KR20010029663A - Radiosensitive Compositions for Color Filter and Color Filters - Google Patents

Abstract

The present invention provides an organic amino compound having at least one amino group in the (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) triazine-based compound, and (E) molecule. It is related with the color filter characterized by including the radiation sensitive composition for color filters containing, and the pixel formed from the radiation sensitive composition for color filters.

When using a photoinitiator containing a triazine-based compound according to the present invention, a mask deposit does not occur at the time of radiation irradiation and can provide a pixel excellent in developability and excellent in adhesion to a substrate and a light shielding layer. There is provided a radiation sensitive composition for a color filter, and a color filter formed from the composition.

Description

Radiosensitive Compositions for Color Filters and Color Filters

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a radiation-sensitive composition for color filters and a color filter, and more particularly, to a transmissive or reflective color liquid crystal display device, a color image tube device, etc., in which no mask deposit is generated during radiation irradiation, and also excellent in developability. It relates to a radiation sensitive composition for color filters useful in the production of color filters used, and a color filter formed of the radiation sensitive composition for color filters.

In manufacturing a color filter using a conventionally colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or on a substrate on which a light-shielding layer of a desired pattern is formed in advance, it is dried for the purpose of a dry coating film. Formation methods (see Japanese Patent Application Laid-Open Nos. 90-144502 and 91-53201) are known, in which respective color pixels are obtained by irradiation with radiation (hereinafter referred to as "exposure") and developing in a pattern shape. have.

However, in the case of the color filter obtained by such a method, residues or background stains may occur on the substrate or the light shielding layer of the unexposed part at the time of development, and in the conventional colored radiation-sensitive composition, such residues or background stains may be brush-washed or the like. In this case, the surface of the pixel is scratched or a pattern defect is generated, which is a major cause of pattern defects.

Moreover, in the radiation sensitive composition for color filters using a halomethyloxadiazole type compound or a halomethyl-s-triazine type compound as a photoinitiator, in order to suppress the influence of the hydrogen halide byproduced from these compounds, it is a (di) glycol. The technique which mix | blends the organic compound which has epoxy groups, such as cyl ether, or an epoxy resin is proposed (Unexamined-Japanese-Patent No. 89-254918 (patent publication 96-95238) and the same patent publication 96-94824) Reference).

Although the radiation sensitive composition for color filters can produce a color filter excellent in electrical and chemical stability or can suppress a mask deposit, especially when using a triazine type compound, such as a halomethyl-s-triazine type compound. It was not enough in the point which suppresses the mask deposit of this.

Therefore, the subject of this invention is a novel thing which can provide the pixel which does not generate a mask deposit at the time of exposure, and is excellent in developability and also excellent in adhesiveness to a board | substrate and a light shielding layer when using the photoinitiator containing a triazine type compound. The radiation sensitive composition for a color filter, and the color filter formed from the radiation sensitive composition for a color filter are provided.

According to the present invention, the above object of the present invention firstly,

(A) a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, photopolymerization initiator containing (D) triazine type compound, and (E) molecule | numerator containing organic amino compound which has one or more amino groups It is achieved by the radiation sensitive composition for color filters (henceforth "the 1st invention") characterized by the above-mentioned.

According to the present invention, the above object of the present invention is second,

A color containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) a photoinitiator containing a triazine-based compound, and (E) an organic amino compound having at least one amino group in a molecule. It is achieved by the color filter (henceforth "the 2nd invention") characterized by having the pixel formed from the radiation sensitive composition for filters.

"Radiation" as used in the present invention means visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

(A) colorant

The coloring agent in this invention is not specifically limited in color tone, It selects suitably according to the use of the color filter obtained, Any of a pigment, dye, or a natural pigment may be sufficient.

Since the color filter requires high color development and heat resistance, the colorant in the first invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance, and a pigment, particularly preferably an organic pigment, is used. do.

As the organic pigment, for example, a compound which is classified as a pigment in the color index (issued by The Society of Dyers and Colorists, Inc.), and specifically, the following color index (CI) number is given. It can be mentioned.

C.I. Pigment Yellow 83, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 175, C.I. Pigment yellow 185;

C.I. Pigment Orange 71, C.I. Pigment orange 73;

C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment red 265;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment blue 60;

C.I. Pigment Green 7, C.I. Pigment green 36;

C.I. Pigment Brown 23, C.I. Pigment brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

In addition, these organic pigments can be refine | purified and used, for example by the sulfuric acid recrystallization method, the solvent washing method, or a combination thereof.

The said organic pigment can be used individually or in mixture of 2 or more types.

In addition, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zincation, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), cadmium, ultramarine blue, bluish orange oxide, chromium oxide, and cobalt rust. , Amber, titanium black, synthetic iron black, carbon black and the like.

These inorganic pigments can be used individually or in mixture of 2 or more types.

In the present invention, each colorant may be used by modifying its particle surface with a polymer as desired. As a polymer which modifies the particle surface of a coloring agent, the polymer of Unexamined-Japanese-Patent No. 96-259876 grade | etc., Etc., the polymer for various pigment dispersions, or oligomer etc. are mentioned, for example.

In addition, in this invention, a coloring agent can be used with a dispersing agent as desired.

As such a dispersing agent, surfactant, such as a cationic type, an anionic type, a nonionic type, an amphoteric, a silicone type, and a fluorine type, is mentioned, for example.

As a specific example of the said surfactant, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl 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; In addition to polyethyleneimine, etc., KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (made by Tochem Prodact Corporation), Mega Pack (in the following brand names) Dainippon Inkaku Kogyo Co., Ltd., Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahigarasu Co., Ltd.), Disperbyk (Bikkemi Japan Co., Ltd.) Products), Solsperth (Geneca Co., Ltd.), etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The usage-amount of surfactant is 50 weight part or less normally with respect to 100 weight part of coloring agents, Preferably it is 30 weight part or less.

Moreover, in the radiation sensitive composition of this invention, although the ratio of the said pigment to all the components except a solvent can be made into a suitable ratio, it is preferable that it is 20 to 50%. The ratio of the pigment in the composition can adopt a suitable value within the range according to the use, for example, 20 to 40% for the liquid crystal monitor of the notebook personal computer or computer, and 35 to 50% for the liquid crystal television Can be.

(B) alkali soluble resin

In the present invention, the alkali-soluble resin is particularly limited as long as it acts as a binder to the colorant (A) and has solubility in a developer, particularly preferably an alkali developer, used in the development treatment step when producing a color filter. Although it is not necessary, alkali-soluble resin which has a carboxyl group is preferable, and ethylenically unsaturated monomer copolymerizable with other ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth simply called "carboxyl group-containing unsaturated monomer" hereafter) (henceforth) And a copolymer (hereinafter simply referred to as a "carboxyl group-containing copolymer") with a "copolymerizable unsaturated monomer" are preferable.

As a carboxyl group-containing unsaturated monomer, for example

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyhydric carboxylic acid;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone monoacrylate and? -carboxypolycaprolactone monomethacrylate.

Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are trademarks of M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. It is commercially available.

The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

As the copolymerizable unsaturated monomer, for example,

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

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-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, 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 meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nylacrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters;

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 and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Monoacryloyl group or monomethacryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane The macromonomer which has, etc. are mentioned.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

In the present invention, as the carboxyl group-containing copolymer, ① acrylic acid and / or methacrylic acid are essential components, and monosuccinic acid mono (2-acryloyloxyethyl) and monosuccinate mono (2-methacryloyloxy Ethyl), ω-carboxypolycaprolactone monoacrylate, and carboxyl group-containing unsaturated monomer component further containing at least one member selected from the group of ω-carboxypolycaprolactone monomethacrylate, and (2) styrene and 2-hydroxy. Ethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macro Copolymer with at least one selected from the group consisting of monomers and polymethyl methacrylate macromonomers (hereinafter referred to as "ka Is called a repeat group-containing copolymer (I) ") is preferred.

As a specific example of a carboxyl group-containing copolymer (I),

(Meth) acrylic acid / benzyl (meth) acrylate copolymers,

(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 / polymethylmethacrylate 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,

(Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer

(Meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer

Etc. can be mentioned.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility in the alkaline developer of the resulting radiation-sensitive composition tends to decrease, while when it exceeds 50% by weight, the solubility in the alkaline developer is excessively high and alkali. When developing with a developing solution, there is a fear that dropping from the pixel substrate or roughness of the pixel surface film is likely to occur.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin becomes like this. Preferably it is 3,000-300,000, More preferably, it is 5,000- 100,000.

The polystyrene reduced number average molecular weight (hereinafter, referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin becomes like this. Preferably it is 3,000-60,000, More preferably, 5,000 to 25,000.

By using an alkali-soluble resin having such specific Mw or Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a clear pattern edge can be formed, and at the same time, on the substrate of the unexposed part at the time of development And residues, background stains, film residues, etc., are less likely to occur on the light shielding layer.

In addition, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin is 1-5 normally, Preferably it is 1-4.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

The use amount of alkali-soluble resin in this invention is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, when the usage-amount of alkali-soluble resin is less than 10 weight part, alkali developability may fall, for example, there exists a possibility that a back surface stain or a film | membrane residue may arise on the board | substrate or light-shielding layer of an unexposed part, and 1,000 weight part When exceeding, since the coloring agent density | concentration falls relatively, it may become difficult to achieve the density | concentration of the target color as a thin film.

(C) polyfunctional monomer

The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.

As a polyfunctional monomer, for example

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;

Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, or dicarboxylic acid modified substances thereof;

Oligoacrylates or oligomethacrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins and spiran resins;

Diacrylates or dimethacrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactones; or

Tris (2-acryloyloxyethyl) phosphate, a tris (2-methacryloyl oxyethyl) phosphate, etc. are mentioned.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols or dicarboxyl modifications thereof are preferable, specifically trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentarita Erythritol hexamethacrylate, the compound represented by following formula (1), etc. are preferable, Especially trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high pixel intensity, and smooth the surface of a pixel. It is excellent and preferable in the difficulty of generating a background stain, such as film remaining on the substrate and the light shielding layer of the unexposed portion.

In this invention, a polyfunctional monomer can be used individually or in mixture of 2 or more types.

The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the intensity or surface smoothness of the pixel tends to be lowered. On the other hand, when it exceeds 500 parts by weight, for example, alkali developability is decreased, Background spots, film residues and the like tend to be easily generated on the light shielding layer.

Moreover, in this invention, you may use together a monofunctional monomer with the said polyfunctional monomer as needed.

Examples of such monofunctional monomers include the carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the carboxyl group-containing copolymer or N-acryloyl morpholine, N-methacryloyl morpholine, N-vinylpyrrolidone, In addition to N-vinyl- epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The use ratio of monofunctional monomer is 90 weight% or less normally with respect to the sum total of a polyfunctional monomer and a monofunctional monomer, Preferably it is 50 weight% or less. In this case, when the use ratio of monofunctional monomer exceeds 90 weight%, there exists a tendency for the intensity | strength or surface smoothness of the obtained pixel to fall.

(D) photoinitiator

The photopolymerization initiator in the present invention contains a triazine-based compound, and generates an active species capable of initiating polymerization of the (C) polyfunctional monomer by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. It can be an ingredient.

As a specific example of the said triazine type compound,

2,4,6-tris (trichloromethyl) -s-triazine,

2-methyl-4,6-bis (trichloromethyl) -s-triazine,

2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

A compound represented by the following general formula (2) (hereinafter referred to as "triazine compound (2)")

A compound represented by the following formula (hereinafter referred to as "triazine compound (3)")

Triazine type compounds which have halomethyl groups, such as these, are mentioned.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, triazine compound (2), triazine compound ( 3) etc. are preferable.

The said triazine type compound can be used individually or in mixture of 2 or more types.

The amount of the triazine-based compound used in the present invention is usually 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer used in some cases, More preferably, it is 1-20 weight part. In this case, when the amount of the triazine-based compound used is less than 0.01 part by weight, curing due to exposure is insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged in accordance with a predetermined arrangement, while exceeding 40 parts by weight. There is a tendency for the formed pixels to fall off from the substrate during development.

In addition, in this invention, another compound (henceforth "other photoinitiator") can be used together with a triazine type compound as a structural component of a photoinitiator.

As another photoinitiator, an acetophenone type compound, a biimidazole type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound etc. are mentioned, for example. Among them, at least one selected from the group of acetophenone compounds and biimidazole compounds is preferable.

As a specific example of the acetophenone-based compound,

2-hydroxy-2-methyl-1-phenylpropan-1-one,

2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,

2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,

1-hydroxycyclohexylphenyl ketone,

2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one etc. are mentioned.

Among these acetophenone compounds, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 is particularly preferable.

The acetophenone compounds may be used alone or in combination of two or more thereof.

In the present invention, when the acetophenone compound is used in combination with the triazine compound as a constituent of the photopolymerization initiator, the use ratio is usually 90% by weight or less, preferably 30, based on the total of the triazine compound and the acetophenone compound. To 80% by weight. In this case, when the use ratio of an acetophenone type compound exceeds 90 weight%, there exists a tendency for the formed pixel to fall out from a board | substrate at the time of image development.

In addition, as a specific example of the said biimidazole type compound, 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-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 is mentioned.

Preferred of these compounds are 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, particularly preferred compounds are 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.

These biimidazole-based compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved products, precipitates, etc., and have high sensitivity, sufficiently proceeding the curing reaction by exposure of a small amount of energy, and contrast. Since the curing reaction does not occur in the unexposed portion, the coated film after exposure is clearly divided into a hardened portion insoluble in the developer and an uncured portion having high solubility in the developer, thereby providing a pixel pattern without undercut. It is possible to form a highly precise pixel array arranged in accordance with this predetermined arrangement.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

In the present invention, when the non-imidazole-based compound is used in combination with the triazine-based compound as a constituent of the photopolymerization initiator, the use ratio is usually 90% by weight or less based on the total of the triazine-based compound and the non-imidazole-based compound. Is 5 to 80% by weight. In this case, when the use ratio of a biimidazole type compound exceeds 90 weight%, there exists a tendency for the formed pixel to fall out from a board | substrate at the time of image development.

<Hydrogen donor>

In this invention, when using a biimidazole type compound as a structural component of a photoinitiator, using the following hydrogen donor together is preferable at the point which can improve a sensitivity further.

The "hydrogen donor" here means a compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As the hydrogen donor, mercaptan compounds defined below, amine compounds defined below and the like are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having one or more, preferably one to three, more preferably one to two mercapto groups directly bonded to the mother nucleus (hereinafter, " Mercaptan-based hydrogen donor. "

The amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as "amine System hydrogen donor ”.

These hydrogen donors may also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described in more detail.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both benzene rings and heterocycles. When two or more of these rings have a condensed ring, the mercaptan-based hydrogen donor may not be formed.

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group, and further, one or more mercapto groups. As long as the free mercapto group remains, two sulfur atoms may have a structural unit bonded via a divalent organic group such as an alkylene group, or two sulfur atoms in the form of disulfide.

The mercaptan-based hydrogen donor may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a portion other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine etc. are mentioned.

Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzooxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Subsequently, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both benzene rings and heterocycles, and in the case of having two or more rings, even if a condensed ring is not formed, good.

In the amine-based hydrogen donor, at least one amino group may be substituted with an alkyl group or a substituted alkyl group, and at a portion other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, nitrile group, or the like. It may be substituted.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiope. Non-methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid i-amyl, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, etc. are mentioned.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferred. This is preferred.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. However, a pixel formed by using one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination may be removed from the substrate during development. It is preferable in that it is hard to drop out, and also the pixel intensity and sensitivity are high.

Specific examples of preferred combinations of mercaptan-based hydrogen donors and amine-based hydrogen donors include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4 '. -Bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) Benzophenone etc. are mentioned, A more preferable combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (di Ethylamino) benzophenone, with a particularly preferred combination being 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The weight ratio of the mercaptan-based hydrogen donor to the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is usually 0.01 to 40 parts by weight, preferably 100 parts by weight based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer used in some cases. It is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, when the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed pixels tend to fall off the substrate during development.

(A) Combination of triazine compound and acetophenone compound, (b) Combination of triazine compound and biimidazole compound in the present invention, (c) Triazine compound, acetophenone compound and biimi Combination of a dazole compound, (d) a combination of a triazine compound, a biimidazole compound, a mercaptan hydrogen donor and an amine hydrogen donor, (e) a triazine compound, an acetophenone compound, a biimidazole compound, a mercap If the especially preferable specific example of the combination of a carbon-based hydrogen donor and an amine hydrogen donor is shown, the following are mentioned.

Particularly preferred combinations of the above (a) are

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine / 2-benzyl-2-dimethylamino-1- (4-morpholi Nophenyl) butanone-1,

Triazine-based compound (2) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,

Triazine compound (3) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1

And so on.

Particularly preferred combination of (b) is

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine / 2,2'-bis (2,4-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

Triazine-based compound (2) / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

Triazine Compound (3) / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

And so on. Further, in the above combination, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is converted to 2,2'-bis The combination substituted with (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole can also be used especially preferably.

Particularly preferred combination of (c) is

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine / 2-benzyl-2-dimethylamino-1- (4-morpholi Nophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, triazine-based compound (2 ) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5' -Tetraphenyl-1,2'-biimidazole,

Triazine Compound (3) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ' , 5,5'-tetraphenyl-1,2'-biimidazole

And so on. Further, in the above combination, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is converted to 2,2'-bis The combination substituted with (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole can also be used especially preferably.

Particularly preferred combination of (d) is

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine / 2,2'-bis (2,4-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone,

Triazine Compound (2) / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothia Sol / 4,4'-bis (diethylamino) benzophenone,

Triazine Compound (3) / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothia Sol / 4,4'-bis (diethylamino) benzophenone

And so on. Further, in the above combination, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is converted to 2,2'-bis Combinations substituted with (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole can also be preferably used.

Particularly preferred combinations of the above (e) are

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine / 2-benzyl-2-dimethylamino-1- (4-morpholi Nophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzo Thiazole / 4,4'-bis (diethylamino) benzophenone,

Triazine compound (2) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ' , 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone,

Triazine Compound (3) / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4,4 ' , 5,5'-tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone

And so on. Further, in the above combination, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is converted to 2,2'-bis The combination substituted with (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole can also be used especially preferably.

(E) organic amino compounds

The organic amino compound in this invention is an organic amino compound (henceforth "(E) organic amino compound") which has one or more amino groups in a molecule | numerator.

(E) The organic amino compound is an active radical generated from a triazine-based compound contained in the photopolymerization initiator in the radiation-sensitive composition for color filters at the time of exposure, or a volatile product formed by reaction of the active radical with the organic compound in the radiation-sensitive composition. An acid compound (e.g., hydrogen halide, etc.) is trapped to prevent the occurrence of mask deposits and to improve adhesion of the formed pixel to the substrate and the light shielding layer. The amine-based hydrogen donor itself has such a function, but the amine-based hydrogen donor is consumed by the interaction with the biimidazole-based compound which is the main component of the (C) photopolymerization initiator. Itself does not actually exhibit this action.

As the (E) organic amino compound, an aliphatic amine or a phenyl group-containing amine is preferable.

As an example of the said aliphatic amine,

n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine, o-ethyl Mono (cyclo) alkylamines such as cyclohexylamine, m-ethylcyclohexylamine and p-ethylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri -i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclo Tri (cyclo) alkylamines such as hexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino Mono (cyclo) alkanolamines such as -1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di ( Di (cyclo) alkanolamines such as 4-cyclohexanol) amine;

Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 Tri (cyclo) alkanolamines such as -cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2- Cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3- Amino (cyclo) alkanediols such as propanediol and 2-diethylamino-1,3-propanediol;

1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol and 4-diethylaminocyclohexanemethanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Moreover, as a phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the amino group couple | bonded with the phenyl group via the bivalent bonding group, etc. are mentioned, for example.

As an example of a phenyl group containing amine,

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, 1-naphthylamine, 2- Aromatic amines such as naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and p-methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;

aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;

aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid

Etc. can be mentioned.

Among these (E) organic amino compounds, mono (cyclo) alkanolamines and aminos are used as aliphatic amines from the viewpoints of solubility in a solvent to be described later, prevention of unevenness of the substrate on the unexposed portion, or prevention of film residue. (Cyclo) alkanoldiols are preferable, and 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol and 2-amino-1 , 3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable, and o-aminophenol, m-aminophenol, p-aminophenol, etc. are especially preferable.

In this invention, (E) organic amino compound can be used individually or in mixture of 2 or more types.

The usage-amount of the (E) organic amino compound in this invention is 0.01 to 15 weight% normally with respect to the whole radiation sensitive composition, Preferably it is 0.01 to 10 weight%. In this case, when the amount of the organic amino compound (E) used is less than 0.01% by weight, the inhibitory effect of the mask deposit or the improvement effect of adhesion of the formed pixel to the substrate or the light shielding layer tends to be lowered. There exists a tendency for the adhesiveness with the board | substrate of the formed pixel to fall rather.

<Additive>

In this invention, the radiation sensitive composition for color filters may contain various additives as needed.

As said additive, the organic acid etc. which show the effect which further improves the dissolution characteristic with respect to the alkaline developing solution of the radiation sensitive composition for color filters, and further suppresses the remainder of the undissolved matter after image development, etc. are mentioned.

Organic acids

As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has one or more carboxyl groups in a molecule, and whose molecular weight is 1,000 or less is preferable.

As an example of the said aliphatic carboxylic acid,

Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivaric acid, capronic acid, diethylacetic acid, enanthic acid, caprylic acid, etc .;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;

And aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, or a compound in which a carboxyl group is bonded to a phenyl group via a divalent bonding group.

As an example of a phenyl group containing carboxylic acid,

Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; or

Phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamiledic acid, cumalic acid, unberlic acid, and the like.

As aliphatic carboxylic acid, aliphatic dicarboxylic acids are preferable from a viewpoint of alkali solubility in these organic acids, the solubility with respect to the solvent mentioned later, the prevention of the back unevenness and film | membrane remainder on the board | substrate and light-shielding layer of an unexposed part, Malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. Moreover, as phenyl group containing carboxylic acid, aromatic dicarboxylic acids are preferable and phthalic acid is especially preferable.

The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic acid exceeds 15 weight%, adhesiveness with respect to the board | substrate of the formed pixel tends to fall.

In addition, as an additive other than the above, for example,

Dispersing aids such as blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives; Fillers such as glass and alumina;

Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (fluoroalkyl acrylates);

Surfactants such as nonionic, cationic and anionic systems;

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxyoxytrimethylsilane, 3-glycidoxyoxymethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylooxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane accelerant;

Antioxidants such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;

Aggregation inhibitors such as sodium polyacrylate;

Thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile;

A compound represented by Formula 4,

To a compound represented by the formula (5),

Oxetane type compounds, such as these, etc. are mentioned.

<Solvent>

In this invention, the radiation sensitive composition for color filters contains the photoinitiator containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) triazine type compound, and (E) organic amino compound. It is made as an essential component, contains the said additive component as needed, Preferably it mixes a solvent and is manufactured as a liquid composition.

The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (E) and the additive component constituting the radiation-sensitive composition and does not react with these components and has appropriate volatility.

As such a solvent, for example

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, diethylene glycol mono-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, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

(Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates;

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;

Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n Butyl, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetoamide, and the like.

Propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene from the viewpoint of solubility, pigment dispersibility, coating properties, etc. Glycolmethylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl 3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyric acid i-propyl, n-butyl butyrate, ethyl pyruvate Etc. are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

The said high boiling point solvent can be used individually or in mixture of 2 or more types.

Although the usage-amount of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of a liquid composition becomes like this. Preferably it is 5-50 weight%, More preferably, it is 10-10. Amounts of 40% by weight are preferred.

<Formation method of color filter>

Next, the method of forming the color filter of 2nd invention using the radiation sensitive composition for color filters of 1st invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a part which forms a pixel as needed, and after apply | coating the liquid composition of the radiation sensitive composition in which the red pigment was disperse | distributed on this board | substrate, for example, Baking evaporates a solvent and forms a coating film. Subsequently, after exposing through a photo mask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes thereafter, and the red pixel pattern is arrange | positioned in a predetermined | prescribed arrangement. Form a pixel array.

Subsequently, using the liquid composition of each radiation-sensitive composition in which green or blue pigments were dispersed, the same procedure as above was applied, prebaked, exposed, developed and postbaked, and the pixel array of green and blue By sequentially forming pixel arrays of pixels on the same substrate, color filters in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate are obtained.

As a board | substrate used at the time of forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, or vacuum deposition.

When apply | coating the liquid composition of a radiation sensitive composition to a board | substrate, the appropriate application | coating methods, such as rotational coating, casting | flow_spread coating, roll coating, can be employ | adopted.

The coating thickness is a film thickness after drying, which is usually 0.1 to 10 mu m, preferably 0.2 to 8.0 mu m, more preferably 0.2 to 6.0 mu m.

As a radiation used when producing a color filter, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The exposure dose of radiation is preferably about 1 to 1,000 mJ / cm 2.

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, corin, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabi Aqueous solutions, such as cyclo [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali image development, it washes with water normally.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddling (liquid immersion) developing method, and the like can be applied, and the developing conditions are preferably 5 to 300 seconds at room temperature.

The color filter of the second invention thus formed is very useful, for example, in a transmissive or reflective color liquid crystal display device, a color image tube element, a color sensor, or the like.

The radiation sensitive composition for color filters of 1st invention contains the photoinitiator containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) triazine type compound, and (E) organic amino compound. It is set as an essential component and it is as follows (a)-(e), if a preferable composition is concretely illustrated.

(A) The radiation sensitive composition for color filters in which (B) alkali-soluble resin contains a carboxyl group-containing copolymer (I).

(B) Radiation-sensitive for color filters (A), wherein the polyfunctional monomer (C) comprises at least one member selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Composition.

(C) The radiation sensitive composition for color filters of said (A) or (B) in which (D) photoinitiator also contains 1 or more types chosen from the group of acetophenone type compound and a biimidazole type compound.

(D) (E) at least one organic amino compound selected from the group of mono (cyclo) alkanolamines, amino (cyclo) alkanediols and aminophenols, more preferably 2-aminoethanol, 3-amino- 1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1, 2-butanediol, o-aminophenol, The radiation sensitive composition for color filters of said (A), (B) or (C) containing 1 or more types chosen from the group of m-aminophenol and p-aminophenol.

(E) The radiation sensitive composition for color filters of said (A), (B), (C) or (D) whose (A) coloring agent contains an organic pigment.

Moreover, the preferable color filter of 2nd invention is

(E) a color filter having a pixel formed from the radiation-sensitive composition for color filters of (a), (b), (c), (d) or (e) above,

Is made of.

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

<Example 1>

(A) As a coloring agent, C.I. Pigment Red 177 and C.I. 80 parts by weight of a 65/35 (weight ratio) mixture of Pigment Red 224, (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymer weight ratio) as alkali-soluble resin = 15/15/35/10/25, Mw = 30,000, Mn = 10,000) 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) a triazine compound as a photopolymerization initiator ( 2) 9 parts by weight, (E) 2 parts by weight of 2-aminoethanol as an organic amino compound and 1,000 parts by weight of a 95/5 (weight ratio) mixture of propylene glycol monomethyl ether acetate and cyclohexanone as a solvent to the radiation-sensitive composition Liquid composition (Rl) was prepared.

<Formation of color filter>

A liquid composition (Rl) was applied on the surface of a soda glass substrate on which a SiO ₂ film was formed to prevent elution of sodium ions on the surface using a spin coater, and then prebaked in a clean oven at 80 ° C. for 10 minutes to obtain a film thickness of 1.8 μm. The coating film of was formed.

Subsequently, after cooling this board | substrate to room temperature, the ultraviolet-ray containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film in the exposure amount of 50 mJ / cm <2> through the photomask using the high pressure mercury lamp. Then, this board | substrate was immersed for 1 minute in 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and was developed. Thereafter, the substrate was washed with ultrapure water and air dried, and then postbaked in a clean oven at 200 ° C. for 30 minutes to form a red striped color filter on the substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

The liquid composition (Rl) was applied onto the surface of a 15 cm x 15 cm soda glass substrate with a SiO ₂ film to prevent elution of sodium ions on the surface using a spin coater and then freed for 10 minutes in a clean oven at 80 ° C. It baked and produced the coating substrate 1 in which the coating film of 1.8 micrometers in thickness was formed. Separately from this, along the outer periphery of one surface of the said soda glass board | substrate, the opposing board | substrate 1 was produced by sticking the double-sided adhesive tape (brand name IC tape red, the Izumiya Aishi Co., Ltd. product) of width 5mm and 43 micrometers in thickness.

The coated substrate 1 and the opposing substrate 1 are bonded together with the double-sided adhesive tape with the coated film surface of the coated substrate 1 inward, and then exposed through an opposing substrate 1 at an exposure dose of 150 mJ / cm 2. And this operation was repeated 10 times, replacing only the coating substrate 1. Thereafter, the counter substrate 1 was removed and observed using a light projector. No deposit was observed on the counter substrate 1.

<Example 2>

(A) As a coloring agent, C.I. Pigment Red 177 and C.I. 65 parts by weight of 80/20 (weight ratio) mixture of Pigment Yellow 83, (B) methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer as alkali-soluble resin (copolymer weight ratio = 20 / 18.8 / 30) /31.2, Mw = 45,000, Mn = 18,000) 60 parts by weight, (C) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 5 parts by weight of a triazine compound (3) as a photopolymerization initiator, 2- 20 parts by weight of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5' 5 parts by weight of -tetraphenyl-1,2'-biimidazole and 2.5 parts by weight of 2-mercaptobenzothiazole and 5 parts by weight of 4,4'-bis (diethylamino) benzophenone as hydrogen donors, (E) 5 parts by weight of 3-amino-1-propanol as an organic amino compound and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were prepared to prepare a liquid composition (R2) of the radiation-sensitive composition. The.

Subsequently, a red stripe-like color filter was formed on the substrate in the same manner as in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (Rl).

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used liquid composition (R2) instead of liquid composition (R1), it carried out similarly to Example 1, the coating board | substrate 2 and the opposing board | substrate 2 were produced, and the mask attachment was evaluated.

As a result, no deposit was found on the removed counter substrate 2.

<Example 3>

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 75 parts by weight of a 75/25 (weight ratio) mixture of Pigment Yellow 139, (B) methacrylic acid / ω-carboxypolycaprolactone monoacrylate / styrene / benzyl methacrylate / glycerol monomethacrylate / as alkali-soluble resin 75 parts by weight of N-phenylmaleimide copolymer (copolymerization weight ratio = 15/10 / 11.3 / 35/10 / 18.7, Mw = 40,000, Mn = 20,000), (C) dipentaerythritol hexaacrylate 75 weight as a polyfunctional monomer 8 parts by weight of the triazine compound (2), 10 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator (2), 2,2'- 3 parts by weight of bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 1.5 parts by weight of 2-mercaptobenzothiazole and 4 as a hydrogen donor 3 parts by weight of 4'-bis (diethylamino) benzophenone, (E) 10 parts by weight of p-aminophenol as the organic amino compound, and propylene glycol monomethyl ether acetate 1 as the solvent; 000 parts by weight were mixed to prepare a liquid composition (R3) of the radiation sensitive composition.

Subsequently, a red striped color filter was formed on the substrate in the same manner as in Example 1 except that the liquid composition (R3) was used instead of the liquid composition (Rl).

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used the liquid composition (R3) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating board | substrate 3 and the counter board | substrate 3 were produced, and the mask attachment was evaluated.

As a result, no deposit was found on the removed counter substrate 3.

<Example 4>

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 90 parts by weight of a 70/30 (weight ratio) mixture of Pigment Yellow 150, (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymer weight ratio) as alkali-soluble resin = 15/15/35/10/25, Mw = 35,000, Mn = 17,500) 60 parts by weight, (C) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) a triazine compound as a photopolymerization initiator ( 2) 10 parts by weight, and 15 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone 1, (E) 7.5 parts by weight of 5-amino-1-pentanol as an organic amino compound Part and a 1,000 parts by weight of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a liquid composition (Gl) of the radiation sensitive composition.

Next, except having used the liquid composition (Gl) instead of the liquid composition (R1), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

The coating substrate 4 and the opposing substrate 4 were produced in the same manner as in Example 1 except that the liquid composition (Gl) was used instead of the liquid composition (Rl), and the evaluation of the mask deposit was performed.

As a result, no deposit was found on the removed counter substrate 4.

<Example 5>

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 80 parts by weight of 75/25 weight ratio mixture of Pigment Yellow 138, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl methacrylate / N-phenylmaleimide air as alkali-soluble resin 65 weight part of copolymerization (copolymerization weight ratio = 15/10 / 18.8 / 25 / 31.2, Mw = 15,000, Mn = 6,000), (C) 80 weight part of dipentaerythritol hexaacrylates as a polyfunctional monomer, (D) as a photoinitiator 10 parts by weight of triazine-based compound (3), 6 parts by weight of 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, And 3 parts by weight of 2-mercaptobenzothiazole as hydrogen donor and 6 parts by weight of 4,4'-bis (diethylamino) benzophenone, (E) 3-amino-1,2-propanediol 2 as organic amino compound A liquid composition (G2) of the radiation sensitive composition was prepared by mixing parts by weight and 1,000 parts by weight of ethyl 3-ethoxypropionate as a solvent.

Next, except having used liquid composition (G2) instead of liquid composition (Rl), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part. Moreover, the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used liquid composition (G2) instead of liquid composition (Rl), it carried out similarly to Example 1, the coating board | substrate 5 and the opposing board | substrate 5 were produced, and the mask attachment was evaluated.

As a result, no deposit was confirmed on the removed counter substrate 5.

<Example 6>

(A) As a coloring agent, C.I. Pickition Green 7 and C.I. 60 parts by weight of a 65/35 (weight ratio) mixture of Pigment Yellow 83, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl methacrylate / N-phenylmaleic as alkali-soluble resin 75 weight part of mid copolymer (copolymerization weight ratio = 15/10 / 18.8 / 25 / 31.2, Mw = 24,000, Mn = 10,000), (C) 75 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) photopolymerization 12 parts by weight of a triazine compound (3) as an initiator, (E) 5 parts by weight of 2-aminoethanol as an organic amino compound, and 1,000 parts by weight of 90/10 (weight ratio) of ethyl 3-ethoxypropionate and cyclohexanone as a solvent It mixed and prepared the liquid composition (G3) of a radiation sensitive composition.

Next, except having used liquid composition (G3) instead of liquid composition (Rl), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used the liquid composition (G3) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 6 and the opposing board | substrate 6 were produced, and the mask attachment was evaluated.

As a result, no deposit was found on the removed counter substrate 6.

<Example 7>

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 110 parts by weight of a 75/25 (weight ratio) mixture of Pigment Yellow 139, (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymer weight ratio) as alkali-soluble resin = 15/15/35/10/25, Mw = 30,000, Mn = 10,000) 60 parts by weight, (C) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) a triazine compound as a photopolymerization initiator ( 2) Radiation-sensitive properties by mixing 15 parts by weight, (E) 5 parts by weight of 2-aminoethanol as an organic amino compound, and 1,000 parts by weight of a 95/5 (weight ratio) mixture of propylene glycol monomethyl ether acetate and cyclohexanone as a solvent A liquid composition (R4) of the composition was prepared.

Next, except having used liquid composition (R4) instead of liquid composition (R1), it carried out similarly to Example 1, and formed the red striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used the liquid composition (R4) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 7 and the opposing board | substrate 7 were produced, and the mask adhesion was evaluated.

As a result, no deposit was found on the removed counter substrate 7.

<Example 8>

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 120 parts by weight of a 70/30 (weight ratio) mixture of Pigment Yellow 150, (B) methacrylic acid / ω-carboxypolycaprolactone monoacrylate / styrene / benzyl methacrylate / glycerol monomethacrylate / as alkali-soluble resin 60 parts by weight of N-phenylmaleimide copolymer (copolymerization weight ratio = 15/10 / 11.3 / 35/10 / 18.7, Mw = 40,000, Mn = 20,000), (C) 90 weights of dipentaerythritol hexaacrylate as a polyfunctional monomer (D) 20 parts by weight of a triazine compound (2) as a photopolymerization initiator, (E) 10 parts by weight of 2-aminoethanol as an organic amino compound, and 95/5 of propylene glycol monomethyl ether acetate and cyclohexanone as a solvent. (Weight Ratio) 1,000 parts by weight of the mixture was mixed to prepare a liquid composition (G4) of the radiation sensitive composition.

Next, except having used liquid composition (G4) instead of liquid composition (Rl), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used the liquid composition (G4) instead of the liquid composition (R1), it carried out similarly to Example 1, the coating substrate 8 and the counter substrate 8 were produced, and the mask adhesion material was evaluated.

As a result, no deposit was found on the removed counter substrate 8.

<Example 9>

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. Instead of 120 parts by weight of a 70/30 (weight ratio) mixture of Pigment Yellow 150, C.I. A liquid composition (Bl) of a radiation sensitive composition was produced in the same manner as in Example 8 except that 60 parts by weight of Pigment Blue 15: 6 was used.

Subsequently, a blue striped color filter was formed on the substrate in the same manner as in Example 1 except that the liquid composition (Bl) was used in place of the liquid composition (Rl).

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment)

The coating substrate 9 and the opposing board | substrate 9 were produced like Example 1 except having used the liquid composition (Bl) instead of the liquid composition (Rl), and the mask adhesion material was evaluated.

As a result, no deposit was found on the removed counter substrate 9.

<Example 10>

(A) As a coloring agent, C.I. A liquid composition (B2) of the radiation sensitive composition was produced in the same manner as in Example 9, except that 120 parts by weight of Pigment Blue 15: 6 was used.

Next, except having used the liquid composition (B2) instead of the liquid composition (R1), it carried out similarly to Example 1, and formed the blue striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the residue and the background unevenness were not confirmed on the board | substrate of an unexposed part, and also the adhesiveness with the board | substrate of the obtained pixel was also excellent.

<Evaluation of Mask Attachment>

Except having used the liquid composition (B2) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 10 and the opposing board | substrate 10 were produced, and the mask attachment was evaluated.

As a result, no deposit was found on the removed counter substrate 10.

<Comparative Example 1>

(E) Liquid composition (g1) of the radiation sensitive composition was produced in the same manner as in Example 4 except that 5-amino-1-pentanol which was an organic amino compound was not added. Next, except having used the liquid composition (gl) instead of the liquid composition (Rl), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the milky white background unevenness was confirmed on the board | substrate of an unexposed part.

<Evaluation of Mask Attachment>

Except having used the liquid composition (g1) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 7 and the opposing board | substrate 7 were produced, and the mask adhesion material was evaluated.

As a result, white deposits were observed on the removed counter substrate 7.

<Comparative Example 2>

(E) Example except having added 5 parts of alicyclic epoxy resin cell oxide 2021P (brand name, the product made by Daicel Chemical Industries, Ltd.) instead of 5-amino-1-pentanol which is an organic amino compound. In the same manner as 4, a liquid composition (g2) of the radiation sensitive composition was prepared.

Next, except having used liquid composition (g2) instead of liquid composition (Rl), it carried out similarly to Example 1, and formed the green striped color filter on the board | substrate.

When the obtained color filter was observed using the optical microscope, the milky white background unevenness was confirmed on the board | substrate of an unexposed part.

<Evaluation of Mask Attachment>

Except having used the liquid composition (g2) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 8 and the opposing board | substrate 8 were produced, and the mask attachment was evaluated.

As a result, white deposits were confirmed on the removed counter substrate 8.

<Comparative Example 3>

(E) 5 parts of polyfunctional alicyclic epoxy resin eporide GT401 (brand name, the product made by Daicel Chemical Industries, Ltd.) were added instead of 5-amino-1-pentanol which is an organic amino compound, In the same manner as in Example 4, a liquid composition (g3) of the radiation sensitive composition was prepared.

Subsequently, a green striped color filter was formed on the substrate in the same manner as in Example 1 except that the liquid composition (g3) was used instead of the liquid composition (Rl).

When the obtained color filter was observed using the optical microscope, the milky white background unevenness was confirmed on the board | substrate of an unexposed part.

<Evaluation of Mask Attachment>

Except having used the liquid composition (g3) instead of the liquid composition (Rl), it carried out similarly to Example 1, the coating substrate 9 and the opposing board | substrate 9 were produced, and the mask attachment was evaluated.

As a result, white deposits were observed on the removed counter substrate 9.

The radiation sensitive composition for color filters of 1st invention contains the active radical or volatile acidic compound (for example, hydrogen halide etc.) which generate | occur | produce or generate | occur | produce from the triazine type compound contained in a photoinitiator by containing (E) organic amino compound. ), It not only prevents the occurrence of a mask deposit during exposure, but also has excellent developability, and does not cause residue and background stains on the substrate of the unexposed portion, and also serves as a substrate and a light shielding layer. The pixel which is excellent also in the adhesiveness of can be provided.

In addition, the color filter of the second invention is formed of the radiation-sensitive composition for color filters of the first invention, and does not require an operation of removing residues and uneven spots of the unexposed portion by brush cleaning or sponge cleaning in the process of forming the same. Therefore, there is no fear of damaging the pixel pattern, the adhesion of the pixel to the substrate is excellent, high reliability, and industrially advantageously produced without the occurrence of a mask deposit during exposure.

Therefore, the radiation sensitive composition for color filters of the first invention and the color filter of the second invention are very useful for a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Claims (5)

(A) a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) photoinitiator containing triazine type compound, and (E) molecule | numerator containing organic amino compound which has 1 or more amino group in what is contained. The radiation sensitive composition for color filters characterized by the above-mentioned. The radiation sensitive composition for color filters of Claim 1 in which (D) photoinitiator further contains 1 or more types chosen from the group of acetophenone type compound and a biimidazole type compound. The organic amino compound of the component (E) comprises at least one member selected from the group consisting of monoalkanolamines, monocycloalkanolamines, aminoalkanediols, aminocycloalkanediols and aminophenols. The radiation sensitive composition for color filters characterized by the above-mentioned. The radiation sensitive composition for color filters according to claim 1, wherein the proportion of the pigment in all the components except the solvent in the composition is 20 to 50% by weight. It has a pixel formed from the radiation sensitive composition for color filters in any one of Claims 1-4, The color filter characterized by the above-mentioned.