JP4882396B2 - Radiation-sensitive composition for forming colored layer, color filter, and liquid crystal display device - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display device, and more particularly useful for a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube device, and the like. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter having a colored layer formed from the radiation-sensitive composition, and a liquid crystal display device including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, in the technical field of color filters, the movement to reduce the tact time by reducing the exposure amount or increasing the substrate conveyance speed in the development process has become mainstream. However, since the development conditions become severe due to a decrease in the exposure amount and an increase in the substrate conveyance speed, the conventional colored radiation-sensitive composition tends to cause chipping of the pattern edge and undercut during development, thereby reducing the tact time. However, it has been difficult to obtain a pixel and a black matrix having a good pattern shape.

JP-A-2-144502 JP-A-3-53201

  An object of the present invention is to provide a radiation-sensitive composition for forming a colored layer exhibiting excellent developability, more specifically, without causing pattern edge chipping and undercut even under low exposure and severe development conditions. Another object of the present invention is to provide a novel radiation-sensitive composition for forming a colored layer that provides a pixel and a black matrix that do not leave undissolved substances during development or cause scum at pattern edges.

The present invention, first,
(A) a colorant, (B) an alkali-soluble resin containing a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer , ( C) a polyfunctional monomer, and (D) at least one component selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), a thioxanthone compound, And at least one component selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2), and a thioxanthone series A radiation-sensitive composition for forming a colored layer by ultraviolet irradiation using a high-pressure mercury lamp, characterized in that the content is 10 to 50% by weight based on the total amount of the compound.

[In the formulas (1) and (2), each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² is independent from each other. Represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ³ is independently a hydrogen atom or a linear or branched chain having 1 to 12 carbon atoms. Alternatively, it represents a cyclic alkyl group, and each R ⁴ , each R ⁵ and each R ⁶ independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. However, the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a group of straight, branched or cyclic alkoxyl groups having 1 to 6 carbon atoms, phenyl groups and halogen atoms. And the phenyl groups of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear group having 1 to 6 carbon atoms. Further, it may be substituted with a substituent selected from the group consisting of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom. ]
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

The present invention secondly,
It comprises a color filter having a colored layer formed through a step of exposing the coating film of the radiation-sensitive composition for forming the colored layer to ultraviolet rays using a high-pressure mercury lamp .

Third, the present invention
A liquid crystal display element comprising the color filter.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer- (A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include compounds classified as Pigment in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the color index (C .. I.) Numbers can be mentioned.

C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185;

C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97,

C. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60;
C. I. Pigment green 7, C.I. I. Pigment green 36;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

    Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  In the present invention, the organic pigment and the inorganic pigment can be used alone or in admixture of two or more, and the organic pigment and the inorganic pigment can be used in combination. Preferably, one or more organic pigments are used, and two or more organic pigments and / or carbon black are preferably used in forming the black matrix.

  In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in Patent Document 3 and the like, and various commercially available polymers or oligomers for dispersing pigments.

JP-A-8-259876

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-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; polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Disperbyk (Bicchemy Japan Co., Ltd.), Sol Sparse (Seneca Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

-(B) Alkali-soluble resin-
Alkali-soluble resin in the present invention, (A) soluble and acts as a binder with respect to the colorant, and when manufacturing a color filter, a developing solution used in the developing process, particularly preferably an alkali developing solution resins having, preferably an alkali-soluble resin having a carboxyl group, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter, referred to as "carboxyl group-containing unsaturated monomer".) and the other copolymerizable ethylenically unsaturated monomer (hereinafter, referred to as "copolymerizable unsaturated monomer".) copolymer (hereinafter referred to as "carboxyl group-containing copolymer".) is intended to include.

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Of these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are M-5300 and M-5400 (Toagosei Co., Ltd.), respectively. It is commercially available under the trade name of
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the copolymerizable unsaturated monomer include:
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturated carboxylic esters such as (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer in the present invention, (b1) (meth) acrylic acid is an essential component, and in some cases, succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meta). ) A carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group of acrylates, and (b2) styrene, N-phenylmaleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) Copolymerization with at least one copolymerizable unsaturated monomer selected from the group of acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Polymer (hereinafter referred to as “cal Cyclohexyl group-containing copolymer (B1) "hereinafter.) Are preferred.

As specific examples of the carboxyl group-containing copolymer (B1),
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / styrene / N-phenylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / styrene / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene / N-phenylmaleimide / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene / N-phenylmaleimide / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-phenylmaleimide / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-phenylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-cyclohexylmaleimide / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / N-cyclohexylmaleimide / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer and the like.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be reduced, whereas when it exceeds 50% by weight, the solubility in an alkali developer is low. When the development is performed with an alkaline developer, the colored layer tends to drop off from the substrate or the surface of the colored layer becomes rough.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000 to 300,000, preferably Is 5,000 to 100,000.
Further, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually from 3,000 to 60,000. , Preferably 5,000 to 25,000.
In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby pixels and black having sharp pattern edges can be obtained. A matrix can be formed, and residues, background stains, film residues, and the like are less likely to occur on the unexposed portion of the substrate and the light shielding layer during development.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1 to 5, and more preferably 1 to 4.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
The usage-amount of the 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, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. If the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, so that it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,

Compound represented by the following formula (3)

And a compound represented by the following formula (4):

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
The said 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, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include (B) compounds similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin, and N- (meth). In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, examples of commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.

  The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be lowered. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is lowered or unexposed parts There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.

-(D) Photoradical generator-
The photoradical generator in the present invention is at least one component selected from the group of the compound represented by the formula (1) and the compound represented by the formula (2) (hereinafter referred to as “photoradical generator (D1)”. ) ") And a thioxanthone compound, and upon exposure to ultraviolet light, (C) a radical capable of initiating polymerization of the polyfunctional monomer and optionally used monofunctional monomer is generated. Consists of ingredients.

In formula (1) and formula (2), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ¹ , R ² and R ³ include, for example, a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Examples of the linear, branched or cyclic alkyl group having 1 to ⁶ carbon atoms of R ⁴ , R ⁵ and R ⁶ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Of the substituents for the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and the substituents for the phenyl groups of R ¹ and R ² , a straight chain having 1 to 6 carbon atoms Examples of the branched or cyclic alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group. As the halogen atom, For example, a fluorine atom, a chlorine atom, etc. can be mentioned.
Among the substituents for each phenyl group of R ¹ and R ² , examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, An i-propyl group, an n-butyl group, a t-butyl group, etc. can be mentioned.
One or more of these substituents may be present in each alkyl group and each phenyl group.

In Formula (1) and Formula (2), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a phenyl group or the like, and R ² is a hydrogen atom , methyl group, ethyl group, n- propyl group, i- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, preferably such as n- octyl group, a R ³ is A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and the like are preferable. Further, as R ⁴ , R ⁵ and R ⁶ , a hydrogen atom, a methyl group, an ethyl group, n- A propyl group, i-propyl group, n-butyl group and the like are preferable.

  Specific examples of the preferred photoradical generator (D1) in the present invention include 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate and the like.

Of these photoradical generators (D1), 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate is preferred.
The said photoradical generator (D1) can be used individually or in mixture of 2 or more types.

  Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-i-propylthioxanthone.

In the present invention, the thioxanthone compound is preferably 2,4-diethylthioxanthone.
The thioxanthone compounds can be used alone or in admixture of two or more.

The photoradical generator in the present invention may further contain components other than the photoradical generator (D1) and the thioxanthone compound (hereinafter referred to as “other photoradical generator”).
Examples of other photo radical generators include other O-acyloxime compounds, benzoin compounds, acetophenone compounds, α-diketone compounds, polynuclear quinone compounds, phosphine compounds, triazine compounds, and the like. Can do.

Examples of the other O-acyloxime compounds include 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4. -(Phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octadione-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- [O- (4-methylbenzoyloxime)] and the like Can be mentioned.
Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.

  Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl Examples include phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one. Kill.

Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-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- Kishisuchiriru) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

Compound represented by the following formula (6)

等のハロメチル基を有する化合物等を挙げることができる。
本発明において、他の光ラジカル発生剤は、単独でまたは２種以上を混合して使用することができる。 And a compound represented by the following formula (7):

Examples thereof include compounds having a halomethyl group.
In the present invention, other photo radical generators can be used alone or in admixture of two or more.

  In the present invention, the total use amount of the photo radical generator is usually 0.01 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer optionally used. It is -200 weight part, Preferably it is 1-120 weight part, Most preferably, it is 1-100 weight part. In this case, if the total use amount of the photo radical generator is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 200 parts by weight, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer. .

The proportion of thioxanthone compounds, based on the total of the photoradical generator and (D1) and thioxanthone compounds, 10 to 50 wt%, preferably from 10 to 30 wt%. In this case, if the use ratio of the thioxanthone compound is less than 10% by weight, it may be difficult to obtain a pixel pattern, while if it exceeds 50% by weight, the intended effect of the present invention may be impaired. There is.

Moreover, the usage-amount of another photoradical generator is 50 weight% or less normally with respect to the sum total of a photoradical generator, Preferably it is 30 weight% or less. In this case, if the use ratio of the other photoradical generator exceeds 50% by weight, the intended effect of the present invention may be impaired.
In the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking / sensitizer can be used in combination with the photoradical generator as necessary.

-Additives-
The radiation-sensitive composition for forming a colored layer of the present invention can contain various additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (provided that the solubility of the radiation-sensitive composition in an alkaline developer is further improved and the action of further suppressing the remaining undissolved product after development, etc.) The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
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 organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
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, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, 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, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine 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 (4-cyclo Di (cyclo) alkanolamines such as hexanol) 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-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as 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-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the solvent described later, prevention of soiling and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, in particular 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 and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound 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 amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

(Poly) alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl Rubin acid and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.

  The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

Color filter The color filter of this invention has a colored layer formed through the process of irradiating an ultraviolet-ray to the coating film of the radiation sensitive composition for colored layer formation of this invention using a high pressure mercury lamp .
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the product, pre-baking is performed to evaporate the solvent, thereby forming a coating film.
Next, this coating film is exposed to ultraviolet rays using a high-pressure mercury lamp through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portion of the coating film, and then post-baking, A pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
The black matrix can be formed in the same manner as in the pixel formation using the radiation-sensitive composition for forming a colored layer of the present invention.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

The ultraviolet radiation used in forming the pixel and / or a black matrix, ultraviolet rays having a wavelength in the range of 190~450nm is preferred.
Exposure of ultraviolet rays is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

Liquid crystal display element The liquid crystal display element of this invention comprises the color filter of this invention.
Moreover, as one embodiment of the liquid crystal display element of the present invention, a pixel and / or a black matrix is formed on a thin film transistor substrate array as described above using the radiation-sensitive composition for forming a colored layer of the present invention. By forming, a liquid crystal display element having particularly excellent characteristics can be manufactured.

The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are as follows. (C)
(A) (B) A radiation-sensitive composition for forming a colored layer, wherein the alkali-soluble resin contains a carboxyl group-containing copolymer (B1).
(B) (C) The radiation sensitive material for forming a colored layer according to (a), wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Sex composition.
(C) The photoradical generator (D1) is 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. The radiation-sensitive composition for forming a colored layer according to the above (a) or (b), comprising: -carbazol-3-yl] -ethane-1-one oxime-O-acetate.

Further, the preferred color filter of the present invention is
(D) Pixels and / or black matrix formed through a step of exposing the coating film of the radiation-sensitive composition for forming a colored layer according to (i), (b) or (c) above to ultraviolet rays using a high-pressure mercury lamp. Have

The preferred liquid crystal display element of the present invention is
(E) comprising the color filter of (d),
A more preferred liquid crystal display element of the present invention is
(F) The above-mentioned (d) color filter is provided on the thin film transistor substrate array.

The radiation-sensitive composition for forming a colored layer of the present invention has a low exposure (for example, by using a photoradical generator containing a photoradical generator (D1) and a thioxanthone compound that are highly sensitive to radiation. No pattern edge chipping or undercut occurs even under a set exposure amount of 400 J / m ² ) and severe development conditions (for example, development temperature 30 ° C., shower pressure 110 KPa, developer flow rate 1.2 liters / minute). In addition, it is possible to form a good pixel pattern and a black matrix pattern in which undissolved substances remain during development and no scum is generated at the pattern edge.
Furthermore, the pixels and black matrix formed using the radiation-sensitive composition for forming a colored layer of the present invention have high surface smoothness and excellent adhesion to the substrate.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for liquid crystal display elements in the electronic industry.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Here, parts and% are based on weight.
<(B) Production of alkali-soluble resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate, followed by 15 parts of methacrylic acid, 15 parts of styrene, N— After charging 25 parts of phenylmaleimide, 35 parts of benzyl methacrylate, 10 parts of glycerol monomethacrylate and 5 parts of α-methylstyrene dimer, which is a chain transfer agent, the mixture was purged with nitrogen, and then gently stirred to raise the temperature of the reaction solution to 80 ° C. The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further performed for 1 hour, whereby a resin solution (solid content concentration = 33.0%).
The obtained resin was Mw = 10,000 and Mn = 5,900. This resin is referred to as “resin (B-1)”.

Example 1
<Preparation of liquid composition>
(A) 78 parts of 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a coloring agent, (B) Resin (B-1) 60 parts as an alkali-soluble resin, (C) Many 90 parts of dipentaerythritol hexaacrylate as a functional monomer and 1- [9-ethyl-6- (2-methylbenzoyl) -9. As a photo radical generator (D1). H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals, the same shall apply hereinafter) and 2, as a photoradical generator (D2) 15 parts of 4-diethylthioxanthone (trade name KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) and 1,000 parts by weight of 80/20 (weight ratio) mixture of cyclohexanone and propylene glycol monomethyl ether acetate as a solvent were mixed. Thus, a liquid composition (B1) of a radiation sensitive composition was prepared.

<Formation of colored layer>
The liquid composition (B1) was applied on a soda glass substrate having a SiO2 film formed on the surface thereof to prevent elution of sodium ions, using a spin coater, and then pre-baked on a hot plate at 80 ° C. for 100 seconds. A film having a thickness of 2.5 μm was formed.
Next, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays including 365 nm, 405 nm, and 436 nm through a photomask (slit width 90 μm) using a high pressure mercury lamp. The exposure amount at this time was set to a low value of 400 J / m ² . Thereafter, the substrate was shower-developed using a 0.04% aqueous potassium hydroxide solution at a development temperature of 30 ° C., a shower pressure of 110 KPa, and a developer flow rate of 1.2 liters / minute. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a 220 ° C. clean oven for 30 minutes to form a pixel array in which blue stripe pixel patterns were arranged on the substrate.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

Comparative Example 1
<Preparation of liquid composition and formation of colored layer>
As a photo radical generator, 1- [9-ethyl-6- (2-methylbenzoyl) -9. Which is a photo radical generator (D1). H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate was used in the same manner as in Example 1 to prepare a liquid composition (b1) of a radiation-sensitive composition except that 10 parts were used.
Next, a pixel array in which blue stripe pixel patterns were arranged on the substrate was formed in the same manner as in Example 1 except that the liquid composition (b1) was used instead of the liquid composition (B1).

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed substrate, but chipping of the edge of the pixel pattern and peeling of the pattern itself were observed.
Moreover, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed.

Comparative Example 2
<Preparation of liquid composition and formation of colored layer>
(A) 80 parts of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, (B) 60 parts of a resin (B-1) as an alkali-soluble resin, (C) Many 90 parts of dipentaerythritol hexaacrylate as a functional monomer and 1- [9-ethyl-6- (2-methylbenzoyl) -9. Which is a photo radical generator (D1) as a photo radical generator. H. -Carbazol-3-yl] -ethane-1-one oxime-O- acetate and 1,000 parts by weight of 80/20 (weight ratio) mixture of cyclohexanone and propylene glycol monomethyl ether acetate as solvent , A liquid composition (b2) of a radiation sensitive composition was prepared.
Next, a pixel array in which blue stripe pixel patterns were arranged on the substrate was formed in the same manner as in Example 1 except that the liquid composition (b2) was used in place of the liquid composition (B 1 ). .

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed substrate, but chipping of the edge of the pixel pattern and peeling of the pattern itself were observed.
Moreover, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), an undercut was observed.

Claims (3)

(A) a colorant, (B) an alkali-soluble resin containing a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer , ( C) a polyfunctional monomer, and (D) at least one component selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), a thioxanthone compound, And at least one component selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2), and a thioxanthone series A radiation-sensitive composition for forming a colored layer by ultraviolet irradiation using a high-pressure mercury lamp, characterized in that the content is 10 to 50% by weight based on the total amount of the compound.

[In the formulas (1) and (2), each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² is independent from each other. Represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ³ is independently a hydrogen atom or a linear or branched chain having 1 to 12 carbon atoms. Alternatively, it represents a cyclic alkyl group, and each R ⁴ , each R ⁵ and each R ⁶ independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. However, the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a group of straight, branched or cyclic alkoxyl groups having 1 to 6 carbon atoms, phenyl groups and halogen atoms. And the phenyl groups of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear group having 1 to 6 carbon atoms. Further, it may be substituted with a substituent selected from the group consisting of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom. ]   The color filter which has a colored layer formed through the process of irradiating an ultraviolet-ray to the coating film of the radiation sensitive composition for colored layer formation of Claim 1 using a high pressure mercury lamp.   A liquid crystal display device comprising the color filter according to claim 2.