a cured area insoluble in the developer and an uncured area having a high solubility in the developer. As a result, a pixel pattern without undercuts can be obtained, and a high-definition pixel array in which the pixels are arranged according to a predetermined arrangement can be formed.

Further, specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoylbenzoate and the like. Specific examples of the acetophenone-based compound include 2,2-dimethoxy-2-phenylacetophenone and 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-i-propylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl- (4- Methylthiophenyl) -2-morpholino-1-propane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 4-azidoacetophenone, 4-azidobenzalacetophenone and the like. it can. Specific examples of the benzophenone-based compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and 3,3-dimethyl-4-.
Methoxybenzophenone and the like can be mentioned. Specific examples of the α-diketone compound include diacetyl,
Examples thereof include dibenzoyl and methylbenzoyl formate. Specific examples of the polynuclear quinone-based compound include anthraquinone, 2-ethylanthraquinone,
Examples thereof include t-butylanthraquinone and 1,4-naphthoquinone. Specific examples of the xanthone-based compound include xanthone, thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. Specific examples of the diazo compound include 4-diazodiphenylamine, 4-diazo-4′-
Methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like can be mentioned. Specific examples of the triazine-based compound include 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (3 ', 4'-dimethoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-
Bromo-4'-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like. be able to. Further, as other photopolymerization initiators, 4-azidobenzaldehyde, azidopyrene, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, N-phenylthioacridone, triphenylpyridone Lium perchlorate can also be used.

These photopolymerization initiators can be used alone or
A mixture of more than one species can be used. The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer. It is preferably 1 to 120 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, if the used amount is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel array arranged in accordance with a predetermined arrangement, while exceeding 200 parts by weight. In such a case, the formed pixels are likely to fall off the substrate during development, and background contamination and film residue are more likely to occur in a region on the substrate other than the portion where the pixels are formed.

Further, in the present invention, a sensitizer, a curing accelerator or a polymer photocrosslinking / sensitizing agent (hereinafter, these components are collectively referred to as “curing”) together with the photopolymerization initiator, if necessary. ) May be used in combination. Specific examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate,
Ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4′-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like. it can. These sensitizers can be used alone or in combination of two or more. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5
-Dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, 3-mercapto-4-methyl-4H-1,2,4 A chain transfer agent such as triazole. These curing accelerators can be used alone or in combination of two or more. Further, the polymer photocrosslinking / sensitizer is a polymer compound having at least one kind of functional group capable of acting as a crosslinking agent and / or a sensitizer upon exposure in a main chain and / or a side chain, Specific examples thereof include a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, a condensate of 4-azidobenzaldehyde and a phenol novolak resin, and a homopolymer or copolymer of 4-acryloylphenylcinnamoyl ester; −
Examples thereof include polybutadiene and 1,2-polybutadiene. These polymer photocrosslinking / sensitizers can be used alone or in combination of two or more. The amount of the curing aid used is usually 300 parts by weight or less, preferably 5-200 parts by weight, per 100 parts by weight of the photopolymerization initiator (D).
Parts by weight, more preferably 10 to 100 parts by weight.
In the present invention, the use of a combination of a biimidazole compound and a benzophenone compound and / or a thiazole curing accelerator, in particular, as a photopolymerization initiator makes it difficult for formed pixels to fall off the substrate during development.
This is preferable in that the pixel intensity and sensitivity are also increased. In the present invention, when a biimidazole-based compound is used in combination with another component as a photopolymerization initiator, the proportion of the other component used is preferably 80% by weight or less of the entire photopolymerization initiator.

Here, a particularly preferred photopolymerization initiator in the present invention is shown as a combination of its components.
The following can be mentioned. That is, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'
-Biimidazole / 4,4'-bis (diethylamino)
Benzophenone, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole /
4,4'-bis (diethylamino) benzophenone / 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2'-bis (2
-Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, , 2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'
-Biimidazole / 4,4'-bis (diethylamino)
Benzophenone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,
2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2'-bis (2 4-dichlorophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) butan-1-one / 2-
Mercaptobenzothiazole, 2,2′-bis (2,4
-Dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
Butan-1-one, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-
1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole.

Other Additives The radiation-sensitive composition for a color filter of the present invention contains an organic acid in order to further improve its solubility in an alkali developing solution and to suppress the remaining of undissolved materials after development. Can be contained. As such an organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having a molecular weight of 1,000 or less is preferable. Specific examples of the aliphatic carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid,
Monocarboxylic acids such as valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Dicarboxylic acids such as brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; tricarballylic acid And tricarboxylic acids such as aconitic acid and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include an aromatic carboxylic acid having a carboxyl group directly bonded to a phenyl group and a carboxylic acid having a carboxyl group bonded to a phenyl group via a carbon chain. Specific examples thereof include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; trimellitic acid and trimesin Trivalent or higher aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid and coumaric acid Acids, umbellic acid, and the like. Of these organic acids,
Aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble, soluble in solvents, and pixels on the substrate are formed. It is preferable from the viewpoint of prevention of background contamination and film residue in a region other than the portion. The organic acids can be used alone or in combination of two or more. The amount of the organic acid used is usually 10% by weight or less, preferably 0.001 to 10% by weight, more preferably 0.01 to 10% by weight, based on the whole radiation-sensitive composition.
1% by weight. In this case, if the amount of the organic acid used exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to decrease.

Further, the radiation-sensitive composition for a color filter of the present invention may contain various additives other than the organic acid, if necessary. Examples of such additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers and poly (fluoroalkyl acrylate); vinyl trimethoxysilane and vinyl triethoxysilane , Vinyl tris (2-methoxyethoxy)
Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)
-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl)
Adhesion promoters such as ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4 Antioxidants such as -methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2- (3-t-butyl-5-methyl-
UV absorbers such as 2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;
Aggregation inhibitors such as sodium polyacrylate; thermal crosslinking agents such as epoxy compounds, melamine compounds and bisazide compounds.

Solvent The radiation-sensitive composition for a color filter of the present invention essentially contains the above components (A) to (D) and optionally contains the above-mentioned other additives. It is prepared as a composition. As the solvent, dissolve or disperse each component constituting the radiation-sensitive composition, and do not react with these components, as long as it has a moderate volatility,
It can be appropriately selected and used. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-ethyl. n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether,
Triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n
-Propyl ether, propylene glycol mono-n-
Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
Dipropylene glycol mono-n-propyl ether,
(Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate and propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Lactic acid alkyl esters; 2-hydroxy-2
-Ethyl methyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,
Methyl-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate; I-Amyl acetate, n-butyl propionate, i-propyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as ethyl; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. Of these solvents, solubility,
From the viewpoint of pigment dispersibility, coatability, etc., ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether,
Cyclohexanone, 2-heptanone, 3-heptanone,
Ethyl 2-hydroxypropionate, 3-methyl-3-
Methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-butyl acetate, i-acetate
Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, i-propyl butyrate, ethyl butyrate, n-butyrate
-Butyl, ethyl pyruvate and the like are preferred. The solvents can be used alone or in combination of two or more.

Further, benzyl ethyl ether, dihexyl ether, acetonylacetone,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A boiling point solvent can be used in combination. Of these high boiling solvents,
γ-butyrolactone is preferred. The high boiling solvent,
They can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited,
In light of the applicability and stability of the obtained radiation-sensitive composition, the total concentration of components excluding the solvent in the composition is usually 5 to 50% by weight, and preferably 10 to 40% by weight. A ratio is desirable.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color filter of the present invention comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Is contained as an essential component, and particularly preferred examples of the composition include the following (a) to (g). (A) A radiation-sensitive composition for a color filter, wherein (B) the alkali-soluble resin contains a carboxyl group-containing copolymer (I). (B) (D) The photopolymerization initiator is 2,2′-bis (2-
(Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromophenyl)-
4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2,4-dichlorophenyl) -4,4 ', 5
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1 ,
2′-biimidazole and 2,2′-bis (2,4,
(6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole The color filter of (a) containing one or more biimidazole compounds selected from the group of Radiation-sensitive composition. (C) (D) The radiation-sensitive composition for a color filter of (A) or (B), wherein the photopolymerization initiator further contains at least one member selected from the group consisting of a benzophenone compound and a thiazole curing accelerator. . (D) (B) a carboxyl group-containing copolymer (I)
(Meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate Copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) Acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid /
2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer Coalescing,
Methacrylic acid / styrene / benzyl methacrylate / N
-Phenylmaleimide copolymer, methacrylic acid / 2-acryloyloxyethylsuccinic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / 2-acryloyloxyethylsuccinic acid / styrene / allyl methacrylate / N -The radiation-sensitive composition for a color filter according to the above (a), (b) or (c), comprising at least one member selected from the group of phenylmaleimide copolymers. (E) (C) the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate, (a), (b), and (c) above. Or (d) the radiation-sensitive composition for a color filter. (F) The radiation-sensitive composition for a color filter of (A), (B), (C), (D) or (E), wherein the colorant (A) contains CI Pigment Blue 15: 4. (G) (A) The colorant is CI Pigment Blue 15: 4.
The radiation-sensitive composition for a color filter according to (a), (b), (c), (d) or (e), comprising a mixture with CI Pigment Green 36.

[0035]

The embodiments of the present invention will be described below more specifically with reference to examples of the present invention. However, the present invention is not limited to these examples. Example 1 (A) CI Pigment Blue 15: 4 as colorant and C.I.
I. 100 parts by weight of a mixture with Pigment Green 7 in a weight ratio of 60/40, (B) methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer (copolymer weight ratio = 15/70) as an alkali-soluble resin
/ 15, Mw = 28,000) 60 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2,2 ′ as a photopolymerization initiator.
-Bis (2,4-dichlorophenyl) -4,4 ', 5
10 parts by weight of 5'-tetraphenylbiimidazole and 4,4'-bis (diethylamino) benzophenone 10
By weight, 1000 parts by weight of ethyl 3-ethoxypropionate was mixed as a solvent to prepare a liquid composition of the radiation-sensitive composition.

[Manufacture of Color Filter] Using the above liquid composition, a cyan striped color filter was manufactured on a transparent substrate as follows. The liquid composition is treated with SiO that prevents sodium ions from being eluted on the surface.
After applying the solution on the surface of the soda glass substrate on which the _two films were formed using a spin coater, the film was pre-baked in a clean oven at 80 ° C. for 10 minutes to form a film having a thickness of 0.8 μm.
m was formed. Thereafter, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet light having a wavelength of 365 nm, 405 nm, and 436 nm at a light exposure of 200 mJ / cm ² through a photomask using a high-pressure mercury lamp. Next, the substrate was immersed in a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C. for 1 minute, developed, and then developed.
It was washed with ultrapure water and dried. Thereafter, post baking was performed in a clean oven at 230 ° C. for 30 minutes to produce a cyan striped color filter on a soda glass substrate.

[Evaluation of Color Filter] The obtained color filters were evaluated as follows. Heat resistance immediately after production of the color filter chromaticity (alpha) and the chromaticity after 1 hour heat treatment at 250 ° C. of the color filter (beta)
Using a microanalyzer ("TC-1" manufactured by Tokyo Denshoku Co., Ltd.)
800M ”), and the heat resistance was evaluated based on the color difference (ΔEab) between chromaticity (β) and chromaticity (α). As a result, ΔEab was 2.65. Light resistance The color filter manufactured in the same manner as described above was irradiated with ultraviolet rays using an ultraviolet long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), and the chromaticity (γ) after 90 hours of irradiation was measured.
Using a microanalyzer ("TC-1" manufactured by Tokyo Denshoku Co., Ltd.)
800M ”), and the light resistance was evaluated based on the color difference (ΔEab) between the chromaticity (γ) and the chromaticity (α) of the color filter immediately after production. As a result, ΔEab was 2.45. Spectral transmittance The spectral transmittance of the color filter was measured using a microanalyzer ("TC-1800M" manufactured by Tokyo Denshoku Co., Ltd.). FIG. 1 shows the measurement results.

Example 2 (A) CI Pigment Blue 15: 4 as a coloring agent
Preparation of a liquid composition, production of a color filter, and evaluation of the color filter were performed in the same manner as in Example 1, except that 100 parts by weight of a mixture having a weight ratio of 70/30 with CI Pigment Green 36 was used. As a result, the heat resistance ΔEab of this color filter was 2.85, and the light resistance ΔEab was 2.57. FIG. 2 shows the measurement results of the spectral transmittance of the color filter.

Comparative Example 1 (A) CI Pigment Blue 15: 4 as a colorant
Preparation of a liquid composition, production of a color filter, and evaluation of the color filter were performed in the same manner as in Example 1 except that 100 parts by weight of a mixture having a weight ratio of 85/15 with CI Pigment Yellow 138 was used. As a result, the heat resistance ΔEab of this color filter was 3.25, and the light resistance ΔEab
Was 3.07. FIG. 3 shows the measurement results of the spectral transmittance of the color filter.

[0040]

The radiation-sensitive composition for a color filter of the present invention has excellent heat resistance and light resistance, and has a spectral transmittance optimized in accordance with the spectrum of ambient light. A subtractive color filter that is optimal for a liquid crystal display device can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a measurement result of a spectral transmittance of a color filter manufactured using the radiation-sensitive composition for a color filter of the present invention.

FIG. 2 is a diagram illustrating a measurement result of a spectral transmittance of another color filter manufactured using the radiation-sensitive composition for a color filter of the present invention.

FIG. 3 is a diagram illustrating a measurement result of a spectral transmittance of a color filter manufactured using a radiation-sensitive composition for comparison.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00 C09D 4/06 C09D 4/06

Claims (1)

[Claims] 1. A radiation-sensitive composition for a subtractive color filter containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. In the above, the colorant (A) is represented by the following structural formula (1)
A mixture of copper phthalocyanine blue represented by the following formula and 50% by weight or less of the total pigment, a green pigment represented by the following structural formula (2) and / or a green pigment represented by the following structural formula (3) A subtractive color mixture type radiation-sensitive composition for a color filter used in a reflective color liquid crystal display device characterized by the following. Embedded image Embedded image Embedded image