JPH10293397A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image forming material having high resolution and surface smoothness, and restrain the occurrence of projections from the surface of the image forming material by specifying the angle of contact of methylene iodide for a hardened film cured under exposure to a radiation. SOLUTION: This radiation sensitive composition used for a color filter is prepared so as to contain a coloring agent A, a binder polymer B, a multifunctional monomer C, a photochemical polymerization initiator D, a solvent E and a surface active agent F, and to have an angle equal to or less than 55 degrees as the angle of contact of methylene iodide for a hardened film cured under exposure to a radiation. In other words, the angle of contact of methylene iodide for the hardened film cured under exposure to a radiation is equal to or less than 55 degrees and in particular, when a red coloring agent is used as an A-component, the angle of contact of methylene iodide for the obtained hardened film is preferably taken at 45 degrees or less. Also, when a green or blue coloring agent is used as the A-component, the angle of contact of methylene iodide for the obtained hardened film is preferably taken at 50 degrees or less.

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 for producing a color filter used for a color liquid crystal display device, a color image pickup tube element and the like.

[0002]

2. Description of the Related Art Generally, a color filter having a pixel array of three primary colors of red, green and blue is used in a color liquid crystal display device or a color solid-state image pickup tube device. As a method of manufacturing such a color filter, for example, using a negative-type radiation-sensitive composition, a photolithography technique is used to form a red, green and blue pixel array on a substrate in accordance with a pixel pattern. Lithography method, after forming a transparent electrode according to the pixel pattern on the substrate, by electrodeposition method of electrodepositing an anionic polymer containing a colorant on the transparent electrode, screen printing, offset printing, etc.
A printing method of applying each of red, green and blue inks on a substrate according to a pixel pattern is known. As a photolithography method, a method using a negative-type radiation-sensitive composition in which a coloring agent is dispersed (hereinafter, a method using a negative-type radiation-sensitive composition)
It is called "colorant dispersion method". A dyeing method is known in which a dye-receiving layer is formed on a substrate according to a pixel pattern using a radiation-sensitive composition, and then the dye-receiving layer is dyed.
Among these, the spectral characteristics, resolution, flatness, and robustness (heat resistance, light resistance, chemical resistance, etc.) of the obtained pixel formed body,
The colorant dispersion method is mainly used because the production cost and the like are well balanced.

According to such a colorant dispersion method, a color filter is manufactured as follows. First, a light-shielding layer is formed on a surface of a substrate so as to partition a pixel formation portion, and a radiation-sensitive composition in which, for example, a red pigment is dispersed is applied on the substrate. Next, the obtained coating film is irradiated with curing radiation through a photomask to perform a radiation irradiation treatment, and then, for example, is subjected to a development treatment using an alkali developer to remove a portion of the coating film where the radiation is not irradiated. The removal forms a red pixel array in which the red pixel formers are arranged according to a particular pattern. Further, using each of the radiation-sensitive composition in which the green pigment is dispersed and the radiation-sensitive composition in which the blue pigment is dispersed, coating, irradiation, and development of the radiation-sensitive composition are performed in the same manner as described above. By doing so, a green pixel array and a blue pixel array are formed on the same substrate, whereby a color filter is manufactured.

However, in the conventional radiation-sensitive composition used for the production of a color filter, the resolution and the surface smoothness of the obtained pixel forming body are not sufficient, and the surface of the pixel forming body has an insufficient resolution. There is a problem that projections are likely to occur and a high yield cannot be obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
A pixel forming body having high resolution and excellent surface smoothness can be formed, and furthermore, the occurrence of projections on the surface of the pixel forming body is suppressed, so that a color filter can be manufactured with a high yield. To provide a radiation-sensitive composition for a color filter that can be used.

[0006]

The radiation-sensitive composition for a color filter of the present invention comprises (A) a colorant, (B) a binder polymer, (C) a polyfunctional monomer, and (D)
It contains a photopolymerization initiator, (E) a solvent, and (F) a surfactant, and the contact angle of methylene iodide to a cured film obtained by curing by irradiation of radiation is 55 ° or less. It is characterized by.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the radiation-sensitive composition for a color filter of the present invention will be described in detail. In the radiation-sensitive composition for a color filter of the present invention, a component (A) composed of a colorant, a component (B) composed of a binder polymer, a component (C) composed of a polyfunctional monomer, and a photopolymerization initiator Component (D), component (E) composed of a solvent, and component (F) composed of a surfactant are used as essential components.

[Colorant] The colorant used as the component (A) is not particularly limited in its color tone, and is appropriately selected depending on the use of the color filter. One or both can be used as component (A). Here, "organic colorant"
The term “colorant” means a colorant made of an organic substance, and specifically includes a dye, an organic pigment, a natural pigment, and the like. Further, the “inorganic colorant” means a colorant made of an inorganic substance, and specifically includes an inorganic pigment called an extender pigment in addition to an inorganic pigment. Among these, it is preferable to use an organic colorant in that the color developing property required for the color filter is obtained,
In particular, it is preferable to use an organic pigment in that the heat resistance required for a color filter can be obtained.

Such organic pigments include, for example, a color index (CI; The Society of).
(Published by Dysers and Colorists)
And various compounds classified as Pigment can be used. Specific examples of the compounds are indicated by color index (CI) numbers. I. Pigment Yellow 12, C.I. I. Pigment Yellow 1
3, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20,
C. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment yellow 55, C.I.
I. Pigment yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment yellow 109, C.I.
I. Pigment yellow 110, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150,
C. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment Yellow 15
5, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 168; I. Pigment Orange 3
6, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment orange 71;
C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 14
9, C.I. I. Pigment red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180,
C. I. Pigment Red 215, C.I. I. Pigment Red 254; I. Pigment Violet 19,
C. I. Pigment Violet 23, C.I. I. Pigment Violet 29; I. Pigment Blue 1
5, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 6; C.I. I. Pigment Green 7, C.I. I. Pigment Green 36; I. Pigment Brown 23, C.I. I. Pigment Brown 25;
C. I. Pigment Black 1, Pigment Black 7
And the like.

[0010] As the inorganic colorant, specifically,
For example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron Black, carbon black and the like can be mentioned. These colorants can be used alone or in an appropriate combination of two or more.

In the present invention, a colorant in which the surface of the pigment particles is modified by a polymer may be used as appropriate. Examples of the polymer for modifying the surface of the pigment particle include a polymer described in JP-A-8-259876 and various commercially available dispersing polymers or oligomers.

[Binder Polymer] The binder polymer used as the component (B) acts as a binder with respect to the colorant used as the component (A), and is used in the development process when producing a color filter. No particular limitation is imposed on the developing solution, particularly preferably as long as it has solubility in an alkali developing solution. In the present invention, a polymer containing a carboxyl group, particularly one or more carboxyl groups (Hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”) and an ethylenically unsaturated monomer copolymerizable with the carboxyl group-containing unsaturated monomer ( Hereinafter, a copolymer (hereinafter simply referred to as “copolymerizable unsaturated monomer”) obtained by polymerizing a monomer mixture comprising Under simply "carboxyl group-containing copolymer" Tou.) Is preferably.

Specific examples of the unsaturated monomer containing a carboxyl group include 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; and tri- or higher unsaturated polycarboxylic acids or anhydrides thereof. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

Specific examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, methoxystyrene, a compound represented by the following formula (1), Aromatic vinyl compounds such as the compounds represented by 2);

[0015]

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[0016]

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Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentadi Enyl methacrylate And unsaturated carboxylic acid esters such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate; and unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate. ;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; acrylonitrile, methacrylonitrile, α-
Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. Saturated amides or unsaturated imides; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polymer molecules such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone Macromonomers having a monoacryloyl group or a monomethacryloyl group at the chain end can be exemplified. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

The carboxyl group-containing copolymer includes at least one unsaturated monomer having a carboxyl group selected from acrylic acid and methacrylic acid, methyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl. A copolymer with at least one copolymerizable unsaturated monomer selected from methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferable. Specific examples of preferred carboxyl group-containing copolymers include (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, and (meth) acrylic acid / benzyl (Meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer Coalescing, (meth) acrylic acid /
Methyl (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 / polymethylmethacrylate macromonomer copolymer, etc. 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. When this proportion is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease. On the other hand, when this proportion exceeds 50% by weight, the solubility in an alkali developing solution becomes excessively large, so that when developing with the alkali developing solution, the pixel forming body tends to fall off the substrate, and Film roughness on the surface of the pixel formation body tends to occur easily.

The binder polymer used as the component (B) is a weight average molecular weight in terms of polystyrene (hereinafter simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). ) Is 3,000-30
It is preferably from 000, especially from 5,000 to 100,000. By using such a binder polymer having a specific weight average molecular weight as the component (B), a radiation-sensitive composition having excellent developability can be obtained, thereby forming a pixel array having sharp pattern edges. In addition, it is possible to prevent the occurrence of background contamination, film residue, and the like at locations other than the pixel formation portion on the substrate during the development process.

The proportion of the binder polymer used as the component (B) is usually 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, based on 100 parts by weight of the colorant used as the component (A). . If this ratio is less than 10 parts by weight, for example, alkali developability may be reduced, and background contamination or film residue may occur at portions other than the pixel formation portion on the substrate. On the other hand, when this proportion exceeds 1000 parts by weight, the concentration of the colorant relatively decreases, so that it may be difficult to obtain a cured film having a color density required for a color filter.

[Monomer] The polyfunctional monomer used as the component (C) has at least two ethylenically unsaturated bonds, and specific examples thereof include:
Diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; 3 such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol Polyacrylates or polymethacrylates of polyhydric alcohols having a valency of 3 or more; polyester, epoxy resin, urethane resin, alkyd resin, silicone resin,
Oligoacrylates or oligomethacrylates such as spirane resin; di (meth) acrylates of hydroxyl-terminated polymers such as hydroxy-terminated polybutadiene, hydroxy-terminated polyisoprene, hydroxy-terminated polyhydroxycaprolactone; trisacryloyloxyethyl phosphate And trismethacryloyloxyethyl phosphate.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferred. Specifically, a compound represented by the following formula (3), trimethylolpropane triacrylate, , Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,
Examples thereof include dipentaerythritol hexamethacrylate.

[0024]

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Among these, a pixel formed body having high strength and excellent surface smoothness can be obtained, and background stains and film residue at portions other than the pixel formation portion on the substrate are less likely to occur. It is preferable to use the compound represented by the above formula (3), trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate.

In the radiation-sensitive composition of the present invention,
(C) Along with the polyfunctional monomer used as the component,
If necessary, monofunctional monomers can be used. Specific examples of such a monofunctional monomer include those exemplified as the carboxyl group-containing unsaturated monomer and the copolymer unsaturated monomer for obtaining the aforementioned carboxyl group-containing copolymer. Yes, in addition to ω-
Carboxy-polycaprolactone mono (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, etc. Can be mentioned.

The proportion of the polyfunctional monomer in the total monomer is 10 to 100% by weight, especially 50 to 100% by weight.
It is preferred that When this ratio is less than 10% by weight, the strength of the obtained pixel forming body or the surface smoothness of the pixel forming body tends to be insufficient.

The proportion of the polyfunctional monomer used as the component (C) and the monofunctional monomer used as needed is usually based on 100 parts by weight of the binder polymer used as the component (B). The total is 5 to 500 parts by weight, preferably 20 to 300 parts by weight. If this ratio is less than 5 parts by weight, the strength of the resulting pixel formed body or the smoothness of the surface of the pixel formed body tends to be insufficient. On the other hand, when this ratio exceeds 500 parts by weight, for example, alkali developability tends to be reduced, and background stains and film residues in portions other than the pixel formation portion on the substrate tend to occur.

[Photopolymerization Initiator] The radiation-sensitive composition of the present invention contains a photopolymerization initiator as the component (D). Here, the photopolymerization initiator refers to a polyfunctional monomer used as the component (C), which is decomposed or broken by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound that generates an active species such as a radical species, a cationic species, or an anionic species that initiates a polymerization reaction of a monofunctional monomer used as needed. As such a photopolymerization initiator, the following formula (4):
In addition to biimidazole compounds having at least one main skeleton represented by the formula (5) or (6), benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Xanthone compounds, diazo compounds, triazine compounds and the like can be used, and among these, biimidazole compounds are preferred.

[0030]

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

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4.6-trichlorophenyl) -4 , 4 ', 5,5'-Tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2'-bis (2,4.6-tribromophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2′-bis (2,4-dicyanophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (2,4.6-tricyanophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2′-bis (2,4-dimethylphenyl) -4,4 ′,
5,5′-tetraphenylbiimidazole, 2,2′-
Bis (2,4.6-trimethylphenyl) -4,4 ′,
5,5′-tetraphenylbiimidazole, 2,2′-
Bis (2,4-diethylphenyl) -4,4 ′, 5
5'-tetraphenylbiimidazole, 2,2'-bis (2,4.6-triethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4 ', 5,5'
-Tetraphenylbiimidazole, 2,2'-bis (2,4.6-triphenylphenyl) -4,4 ',
5,5'-tetraphenylbiimidazole and the like can be mentioned.

Of these biimidazole compounds,
In particular, 2,2'-bis (2-chlorophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-
Ethoxycarbonylphenyl) biimidazole, 2,
2'-bis (2,4-dichlorophenyl) -4,4 ',
5,5′-tetraphenylbiimidazole, 2,2′-
Bis (2,4-dibromophenyl) -4,4 ′, 5
5'-tetraphenylbiimidazole, 2,2'-bis (2,4.6-trichlorophenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and 2,2'-
Bis (2,4.6-tribromophenyl) -4,4 ',
5,5'-Tetraphenylbiimidazole is preferred.
The biimidazole-based compound has excellent solubility in a solvent, and does not generate foreign matters such as undissolved substances and precipitates.
Moreover, the sensitivity is high, and the curing reaction is sufficiently advanced by irradiating a small amount of energy, and the contrast is high, and the curing reaction does not occur in the non-irradiated portion.
A hardened portion that is insoluble in the developer and an unhardened portion that has a high solubility in the developer are clearly divided, whereby a pixel forming body without undercut can be obtained, and the pixel concerned can be obtained. A pixel array in which the formed bodies are arranged according to a required pattern can be formed.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether,
Benzoin i-butyl ether, 4,4′-bis (dimethylamino) besophenone, methyl-2-benzoylbenzoate and the like can be mentioned.

Specific examples of the acetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, 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 -Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
Examples thereof include 1-one, 1-hydroxycyclohexylphenyl ketone, 1-azidoacetophenone, and 4-azidobenzalacetophenone.

Specific examples of the benzophenone compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and 3,3-dimethyl-4-methoxybenzophenone. Can be mentioned. Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate and the like. Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-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.

Specific examples of the triazine 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.

Further, as a photopolymerization initiator other than the above,
4-azidobenzaldehyde, azidopyrene, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, N-phenylthioacridone, triphenylpyrylium perchlorate and the like can also be used. These photopolymerization initiators can be used alone or in combination of two or more as the component (D).

The proportion of the photopolymerization initiator used as the component (D) is based on 100 parts by weight of the total of the polyfunctional monomer used as the component (C) and the monofunctional monomer used as required. Usually 0.01 to 200
It is preferably 1 to 120 parts by weight, particularly preferably 1 to 50 parts by weight. If this proportion is less than 0.01 parts by weight, it is not sufficiently cured by irradiation with radiation,
It may be difficult to form a pixel array according to a required pattern, and an undercut may occur in a pixel formation body. On the other hand, if this ratio exceeds 200 parts by weight, the formed pattern is likely to fall off the substrate during development, and background stains and film residues are likely to occur at portions other than the pixel formation portion on the substrate.

In the present invention, a functional group capable of functioning as a sensitizer, a curing accelerator, a photocrosslinking agent or a photosensitizer may be added to the main chain or the side chain, if necessary, together with the photopolymerization initiator. One or more kinds of polymer compounds (hereinafter, these may be collectively referred to as “curing aid”) may be used in combination.

Specific examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate,
2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4′-diethylaminobenzal)
Examples thereof include cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone. 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 and the like. These curing accelerators can be used alone or in combination.
More than one species can be used in combination.

Specific examples of the polymer compound having a functional group capable of functioning as a photocrosslinking agent or a photosensitizer in a main chain or a side chain thereof include a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, Examples thereof include a condensate of azidobenzaldehyde and a phenol novolak resin, a homopolymer or copolymer of 4-acryloylphenylcinnamoyl ester, 1,4-polybutadiene, and 1,2-polybutadiene. These polymer compounds can be used alone or in combination of two or more.

The use ratio of such a curing assistant is (D)
The amount is usually 300 parts by weight or less, preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator used as a component.

In the present invention, as the photopolymerization initiator,
In particular, using a biimidazole-based compound and using it in combination with a benzophenone-based compound and / or a thiazole-based curing accelerator makes it difficult for the resulting pixel-formed body to fall off the substrate during development, and provides high pixel strength and high sensitivity. Is preferred in that the following is obtained. When a biimidazole compound is used as a part of the photopolymerization initiator, the ratio of the photopolymerization initiator other than the biimidazole compound may be 80% by weight or less of the entire photopolymerization initiator. preferable.

In the present invention, particularly preferred combinations of the photopolymerization initiator and the curing assistant used as the component (D) are as follows. That is, 2,
2'-bis (2-chlorophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
Biimidazole / 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2-chlorophenyl)
-4,4 ', 5,5'-Tetrakis (4-ethoxycarbonylphenyl) 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) biimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, 2,2'-bis (2-chlorophenyl ) -4,4 ′, 5,5′-Tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4 ′
-Bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole / 4 , 4'-bis (diethylamino) benzophenone, 2,2'-bis (2,4-dibromophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole / 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′-
Tetraphenylbiimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, 2,2'-bis (2,4,6-
Trichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole / 4,4'-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole.

[Solvent] The solvent used as the component (E) dissolves or disperses the components (A) to (D), the component (F) described below and other components used as necessary, The material is not particularly limited as long as it does not react with these components and has appropriate volatility. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. Ether, propylene glycol monomethyl ether,
(Poly) such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alkylene glycol monoalkyl ethers; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol Other ethers such as methyl ethyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; lactic acid such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl esters;
Ethyl 2-hydroxy-2-methylpropionate, 3-
Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3- Methoxybutyl acetate,
3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvate Other esters such as propyl acetate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N- Examples thereof include nitrogen-containing (amide-based) solvents such as dimethylacetamide.

Among these, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and cyclohexanone from the viewpoints of solubility, pigment dispersibility, coatability and the like. , 2-heptanone, 3-heptanone, 2-
Ethyl hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, ethyl pyruvate and the like are preferred. These solvents can be used alone or
More than one species can be used in combination.

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. Among these high-boiling solvents, γ-butyrolactone is preferred. These high-boiling solvents can be used alone or in combination of two or more.

The proportion of the solvent used as the component (E) is not particularly limited, but from the viewpoints of the coating properties and stability of the obtained radiation-sensitive composition, It is preferable that the total concentration of the components other than the component (E) be 5 to 50% by weight, particularly 10 to 40% by weight.

[Surfactant] The surfactant used as the component (F) is a fluorine-based surfactant, particularly a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000 and a fluorine element content of 5 to 30% by weight. % Of at least one fluorine-based surfactant. When the weight average molecular weight of the fluorine-based surfactant is less than 1,000, the effects of the present invention cannot be obtained, and the surface of the pixel forming body may be roughened or a projection may be formed. On the other hand, when the weight average molecular weight of the fluorine-based surfactant exceeds 100,000, the solubility in a solvent may be reduced, which is not preferable.
Further, when the fluorine element content of the fluorine-based surfactant is less than 5% by weight, the effect of the present invention cannot be obtained, and the surface of the pixel forming body is roughened or a projection is formed. Sometimes. On the other hand, when the fluorine element content of the fluorine-based surfactant exceeds 30% by weight, the solubility in a solvent may be reduced, which is not preferable.

Examples of such a fluorine surfactant include Megafac F171, F172, F173, and F173.
F177, F178K, F178A, F47
6, R-08 and R-08H (all manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-381, S-3
83, S-393, SC-101, SC-10
5, KH-40, SA-100 (all manufactured by Asahi Glass Co., Ltd.), Florard FC-430, FC-431
(Above, manufactured by Sumitomo 3M Limited).

The proportion of the fluorine-containing surfactant used as the component (F) is from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight of the whole radiation-sensitive composition (including the solvent).
% By weight. If this ratio is less than 0.01% by weight, the effects of the present invention may not be sufficiently obtained. On the other hand, when this proportion exceeds 1% by weight, the radiation-sensitive performance of the composition may be adversely affected.

In the radiation-sensitive composition of the present invention, for example, as a dispersant for a colorant, a surfactant other than a fluorine-based surfactant (hereinafter referred to as “other surfactant”), for example, a nonionic surfactant Surfactants such as surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and silicone surfactants can be used together with the fluorine-based surfactant. Specific examples of such other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl Polyoxyethylene alkyl phenyl ethers such as 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; . These other surfactants can be used alone or in combination of two or more. Also,
The usage ratio of the other surfactant is, for example, usually 30 parts by weight or less, preferably 5 to 2 parts by weight with respect to 100 parts by weight of the colorant.
0 parts by weight.

[Other Components] In the radiation-sensitive composition of the present invention, an organic acid is added in order to further increase the solubility in an alkali developing solution and to reduce the remaining undissolved material after the development processing. It can be contained. As such an organic acid, it is preferable to use an aliphatic carboxylic acid having a molecular weight of 1,000 or less or a phenyl group-containing carboxylic acid.

Specific examples of the aliphatic carboxylic acid include:
(A) monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid, (b) oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, brassic acid,
Methylmalonic acid, ethylmalonic acid, dimethylmalonic acid,
Dicarboxylic acids such as methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

As the phenyl group-containing carboxylic acid, there can be used 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 bond.
Specific examples thereof include (a) aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid and mesitylene acid, (b) phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, Aromatic polycarboxylic acids such as melophanic acid and pyromellitic acid, (c) phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid, umbellic acid, etc. Is mentioned. These organic acids can be used alone or in combination of two or more.

Among 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; It is preferable from the viewpoints of solubility in a solvent used as a component, prevention of background fouling in a portion other than the pixel forming portion of the substrate, and the like.

The use ratio of such an organic acid is usually 10% by weight or less, preferably 0.0% by weight, based on the whole composition.
It is from 0.01 to 10% by weight, more preferably from 0.01 to 1% by weight. When this ratio exceeds 10% by weight, the obtained pixel forming body tends to have low adhesion to the substrate.

Further, the radiation-sensitive composition of the present invention may contain various additives as necessary. Examples of such additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (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) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
An adhesion promoter such as 3-mercaptopropyltrimethoxysilane; an antioxidant such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; t-butyl-5-methyl-2-
Ultraviolet absorbers such as (hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; aggregation inhibitors such as sodium polyacrylate; and thermal crosslinking agents such as epoxy compounds, melamine compounds, and bisazide compounds.

The radiation-sensitive composition for a color filter of the present invention has a contact angle of methylene iodide of 55 ° or less with respect to a cured film obtained by curing by irradiation with radiation, and particularly, as a component (A), When the colorant is used, the contact angle of methylene iodide with the obtained cured film is 45 ° or less, and when the green colorant or the blue colorant is used as the component (A), the obtained cured film has The contact angle of methylene iodide is preferably 50 ° or less. This contact angle can be adjusted by appropriately washing the type of fluorine surfactant used as the component (F) and the ratio of use thereof. Here, the contact angle of methylene iodide with the cured film is measured as follows. In a clean room at a temperature of 23 ° C. and a relative humidity of 50%, a drop having a diameter of about 2 mm is dropped on the surface of the cured film of the radiation-sensitive composition using a syringe or the like, and the contact angle of the methylene iodide with the cured film is brought into contact. The measurement is performed using an angle measuring device (a device in which a droplet is enlarged and measured with a protractor). When the contact angle of methylene iodide to the cured film exceeds 55 °, the resolution and the surface smoothness of the obtained pixel formed body are low, and projections are easily generated on the surface of the pixel formed body. Therefore, the object of the present invention is not achieved.

[Production Method of Color Filter] By using the radiation-sensitive composition of the present invention, a color filter is produced, for example, as follows. First, a light-shielding layer is formed on the surface of the transparent substrate so as to partition the pixel formation portion,
On this substrate, for example, after applying a radiation-sensitive composition in which a red pigment is dispersed, by performing a pre-bake,
The solvent is evaporated to form a coating. Next, the coating film is irradiated with curing radiation through a photomask to perform a radiation irradiation treatment, and then, for example, is subjected to a development treatment using an alkali developing solution to dissolve a portion of the coating film where the radiation is not irradiated. The removal forms a red pixel array in which the red pixel formers are arranged according to a particular pattern. Thereafter, using each of the radiation-sensitive composition in which the green pigment is dispersed and the radiation-sensitive composition in which the blue pigment is dispersed, in the same manner as described above, application of the radiation-sensitive composition, pre-baking, and irradiation. By performing processing and development processing and sequentially forming a green pixel array and a blue pixel array on the same substrate, a color filter in which red, green, and blue pixel arrays are arranged on the substrate can be obtained. .

In the above, as the material of the transparent substrate used for forming the pixel array, for example, glass,
Silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like can be mentioned. For these transparent substrates, if necessary, chemical treatment with a silane coupling agent or the like, plasma treatment,
Ion plating, sputtering, gas phase reaction,
Appropriate pretreatment such as vacuum deposition can also be performed.
As a method of applying the radiation-sensitive composition to a transparent substrate,
An appropriate coating method such as a spin coating method, a casting coating method, and a roll coating method can be employed. The prebaking temperature of the radiation-sensitive composition is, for example, 50 to 150C. The thickness of the coating film formed by pre-baking the radiation-sensitive composition is generally 0.1 to 10 μm, preferably 0.2 to 5.0 μm.
0 μm, particularly preferably 0.2 to 3.0 μm.

As the curing radiation for curing the coating film of the radiation-sensitive composition, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. It is preferable to use one containing radiation in the range. The irradiation energy amount of radiation is 1 to
It is preferably 1000 mJ / cm ² .

Examples of the alkali developing solution used for the developing treatment include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.
0] -7-undecene, 1,5-diazabicyclo-
An aqueous solution such as [4.3.0] -5-nonene is preferred. Also, these alkali developers include, for example, methanol,
An appropriate amount of a water-soluble organic solvent such as ethanol, a surfactant, or the like can be added.

As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method and the like can be applied. The developing condition is 5 to 300 seconds at room temperature. preferable. After the development, the remaining alkaline developer is usually removed by washing with water.

After the development process is completed, post-baking can be performed on the formed pixel array as needed. Such post-baking can be performed for each pixel array forming step, or can be performed after forming three pixel arrays. The temperature of this post bake is, for example, 150 to 300 ° C.

The color filter manufactured in this manner has high resolution of each pixel forming body and excellent surface smoothness. For example, a color liquid crystal display device, a color image pickup tube element, a color sensor, etc. It is extremely useful.

[0069]

EXAMPLES Hereinafter, specific examples of the radiation-sensitive composition for a color filter of the present invention will be described, but the present invention is not limited to these examples.

Example 1 100 parts by weight of a green pigment (CI Pigment 7) as the component (A) and methacrylic acid / benzyl methacrylate / 2 as the component (B)
-Hydroxyethyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio: 15/60/15
/ 10, weight average molecular weight: 28000) 60 parts by weight,
60 parts by weight of dipentaerythritol pentaacrylate as the component (C), 10 parts by weight of 4,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 4 as the component (D) , 4′-bis (diethylamino) benzophenone 10 parts by weight,
As the component (E), 800 parts by weight of propylene glycol monomethyl ether acetate (including those used as a dispersion medium for the pigment dispersion) and 100 parts by weight of cyclohexanone, and as the component (F), a fluorinated surfactant "Megafac R-08" (Dainippon Ink Chemical Industry Co., Ltd.)
Made, weight average molecular weight about 9800, fluorine content about 10
(% By weight), and these components were mixed to prepare a radiation-sensitive composition (G1).

Using the above radiation-sensitive composition (G1),
Form a cured film as follows, the cured film
The contact angle of methylene iodide was measured. Sodium on surface
Silica (SiO 2) to prevent ion elution_Two) Film formed
Spin coating on a transparent soda glass substrate.
The radiation-sensitive composition (G1) is applied using a
Pre-bake for 10 minutes in a clean oven at
As a result, a coating film having a thickness of 2 μm was formed. This coating is shaped
After cooling the formed substrate, using a high-pressure mercury lamp,
Wavelength 365 nm, 405 nm and 436
200 mJ / cm including nm light ^TwoUV light
A green cured film is formed by performing irradiation treatment
did. In a clean room with a temperature of 23 ° C and a relative humidity of 50%
The surface of the formed cured film using a syringe
A methylene iodide droplet having a diameter of about 2 mm is dropped and the cured film is formed.
The contact angle of methylene iodide to
Measured. As a result, the value of the contact angle was 50 °.

As the component (A), a green pigment (C.I.
I. Pigment 7) instead of a red pigment (C.I.
Pigment 177) and a blue pigment (C.I.
gment 15), except that each of the radiation-sensitive composition (R1) and the radiation-sensitive composition (B1) was prepared in the same manner as in Example 1, and the contact angle of methylene iodide with these cured films was measured. Was measured. As a result, in the radiation-sensitive composition (R1), the value of the contact angle was 39 °, and in the radiation-sensitive composition (B1), the value of the contact angle was 47 °.

[Production of Color Filter] Using the above radiation-sensitive composition (G1), radiation-sensitive composition (R1) and radiation-sensitive composition (B1),
A color filter was manufactured by forming a green pixel array, a red pixel array, and a blue pixel array on a transparent substrate.

On a surface of a transparent substrate made of soda glass having a silica (SiO ₂ ) film for preventing elution of sodium ions formed on the surface, a light-shielding layer is formed so as to partition a pixel forming portion. On the surface of the formed transparent substrate,
The radiation-sensitive composition (G1) was applied by a spin coater, and prebaked in a clean oven at 80 ° C. for 10 minutes to form a coating film having a thickness of 2 μm. After cooling this transparent substrate, the wavelength of 365 nm was applied to the coating film of the transparent substrate through a photomask using a high-pressure mercury lamp.
200 mJ / c including 405 nm and 436 nm light
Irradiation treatment was performed by irradiating ultraviolet rays of m ² . Next, this transparent substrate is immersed in a 0.2% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to perform a developing treatment, and then washed with pure water and dried.
By performing post-baking at 0 ° C. for 30 minutes, a green pixel array in which green pixel forming bodies each having a size of 20 μm × 20 μm were arranged on a transparent substrate was formed.
Then, by using each of the radiation-sensitive composition (R1) and the radiation-sensitive composition (B1) and repeating the above steps, 20 μm × 20 μm each on the same transparent substrate.
A red pixel array in which a red pixel formation having a size of is arranged, and a blue pixel array in which a blue pixel formation having a size of 20 μm × 20 μm are formed, whereby red, A color filter having pixel arrays of three primary colors of green and blue was manufactured.

When each of the pixel arrays in this color filter was observed with an optical microscope, no missing or missing pattern was observed. When a cross section of the pixel formed body was observed with a scanning electron microscope, undercuts were observed. It was confirmed that the composition was excellent in resolution. Further, when the surface of the pixel formed body was observed with a scanning electron microscope, it was found that the surface was excellent in surface smoothness, and no projection was observed.

<Comparative Example 1> A radiation-sensitive composition (G2) and a radiation-sensitive composition (G2) were prepared in the same manner as in Example 1 except that the fluorosurfactant “Megafac R-08” was not used. B2) was prepared, and the contact angles of methylene iodide with these cured films were measured. As a result, the radiation-sensitive composition (G2) had a contact angle value of 60 °, and the radiation-sensitive composition (B2) had a contact angle value of 58 °.

Using the radiation-sensitive composition (G2) and the radiation-sensitive composition (B2), a green pixel array and a blue pixel array were formed on a transparent substrate in the same manner as in Example 1. Then, when each of the pixel arrays was observed with an optical microscope, a lack of a pattern was observed. When the surface of the pixel formed body was observed with a scanning electron microscope, film roughness and occurrence of projections were observed.

Reference Example A radiation-sensitive composition was prepared in the same manner as in Example 1 except that a perfluoroalkyl sulfonate having a molecular weight of less than 1000 was used in place of the fluorosurfactant "Megafac R-08". (G3) and the radiation-sensitive composition (B3) were prepared, and the contact angle of methylene iodide with these cured films was measured. As a result, in the radiation-sensitive composition (G3), the value of the contact angle was 51 °, and in the radiation-sensitive composition (B2), the value of the contact angle was 49 °.

Using the radiation-sensitive composition (G3) and the radiation-sensitive composition (B3), a green pixel array and a blue pixel array were formed on a transparent substrate in the same manner as in Example 1. The surface of the pixel formed body in each of the pixel arrays was observed with a scanning electron microscope. As a result, the surface was better than the pixel array according to Comparative Example 1, but film roughness and the occurrence of projections were slightly observed. Was done.

[0080]

According to the radiation-sensitive composition for a color filter of the present invention, the contact angle of methylene iodide to a cured film obtained by curing by irradiation of radiation is 55 ° or less, so that the resolution is improved. It is possible to form a pixel forming body which is high and has excellent surface smoothness, and furthermore, it is possible to suppress the occurrence of projections on the surface of the pixel forming body and manufacture a color filter with a high yield.

Further, according to the present invention, (A) a colorant,
A radiation-sensitive composition comprising (B) a binder polymer, (C) a polyfunctional monomer, (D) a photopolymerization initiator, (E) a solvent, and (F) a surfactant, After coating on a transparent substrate, by performing a removing process of the solvent in the radiation-sensitive composition, a coating film is formed on the transparent substrate, and the coating film is subjected to a radiation irradiation process and a developing process. Accordingly, it is possible to provide a method of manufacturing a color filter including a step of forming a cured film having a contact angle of methylene iodide of 55 ° or less. And the color filter manufactured in this way is excellent in reliability, for example, a desk calculator, a wristwatch, a clock, a coefficient display board,
It is effectively used for display devices such as word processors, personal computers, and liquid crystal televisions.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 155/00 C09D 155/00 (72) Inventor Atsushi Kumano 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] 1. A colorant, (B) a binder polymer, (C) a polyfunctional monomer, (D) a photopolymerization initiator, (E) a solvent, and (F) a surfactant. A radiation-sensitive composition for a color filter, wherein a contact angle of methylene iodide to a cured film obtained by curing by irradiation of radiation is 55 ° or less.