KR20060047458A - Radiation sensitive composition for forming a colored layer, color filter and liquid crystal display panel - Google Patents

Abstract

The present invention relates to colorants, alkali soluble resins, polyfunctional monomers and morpholinophenyls such as 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one It relates to the radiation sensitive resin composition for colored layer formation containing the radiation sensitive polymerization initiator of a compound.

This composition can suppress the contamination of a kiln, a photomask, etc. by sublimation of a radiation sensitive polymerization initiator component, and it does not produce a foreign material in a liquid, and is excellent also in developability and a pattern shape.

Description

Radiation Sensitive Composition for Forming a Colored Layer, Color Filter and Liquid Crystal Display Panel}

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display panel, and more particularly, to the formation of a colored layer of a color filter used in a transmissive or reflective color liquid crystal display device, a color imaging tube element, or the like. A color filter provided with the radiation sensitive composition used, the colored layer formed from this radiation sensitive composition, and the liquid crystal display panel provided with this color filter.

Conventionally, in manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a colored radiation sensitive composition on a board | substrate or the board | substrate in which the light shielding layer of a predetermined pattern was previously formed, and drying, a predetermined | prescribed thing with respect to a coating film The formation method (refer Japanese Unexamined-Japanese-Patent No. 2-144502 and Japanese Unexamined-Japanese-Patent No. 3-53201) by irradiating a pattern shape with radiation (hereinafter called "exposure"), and developing it, and developing each pixel of each color is developed. Known.

In recent years, the size of the mother glass substrate has been enlarged from about 680 × 880 mm to about 1,500 × 1,800 mm due to the larger area of the liquid crystal display panel, the improvement in productivity, and the like. However, as the size of the substrate increases, a problem arises in that the radiation sensitive polymerization initiator component in the radiation sensitive composition sublimes upon the formation of the color filter and contaminates the firing furnace or photomask, resulting in a decrease in production tact. And causing an increase in production costs.

In addition, the present applicant discloses 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane as a radiation sensitive polymerization initiator of a radiation sensitive composition in Japanese Patent Laid-Open No. 2001-235617. Radiation-sensitive polymerization by using a bromine substituted acetophenone-based compound such as -1-one or 1- (3-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one It has been disclosed that contamination of a firing furnace or exhaust duct due to sublimation of the initiator component, clogging of a filter provided in a developing line when the developer is used repeatedly, and the like can be reduced.

Patent Document 1: Japanese Patent Application Laid-Open No. 2-144502

Patent Document 2: Japanese Patent Application Laid-Open No. 3-53201

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-235617

However, as a conventional radiation sensitive composition used for the formation of a color filter including the one disclosed in Japanese Unexamined Patent Application Publication No. 2001-235617, contamination of a firing furnace, a photomask, or the like by sublimation of the radiation sensitive polymerization initiator component, and foreign matter in liquid It cannot be said that it is enough in terms of preventing generation | occurrence | production, and the development of the radiation sensitive composition also provided with these characteristics was strongly desired.

An object of the present invention is to suppress contamination of a firing furnace, a photomask, or the like by sublimation of a radiation-sensitive polymerization initiator component, and to prevent foreign substances from occurring in the liquid, and also to develop, to form a pattern, etc. It is providing the liquid crystal display panel provided with the color filter provided with the radiation sensitive composition used for formation, the colored layer formed from this radiation sensitive composition, and this color filter.

Still other objects and advantages of the invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention, firstly,

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, or monofunctional compound with it, contains a combination and the compound represented by (D) following General formula (1), and is used for formation of a colored layer, It is characterized by the above-mentioned. It is achieved by a radiation sensitive resin composition.

In formula (1), R ¹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and R ² and R ³ are each independently a hydrogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; Or a benzyl group, R ⁴ , R ⁵ , R ⁷ and R 8 are each independently a hydrogen atom; Halogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; Or a linear or branched alkoxyl group having 1 to 4 carbon atoms, R ⁶ is a halogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; C1-C12 linear, branched, or cyclic alkyl group substituted by the substituent chosen from the group containing a hydroxyl group and a C1-C4 linear or branched alkoxyl group; Linear or branched alkoxyl groups having 1 to 4 carbon atoms; Or a straight or branched alkoxyl group having 2 to 4 carbon atoms substituted with a substituent selected from the group comprising a hydroxyl group and a straight or branched alkoxyl group having 1 to 4 carbon atoms.

"Radiation" as used in the present invention means ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular rays, gamma rays, synchrotron radiation, proton beam rays, and the like.

In addition, the "colored layer" used in this invention means the layer containing a pixel and / or a black matrix.

According to the present invention, the above objects and advantages of the present invention are second,

It is achieved by the color filter which comprises the colored layer formed from the radiation sensitive composition of the said invention.

Moreover, according to this invention, the said objective and advantage of this invention are 3rd,

It is achieved by the liquid crystal display panel provided with the said color filter.

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

(A) colorant

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

Since high color development and heat resistance are required for a color filter, as a coloring agent in this invention, the coloring agent which has high coloring property and high heat resistance, especially the coloring agent with high thermal decomposition resistance is preferable. Pigments are preferably used, particularly preferably organic pigments and carbon blacks.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer Sand Colourists), specifically, the following color index (CI) numbers. It can be mentioned.

Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81 CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 1O4, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI . Pigment Yellow 117, C.I. Pigment Yellow 119, C.I. Pigment Yellow 120, C.I. Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 180 CI pigment yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI pigment orange 64, CI pigment orange 71, CI pigment orange 73;

C.I. Pigment Violet 1, 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;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment CIment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI Pigment De 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2 , CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, CI Pigment Red 101,

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

Moreover, such an organic pigment can be refine | purified and used, for example by the sulfuric acid recrystallization method, the solvent washing method, these combinations, etc.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zincated, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), cadmium red, ultramarine blue, blue wire, and chromium oxide. Rust, cobalt rust, amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

In this invention, an organic pigment and an inorganic pigment can be used individually or in mixture of 2 or more types, respectively, and can also use an organic pigment and an inorganic pigment together. When forming a pixel, 1 or more types of organic pigments are used preferably. Also, when forming the black matrix, preferably two or more organic pigments and / or carbon blacks are used.

In the present invention, each of the pigments can be used by modifying the particle surface thereof with a polymer as desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., the polymer for various pigment dispersions, and oligomer etc. which are marketed are mentioned, for example.

In addition, the coloring agent in this invention can be used like a dispersing agent as needed.

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

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and 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 polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and MegaPak (Daintbone Ink) Kagaku Kogyo Co., Ltd.), Flowride (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), Disperbyk (Bikkemi Japan Co., Ltd.), Sol spas (made by Seneca Co., Ltd.) etc. are mentioned.

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

The amount of the surfactant to be used is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight with respect to 100 parts by weight of the colorant.

(B) alkali soluble resin

As alkali-soluble resin in this invention, when it acts as a binder with respect to a coloring agent, and also forms a colored layer, if it has solubility with respect to the developing solution used at the developing process process, Preferably alkaline developing solution, it will be specifically limited. It is not. Especially, alkali-soluble resin which has a carboxyl group is preferable, and ethylenically unsaturated monomer which can copolymerize another ethylenically unsaturated monomer (henceforth "carboxyl group-containing unsaturated monomer") which has one or more carboxyl groups (hereinafter, "copolymerization" Copolymer (hereinafter referred to as "carboxyl group-containing copolymer") is preferred.

As a carboxyl group-containing unsaturated monomer, for example

Unsaturated mono carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

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

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and mono phthalate [2- (meth) acryloyloxyethyl] ester;

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

Among these carboxyl group-containing unsaturated monomers, mono succinate (2-acryloyloxyethyl) and mono phthalate (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.

Moreover, as a 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;

Other polymerizable aromatic compounds such as indene, 1-methylindene and acenaphthylene;

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, cyclohexyl (meth) acrylate, benzyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxy propylene glycol (meth) acrylate, Toxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth Unsaturated carboxylic acid esters such as acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as latex and 3-dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; 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 (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;

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

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

The macromonomer which has a mono (meth) acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, etc. are mentioned.

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

As a carboxyl group-containing copolymer in this invention, (i) (meth) acrylic acid is an essential component, and monosuccinate mono [2- (meth) acryloyloxyethyl] and (omega) -carboxypolycaprolactone mono (meth) A carboxyl group-containing unsaturated monomer component which also contains at least one compound selected from the group comprising acrylate; and (ii) styrene, acenaphthylene, methyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. At least one selected from the group consisting of allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer Preferred is a copolymer with hereinafter (hereinafter referred to as "carboxyl group-containing copolymer I").

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

(Meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate Copolymer,

(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macro monomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macro monomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

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

(Meth) acrylic acid / mono succinate 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,

(Meth) acrylic acid / acenaphthylene / benzyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate /?-Carboxypolycaprolactone mono (meth) acrylate copolymer and the like.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the copolymerization ratio of a carboxyl group-containing unsaturated monomer is less than 5 weight%, there exists a tendency for the solubility to the alkaline developing solution of the radiation sensitive composition obtained to fall. On the other hand, when it exceeds 50 weight%, the solubility with respect to an alkaline developing solution will become large too much, and when developing with an alkaline developing solution, there exists a tendency which becomes easy to cause the fall of the colored layer from the board | substrate and the film | membrane of the colored layer surface.

The polystyrene reduced 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 preferably 3,000 to 300,000, more preferably. Preferably 5,000 to 100,000.

Moreover, polystyrene conversion number average molecular weight (henceforth "Mn") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin in this invention becomes like this. Preferably it is 3,000-60,000, More preferably, it is 5,000-25,000.

In this invention, the radiation sensitive composition excellent in developability is obtained by using alkali-soluble resin which has such specific Mw and Mn. In addition, by using it, a pixel pattern and a black matrix pattern having sharp pattern edges can be formed, and at the time of development, residues, background contamination, film residues, etc. are hardly generated on the substrate and the light shielding layer of the unexposed part. .

Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin in this invention becomes like this. Preferably it is 1-5, Especially preferably, it is 1-4.

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

The usage-amount of alkali-soluble resin in this invention becomes like this. Preferably it is 10-1,000 weight part, More preferably, it is 20-500 weight part with respect to 100 weight part of (A) coloring agents. If the amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may decrease or contamination or film residue may occur on the substrate or the light shielding layer of the unexposed part. On the other hand, when it exceeds 1,00 weight part, since a coloring agent density | concentration falls relatively, it may become difficult to achieve the target density | concentration as a thin film.

(C) a polyfunctional monomer or a combination of a monofunctional compound

The polyfunctional monomer in this invention is a monomer which has a 2 or more polymerizable unsaturated bond.

As an example of a polyfunctional monomer,

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, or modified dicarboxylic acids thereof;

Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin;

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate etc. are mentioned.

Of these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimetholpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic The rate, dipentaerythritol hexamethacrylate, the compound represented by the following formula (2) or formula (3), and the like are preferable.

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and further, on the substrate and the light shielding layer of the unexposed part. It is preferable in that it is difficult to generate background contamination, membrane residues, and the like.

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

In the present invention, the amount of the polyfunctional monomer used is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin. When the usage-amount of a polyfunctional monomer is less than 5 weight part, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall. On the other hand, when it exceeds 500 weight part, alkali developability will fall, for example, tends to generate background contamination, film | membrane residue, etc. on the board | substrate or light shielding layer of an unexposed part.

In addition, in this invention, the combination of the polyfunctional monomer and the monofunctional monomer which has one polymerizable unsaturated bond can be used.

As said monofunctional monomer, N- (meth) acryloyl morpholine and N-vinylpyrrolidone other than the monomer similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer which were illustrated, for example with respect to said (B) alkali-soluble resin M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as N-vinyl- epsilon caprolactam and a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types. The use ratio of the said monofunctional monomer becomes like this. Preferably it is 90 weight% or less, More preferably, it is 50 weight% or less with respect to the sum total of a polyfunctional monomer and a monofunctional monomer. In this case, when the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of a colored layer may become inadequate.

(D) radiation sensitive polymerization initiator

In the present invention, as the radiation-sensitive polymerization initiator, a compound represented by the formula (1) (hereinafter referred to as "polymerization initiator (1)") is used. This compound has the effect | action which produces the active species which can start superposition | polymerization of the said (C) polyfunctional monomer and the monofunctional monomer used optionally by exposure.

In the formula ^{1, R 1, R 2,} R 3, R 4, R 5, R 6, R 7 , and a straight chain of R ⁸ having from 1 to 12, as a branched or cyclic alkyl group such as 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, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Moreover, as a halogen atom of R <^4> , R <^5> , R <^6> , R <^7> and R <^8> , a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example.

Moreover, as a C1-C4 linear or branched alkoxyl group of R <^4> , R <^5> , R <^6> , R <^7> and R <^8> , For example, a methoxy group, an ethoxy group, n-propoxy group, i-prop An aoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, etc. are mentioned.

Moreover, in the C1-C12 linear, branched, or cyclic alkyl group substituted by the substituent chosen from the group containing the hydroxyl group of R <^6> and a C1-C4 linear or branched alkoxyl group, C1-C12 is carbon number of a substituent Examples of the linear or branched alkoxyl group of 1 to 4 include, for example, examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms with respect to R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ . The same thing as a group is mentioned.

As said substituent, a hydroxyl group, a methoxy group, etc. are preferable, for example.

In addition, one or more substituents may be present.

As the straight, branched or cyclic alkyl group of 1 to 12 carbon atoms R ^6, for example, the ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7 , and from 1 to 12 carbon atoms of R ⁸ The same thing as the group illustrated about the linear, branched, or cyclic alkyl group of is mentioned.

In addition, in the C2-C4 linear or branched alkoxyl group substituted by the substituent chosen from the group containing the hydroxyl group of R <^6> and a C1-C4 linear or branched alkoxyl group, carbon number of a substituent As a 1-4 linear or branched alkoxyl group, the C1-C4 linear or branched alkoxyl group of said R <^4> , R <^5> , R <^6> , R <^7> and R <^8> is illustrated, for example. The same thing as a group is mentioned.

As such a substituent, a hydroxyl group, a methoxy group, etc. are preferable, for example. One or more such substituents may be present.

As a C1-C4 linear or branched alkoxyl group of R <^6> , For example, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group and t-butoxy group.

In the formula (I), examples of R ^1, for example, methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, sec- butyl, t- butyl, n- pentyl , n-hexyl group and the like are preferable.

As R ² and R ³ , 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, n-heptyl group, n-octyl group and the like are preferable.

Moreover, as R <^4> , R <^5> , R <^7> and R <^8> , a hydrogen atom, a methyl group, an ethyl group, etc. are preferable.

As R ⁶ , 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-hex Real group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, hydroxymethyl group, 2-hydroxyethyl group, methoxymethyl group, 2-methoxyethyl group, methoxy group, ethoxy group, n- Propoxy group, i-propoxy group, n-butoxy group, hydroxymethoxy group, 2-hydroxyethoxy group, methoxymethoxy group, 2-methoxyethoxy group, etc. are preferable.

As a specific example of the preferable polymerization initiator (1) in this invention,

2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-ethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-i-propylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-n-butylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-i-butylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-n-dodecylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (3,4-dimethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-methoxybenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-ethoxybenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-hydroxymethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- [4- (2-hydroxyethoxy) benzyl] -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- [4- (2-methoxyethoxy) benzyl] -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one,

2- (4-i-propylbenzyl) -2-[(n-butyl) (methyl) amino] -1- (4-morpholinophenyl) butan-1-one,

2- (4-n-butylbenzyl) -2-[(n-butyl) (methyl) amino] -1- (4-morpholinophenyl) butan-1-one,

2- (4-i-propylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) pentan-1-one,

2- (4-i-butylbenzyl) -2-[(n-butyl) (methyl) amino)]-1- (4-morpholinophenyl) pentan-1-one,

2- (4-n-butoxybenzyl) -2-[(n-butyl) (methyl) amino] -1- (4-morpholinophenyl) pentan-1-one,

2- (4-methylbenzyl) -2- [di (n-octyl) amino] -1- (4-morpholinophenyl) hexan-1-one,

2- (4-n-dodecylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) octan-1-one, etc. are mentioned.

Among these polymerization initiators (1), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and 2- (4-ethylbenzyl)-in particular 2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-i-propylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl ) Butan-1-one and the like are preferable.

In this invention, a polymerization initiator (1) can be used individually or in mixture of 2 or more types.

In addition, in this invention, another radiation sensitive polymerization initiator (henceforth "other polymerization initiator") can be used together with a polymerization initiator (1).

As another polymerization initiator, for example, the biimidazole type compound, the acetophenone type compound, the benzophenone type compound, the benzoin type compound, (alpha) which has 1 or more types of main skeleton represented by each of following General formula (4), (5) and (6) -Diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, triazine compounds, carbazole compounds and the like. Among these, a biimidazole type compound, an acetophenone type compound, etc. are preferable.

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 etc. are mentioned.

Among these biimidazole compounds, 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 and 2,2'-bis (2,4,6-trichlorophenyl) -4, Preference is given to 4 ', 5,5'-tetraphenyl-1,2'-biimidazole. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is particularly preferred.

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

In this invention, when using a biimidazole type compound together as another polymerization initiator, it is preferable at the point which can improve a sensitivity further to add the hydrogen donor which follows. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As such a hydrogen donor, the mercaptan type compound defined below, the amine compound defined below, etc. are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having one or more mercapto groups directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, "mercap" Carbon-based hydrogen donor.

In addition, the amine compound is a compound having a benzene ring or a heterocycle as a parent nucleus and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the center of the nucleus (hereinafter, Amine hydrogen donor).

In addition, such a hydrogen donor may have a mercapto group and an amino group simultaneously.

Hereinafter, the hydrogen donor will be described in more detail.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle. In the case of having two or more such rings, a condensed ring may or may not be formed.

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

The mercaptan-based hydrogen donor may be substituted by a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like in portions 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 and the like.

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

Next, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle, and in the case of having two or more such rings, it may or may not form a condensed ring. have.

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 position other than the amino group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, and a nitrile group Or the like.

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. And 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid i-amyl, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) is preferred therein. Benzophenone is particularly preferred. In addition, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone can act as a radiation sensitive polymerization initiator by itself even when a biimidazole type compound does not exist. To indicate.

In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof. When the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors is used in combination, the formed colored layer is less likely to fall off the substrate during development, and the colored layer is preferably high in strength and sensitivity.

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) benzo Phenone etc. are mentioned.

Among these, more preferable combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone And a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

In addition, specific examples of the acetophenone-based compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (methylthio) phenyl] -2-methyl- 2-morpholinopropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- (4-morpholinophenyl) -2-benzyl- 2-dimethylaminobutan-1-one, 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1- (4-morpholinophenyl) -2- (2-bromobenzyl) -2-dimethylaminobutan-1-one, 1- (4-morpholinophenyl) -2- (4-bromobenzyl) -2-dimethylaminobutan-1- On, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 1- (4-morpholinophenyl) -2-benzyl-2 -Dimethylaminobutan-1-one, 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1- (4-morpholinophenyl)- 2- (4-bromobenzyl) -2-dimethylaminobutan-1-one and the like are preferable.

In this invention, even when using an acetophenone type compound together as another polymerization initiator, 1 or more types of said hydrogen donor can be added.

Moreover, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone etc. are mentioned as a specific example of the said benzophenone type compound.

Moreover, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoyl benzoate etc. are mentioned as a specific example of the said benzoin type compound.

Moreover, diacetyl, dibenzoyl, methyl benzoyl formate, etc. are mentioned as a specific example of the said (alpha)-diketone type compound.

Moreover, anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1, 4- naphthoquinone etc. are mentioned as a specific example of the said polynuclear quinone type compound.

Moreover, xanthone, a thioxanthone, 2-chloro thioxanthone etc. are mentioned as a specific example of the said xanthone type compound.

Moreover, bis (2, 4, 6- trimethyl benzoyl) phenyl phosphine oxide, 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as a specific example of the said phosphine type compound.

In addition, specific examples of the triazine-based 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-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 , 6-bis (trichloromethyl) -s-triazine,

And triazine compounds having a halomethyl group, such as compounds represented by the following formulas (7) and (8).

As a specific example of the carbazole compound, for example, 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] nonane-1,2-nonane-2-oxime-0- 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.-carbazole- 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-onoxime-O-acetate, 1- [9-ethyl -6- (2,4,6-trimethylbenzoyl) -9.H.-carbazol-3-yl] ethane-1-onoxime-O-benzoate, 1- [9-n-butyl-6- ( 2-ethylbenzoyl) -9.H.-carbazol-3-yl] ethane-1-one oxime-0-benzoate and the like.

Among these carbazole compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] ethane-1-one oxime-O-acetate is preferable.

These other polymerization initiators can be used individually or in mixture of 2 or more types. The use ratio of the other polymerization initiator is preferably 80% by weight or less, more preferably 70% by weight or less, based on the total of the polymerization initiator (1) and the other polymerization initiator. When the use ratio of another polymerization initiator exceeds 80 weight%, there exists a possibility that the desired effect of this invention may be impaired.

The amount of the polymerization initiator used in the present invention is preferably 0.01 to 200 parts by weight, more preferably 1 to 120 parts by weight, particularly preferably based on 100 parts by weight of the total amount of the (C) polyfunctional monomer or monofunctional monomer. Preferably from 1 to 100 parts by weight. When the usage-amount of a polymerization initiator is less than 0.01 weight part, hardening by exposure may become inadequate and it may become difficult to obtain the pattern array in which the pixel pattern or the black matrix pattern was arrange | positioned according to the predetermined sequence. On the other hand, when it exceeds 200 weight part, the formed colored layer will fall easily from a board | substrate at the time of image development, and background contamination, a film | membrane residue, etc. will be easy to generate | occur | produce on the board | substrate or light shielding layer of an unexposed part.

In addition, in this invention, like the said radiation sensitive polymerization initiator, 1 or more types of a sensitizer, a hardening accelerator, or a high molecular light crosslinking / sensitizer can be used together as needed.

additive

The radiation sensitive composition for colored layer formation of this invention can contain various additives as needed.

As said additive, the organic acid or organic amino compound which exhibits the effect which further improves the dissolution characteristic with respect to the alkaline developing solution of the radiation sensitive composition for colored layer formation, and further suppresses the remainder of the undissolved matter after image development, but the said hydrogen donor And the like).

As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has 1 or more carboxyl group in a molecule | numerator is preferable.

As an example of the said aliphatic carboxylic acid,

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, pimeric acid, suberic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;

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

Moreover, as said phenyl group containing carboxylic acid, the compound which the carboxyl group couple | bonded with the direct phenyl group, the carboxylic acid which the carboxyl group couple | bonded with the phenyl group through a carbon chain, etc. are mentioned, for example.

As an example of a phenyl group containing carboxylic acid,

Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cumic acid, hemeric 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, melanoic acid, pyromellitic acid,

And phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, cinnamiledic acid, cumalic acid, and umbelic acid.

Among these organic acids, as the aliphatic carboxylic acid, an aliphatic dicarboxylic acid is preferable in view of alkali solubility, solubility in a solvent to be described later, prevention of background contamination on a substrate or a light shielding layer of an unexposed part, and prevention of film residues. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferable. Moreover, as phenyl group containing carboxylic acid, aromatic dicarboxylic acid is preferable and phthalic acid is especially preferable.

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

The amount of the organic acid used is preferably 15% by weight or less, and more preferably 10% by weight or less based on the whole radiation-sensitive composition. When the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of a colored layer to fall.

Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator 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, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethyl Mono (cyclo) alkylamines such as cyclohexylamine, 3-ethylcyclohexylamine, 4-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, 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, 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, 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 said phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the compound which the amino group couple | bonded with the phenyl group through the carbon chain, etc. are mentioned, for example.

As an example of a phenyl group containing amine,

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;

And aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines and amino () are used as aliphatic amines from the viewpoints of solubility in a solvent to be described later, prevention of background contamination on a substrate or a light shielding layer of an unexposed part, and prevention of film residues. Cyclo) alkanediols are preferred, and 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 particularly preferred. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.

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

The usage-amount of an organic amino compound becomes like this. Preferably it is 15 weight% or less with respect to the whole radiation sensitive composition, More preferably, it is 10 weight% or less. When the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of a colored layer to fall.

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

Dispersion 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 ether, and poly (fluoroalkyl acrylate);

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-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ;

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;

And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

menstruum

The radiation sensitive composition of this invention makes the said (A)-(D) component an essential component, contains the said additive component as needed, and preferably mix | blends a solvent and is manufactured as a liquid composition.

As said solvent, if the components which comprise a radiation sensitive composition are disperse | distributed or melt | dissolved, and it does not react with such a component and has suitable volatility, it can select suitably and can use.

As such a solvent, for example

Alcohols such as methanol, ethanol, benzyl alcohol;

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

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, (Poly) alkylene glycols such as diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate Monoalkyl ether acetates;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one Ketones such as;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3 -Methyl-3-methoxybutylpropionate, ethyl butyrate, butyric acid n-propyl, butyric acid i-propyl, butyric acid n-butyl, ethyl hydroxyacetic acid, ethyl ethoxyacetic acid, methyl 3-methoxypropionate, 3-meth Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, ethyl 2-hydroxy-2-methylpropionate, 2- Other esters such as methyl hydroxy-3-methyl formate and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

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

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol from the viewpoint of solubility, pigment dispersibility, and applicability. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, N-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Etc. propionate, ethyl pyruvate, is preferred.

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

In addition, with the solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, High boiling point solvents, such as diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, a propylene carbonate, and ethylene glycol monophenyl ether acetate, can 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, storage stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition becomes like this. Preferably it is 5-50 weight%, More preferably, 10 The amount is preferably from 40% by weight.

Colored layer  Formation method

Next, the method of forming a colored layer using the radiation sensitive composition of this invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a portion forming a pixel, if necessary, and a liquid composition of a radiation-sensitive composition in which, for example, a red pigment is dispersed, is coated on the substrate. After that, pre-bake is performed and the solvent is evaporated to form a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using a developing solution, Preferably, an alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes thereafter, and arranges a red pixel pattern in predetermined sequence. The formed pixel array.

Thereafter, using the liquid composition of each radiation-sensitive composition in which green or blue pigments are dispersed, the liquid composition is applied as described above, prebaked, exposed to light, developed, and postbaked to form a green pixel array and By sequentially forming a blue pixel array on the same substrate, it is possible to obtain a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on the substrate. However, in this invention, the order which forms the pixel array of each color is not limited to the said thing.

As a board | substrate used when forming a pixel, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

In addition, such a substrate can be previously subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition, or the like as desired.

When applying the liquid composition of a radiation sensitive composition to a board | substrate, the appropriate coating methods, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the ink jet method, can be employ | adopted. have. Among these, the spin coating method and the slit die coating method are particularly preferable.

The coating thickness is preferably 0.1 to 10 mu m, more preferably 0.2 to 8.0 mu m, and particularly preferably 0.2 to 6.0 mu m as the film thickness after drying.

As the radiation used for exposure, 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 10 to 10, OO J / m ² .

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

A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like can be added to the alkaline developer.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle developing method, and the like can be applied. As for image development conditions, about 5 to 300 second is preferable at normal temperature. Moreover, after image development with alkaline developing solution, it washes with water normally.

The black matrix can also be formed in the same way as the pixel array.

color  filter

The color filter of this invention is equipped with the colored layer containing the pixel and / or black matrix formed as mentioned above, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, etc. Very useful.

Liquid crystal display panel

The liquid crystal display panel of this invention is equipped with the said color filter.

Moreover, as one Embodiment of the liquid crystal display panel of this invention, using the radiation sensitive composition of this invention, forming a colored layer as mentioned above on a thin-film transistor (TFT) substrate array is especially excellent. The liquid crystal display panel which has a characteristic can be manufactured.

The radiation sensitive composition of this invention contains the said (A)-(D) component as an essential component, and when a preferable composition is illustrated more concretely, it is as follows (a)-(bar).

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

(B) Coloring of the above-mentioned (A) containing (C) the polyfunctional monomer containing 1 or more types chosen from the group containing trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation-sensitive composition for layer formation.

(C) Said (A) (D) in which a radiation sensitive polymerization initiator contains 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one Or (b) The radiation sensitive composition for forming a colored layer.

(D) The radiation-sensitive composition for forming a colored layer of (A), (B) or (C), wherein the radiation-sensitive polymerization initiator (D) further comprises a biimidazole-based compound and / or an acetophenone-based compound. .

(E) The radiation sensitive composition for colored layer formation of said (D) in which (D) radiation sensitive polymerization initiator contains 1 or more types of hydrogen donors further.

(F) The radiation sensitive composition for colored layer formation of said (A), (B), (C), (D) or (E) whose (A) colorant contains an organic pigment and / or carbon black.

Moreover, the color filter with which this invention is preferable includes the color filter of the following (g).

(G) The color filter provided with the pixel and / or black matrix formed from the radiation sensitive composition of said (a), (b), (c), (d), (e) or (f).

As described above, according to the radiation sensitive composition of the present invention, contamination of a firing furnace, a photomask, or the like due to sublimation of the radiation sensitive polymerization initiator component can be suppressed, and foreign substances are not generated in the liquid, and the pixel pattern and black It is possible to form a satisfactory pixel pattern and a black matrix pattern without causing debris on the edges of the matrix pattern and without undercuts.

Therefore, the radiation sensitive composition of this invention can be used very suitably for manufacture of various color filters and liquid crystal display panels including the color filter for color liquid crystal display panels in the electronic industry.

<Example>

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is given and embodiment of this invention is described more concretely. However, this invention is not limited to the following Example.

Synthesis Example 1

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid. 15 parts by weight of styrene, 35 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 25 parts by weight of N-phenylmaleimide and 2.5 parts by weight of a chain transfer agent α-methylstyrene dimer were substituted with nitrogen. It stirred gently, the temperature of the reaction solution was heated up at 80 degreeC, this temperature was maintained, and it superposed | polymerized for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour, thereby (B) a solution of alkali-soluble resin ( Solid content concentration = 33.0 wt%).

This (B) alkali-soluble resin was Mw = 17,000 and Mn = 8,000. Let this (B) alkali-soluble resin be "resin (B-1)."

Synthesis Example 2

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid. 15 parts by weight of styrene, 30 parts by weight of benzyl methacrylate, 15 parts by weight of glycerol monomethacrylate, 25 parts by weight of N-phenylmaleimide and 2.5 parts by weight of a chain transfer agent α-methylstyrene dimer were substituted with nitrogen. The mixture was stirred gently, the temperature of the reaction solution was raised to 80 ° C., maintained at this temperature, and polymerized for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour, thereby (B) a solution of alkali-soluble resin ( Solid content concentration = 32.9% by weight).

This (B) alkali-soluble resin was Mw = 19,000 and Mn = 9,000. Let this (B) alkali-soluble resin be "resin (B-2)."

Synthesis Example 3

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid. 15 parts by weight of styrene, 30 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 30 parts by weight of N-phenylmaleimide, and 2.5 parts by weight of a chain transfer agent α-methylstyrene dimer were substituted with nitrogen. The mixture was stirred gently, and the temperature of the reaction solution was raised to 80 ° C. and maintained at this temperature to polymerize for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour, thereby (B) a solution of alkali-soluble resin ( Solid content concentration = 33.2% by weight).

This (B) alkali-soluble resin was Mw = 15,000 and Mn = 7,000. This (B) alkali-soluble resin is called "resin (B-3)."

Synthesis Example 4

 In a flask equipped with a cooling tube and a stirrer, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added, followed by 15 parts by weight of methacrylic acid. Parts, 30 parts by weight of acenaphthylene, 35 parts by weight of benzyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate and a chain transfer agent α-methylstyrene dimer 5 After weight part was added and nitrogen-substituted, it stirred gently, the temperature of the reaction solution was heated up to 80 degreeC, this temperature was hold | maintained, and it superposed | polymerized for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour, thereby (B) a solution of alkali-soluble resin ( Solid content concentration = 31.0 wt%).

This (B) alkali-soluble resin was Mw = 10,000 and Mn = 6,000. Let this (B) alkali-soluble resin be "resin (B-4)."

<Example 1>

(A) 85 parts by weight of an 80/20 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Red 177 as a coloring agent, (B) 70 parts by weight of resin (B-1) as an alkali-soluble resin, (C) a multi-pipe 80 parts by weight of dipentaerythritol hexaacrylate as the functional monomer, (D) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane as the radiation-sensitive polymerization initiator -1-one (trade name Irugacure 379, manufactured by Chiba Specialty Chemical Co., Ltd. as follows.) 70/30 (weight ratio) mixture of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate as 50 parts by weight and solvent 1,000 parts by weight were mixed to prepare a liquid composition (R1) of the radiation sensitive composition.

<Formation of color filter>

The liquid composition (R1) a, a soda glass substrate, SiO ₂ film is formed to prevent the elution of sodium ions on the surface, was applied using a spin coating, it is performed for 2 minutes pre-baking on a hot plate at 90 ℃, thickness 1.7 A coating film of 탆 was formed.

Subsequently, after cooling the substrate to room temperature, using a high-pressure mercury lamp, ultraviolet light containing each wavelength of 365 nm, 405 nm and 436 nm in the coating film through a photomask (slit width of 30 microns) was added to the 5, OO J / m was exposed with an exposure amount of the ^second. Then, the board | substrate was immersed in 23 degreeC 0.04 weight% potassium hydroxide aqueous solution for 1 minute, and developed, and it washed with ultrapure water and air-dried. Then, 30 minutes post-baking was performed in the 220 degreeC clean oven, and the pixel array containing red stripe pixel was formed on the board | substrate.

Developing  evaluation

When the pixel array was observed with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 80%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), undercut was not confirmed.

Sublimation Evaluation

After apply | coating a liquid composition (R1) on a board | substrate, it dried and formed the coating film with a film thickness of 1.7 micrometers. Subsequently, purge conditions were set to 100 ° C / 10 minutes using n-octane (specific gravity = 0.170, injection amount = 0.02 µl) as a standard substance for this coating film, and JHS-100A (trade name, Nihon powder) as a head space sampler. Head Space Gas Chromatography / Mass Spectrometry is performed using JEOL JMS-AX505W type mass spectrometer (trade name, manufactured by Nihon Bunsei Kogyo Co., Ltd.) as a gas chromatography / mass spectrometer. The peak area A derived from the radiation-sensitive polymerization initiator component (D) was obtained, and the volatilization amount in terms of n-octane was calculated by the following formula, and the volatilization amount was 0 µg.

(Calculation formula of volatilization amount by n-octane conversion)

Volatilization (μg) = A × (amount of n-octane) (μg) / (peak area of n-octane)

Underwater  Evaluation of foreign objects

After storing a liquid composition (R1) for 7 days at 5 degreeC, it observed by visually confirming the presence or absence of the recrystallization cargo of the (D) radiation sensitive polymerization initiator component. In addition, when the temperature of the liquid composition (R1) after storage was raised from 5 ° C to 23 ° C, the number of solids (foreign matter in liquid) having a size of 0.5 µm or more remaining without re-dissolving in 1 milliliter of the liquid composition (R1) was determined by using When measured using the submerged particle detector (trade name KS-28B, manufactured by Leon Co., Ltd.), solids were not confirmed.

<Example 2>

(D) 20 parts by weight of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one as a radiation-sensitive polymerization initiator, 2-methyl-1- 20 parts by weight of [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irugacure 907, manufactured by Chiba Specialty Chemical Co., Ltd. below) and 4,4 as an amine hydrogen donor A liquid composition (R2) of the radiation sensitive composition was produced in the same manner as in Example 1 except that 4 parts by weight of '-bis (diethylamino) benzophenone was used.

Next, except having used liquid composition (R2) instead of liquid composition (R1), it carried out similarly to Example 1, formed the pixel array containing red stripe pixel on the board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was O μg, and no foreign matter was found in the liquid.

Comparative Example 1

A radiation sensitive composition was prepared in the same manner as in Example 1 except that 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one was used as the radiation sensitive polymerization initiator. Liquid composition (r1) was prepared.

Next, except having used the liquid composition (r1) instead of the liquid composition (R1), it carried out similarly to Example 1, and formed the pixel array containing the red stripe pixel on the board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, the residual film ratio of the pixel array was 79%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), the undercut was not confirmed. No foreign matter was found in the liquid, but residue or crack was observed at the edge of the pixel pattern, and the volatilization amount of the coating film was 1.0 μg.

<Example 3>

(A) 95 weight part of 60/40 (weight ratio) mixture of CI pigment green 36 and CI pigment yellow 150 as a coloring agent, (B) 70 weight part of resin (B-2) as alkali-soluble resin, (C) polyfunctionality 80 parts by weight of dipentaerythritol hexaacrylate as a monomer, and (D) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane- as a radiation sensitive polymerization initiator 50 parts by weight of 1-one, 1 part by weight of malonic acid as an additive, and 900 parts by weight of a 50/50 (weight ratio) mixture of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a radiation-sensitive composition. Liquid composition (G1) was prepared.

Next, except having used liquid composition (G1) instead of liquid composition (R1), it carried out similarly to Example 1, formed the pixel array containing the green stripe pixel on the board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, when the residual film ratio of the pixel array was 80% and good, and the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), undercut was not confirmed. In addition, the volatilization amount of the coating film was 0 µg, and no foreign matter was found in the liquid.

<Example 4>

(D) 20 parts by weight of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one as a radiation sensitive polymerization initiator, 2,2'-bis 12 parts by weight of (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor A liquid composition (G2) of the radiation sensitive composition was prepared in the same manner as in Example 3 except that 12 parts by weight and 6 parts by weight of 2-mercaptobenzothiazole were used as the mercaptan-based hydrogen donor.

Subsequently, it carried out similarly to Example 1 except having used liquid composition (G2) instead of liquid composition (R1), and formed the pixel array containing the green stripe pixel on the board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 87%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was 0 µg, and no foreign matter was found in the liquid.

Comparative Example 2

Liquid phase of the radiation-sensitive composition was carried out in the same manner as in Example 3 except that 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one was used as the radiation-sensitive polymerization initiator. Composition (g1) was prepared.

Next, except having used the liquid composition (g1) instead of the liquid composition (R1), it carried out similarly to Example 1, the pixel array containing the green striped pixel was formed on the board | substrate, and evaluation was performed.

As a result, no developing residue was observed on the substrate of the unexposed portion, the residual film ratio of the pixel array was 79%, and the cross section of the pixel pattern was observed with a scanning electron microscope (SEM). Undercut was not confirmed. In addition, foreign matter in the liquid was not confirmed, but residues and cracks were observed at the edge of the pixel pattern, and the volatilization amount of the coating film was 1.0 μg.

Example 5

(A) 70 weight part of 95/5 (weight ratio) mixture of CI pigment blue 15: 6 and CI pigment violet 23 as a coloring agent, (B) 60 weight part of resin (B-3) as alkali-soluble resin, (C ) 90 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl as the radiation-sensitive polymerization initiator 50 parts by weight of butan-1-one, 5 parts by weight of nonionic surfactant A-60 (trade name, manufactured by Cao) as an additive, and 60 parts of 3-ethoxypropionate and propylene glycol monomethyl ether acetate as solvents. 900 parts by weight of the / 40 (weight ratio) mixture was mixed to prepare a liquid composition (B1) of the radiation sensitive composition.

Subsequently, except having used the liquid composition (B1) instead of the liquid composition (R1), it carried out similarly to Example 1, the pixel array containing the blue striped pixel was formed on the board | substrate, and evaluation was performed.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was not confirmed at O μg or foreign matter in the liquid.

<Example 6>

(D) 15 parts by weight of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one as a radiation sensitive polymerization initiator, 2,2'-bis 6 parts by weight of (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor 9 parts by weight, 3 parts by weight of 2-mercaptobenzothiazole and 15 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as mercaptan-based hydrogen donors A liquid composition (B2) of the radiation sensitive composition was produced in the same manner as in Example 5 except for the above.

Subsequently, except for using the liquid composition (B2) instead of the liquid composition (R1), it carried out similarly to Example 1, the pixel array containing the blue striped pixel was formed on the board | substrate, and evaluation was performed.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 90%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was O μg, and no foreign matter was found in the liquid.

Comparative Example 3

Liquid composition of a radiation sensitive composition in the same manner as in Example 5 except that 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 was used as the radiation sensitive polymerization initiator. (b1) was prepared.

Next, except having used the liquid composition (b1) instead of the liquid composition (R1), it carried out similarly to Example 1, and formed the pixel array containing a blue striped pixel on a board | substrate, and evaluated.

As a result, no developing residue was observed on the substrate of the unexposed portion, no residue or cracking was observed at the edge of the pixel pattern, the residual film ratio of the pixel array was 84%, the volatilization amount of the coating film was 0 μg, and in the liquid. Although no foreign matter was observed, the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), and undercut was confirmed.

<Example 7>

(A) 250 parts by weight of carbon black (manufactured by Mikuni Dyestuffs Co., Ltd.) as the colorant, (B) 75 parts by weight of the resin (B-4) as the alkali-soluble resin, and (C) dipentaerythritol hexaacrylate as the polyfunctional monomer. 75 parts by weight, (D) 50 parts by weight of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one as a radiation sensitive polymerization initiator and a solvent 1,000 parts by weight of a 50/50 (weight ratio) mixture of propylene glycol monomethyl ether acetate and cyclohexanone was mixed to prepare a liquid composition (BK1) of a radiation sensitive composition.

Next, except having used liquid composition (BK1) instead of liquid composition (R1), it carried out similarly to Example 1, formed the pixel array containing black stripe pixel on a board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 80%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was 0 µg, and no foreign matter was found in the liquid. Moreover, the adhesiveness with the board | substrate of the pixel was also excellent.

<Example 8>

(A) 250 parts by weight of carbon black (manufactured by Mikuni Dyestuffs Co., Ltd.) as the colorant, (B) 75 parts by weight of the resin (B-4) as the alkali-soluble resin, and (C) dipentaerythritol hexaacrylate as the polyfunctional monomer. 75 parts by weight, (D) 20 parts by weight of 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one as a radiation sensitive polymerization initiator and 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] ethane-1-onoxime-O-acetate (trade name CGI-242, manufactured by Chiba Specialty Chemicals Co., Ltd.) 20 parts by weight and 1,000 parts by weight of a 50/50 (weight ratio) mixture of propylene glycol monomethyl ether acetate and cyclohexanone as a solvent were mixed to prepare a liquid composition (BK2) of the radiation-sensitive composition.

Next, except having used the liquid composition (BK2) instead of the liquid composition (R1), it carried out similarly to Example 1, and formed the pixel array containing black stripe pixel on a board | substrate, and evaluated.

As a result, the developing residue was not confirmed on the substrate of the unexposed portion, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was 0 μg, and no foreign matter was found in the liquid. Moreover, the adhesiveness with the board | substrate of the pixel was also excellent.

<Comparative Example 4>

30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a radiation sensitive polymerization initiator, 2,2'-bis (2-chlorophenyl) -4,4 12 parts by weight of ', 5,5'-tetraphenyl-1,2'-biimidazole, 12 parts by weight of 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor and 2 as mercaptan-based hydrogen donor A liquid composition (bk1) of the radiation sensitive composition was produced in the same manner as in Example 7 except that 6 parts by weight of mercaptobenzothiazole was used.

Next, except having used the liquid composition (bk1) instead of the liquid composition (BK1), it carried out similarly to Example 7, the pixel array containing the black striped pixel was formed on the board | substrate, and evaluation was performed.

As a result, no developing residue was observed on the substrate of the unexposed portion, the residual film ratio of the pixel array was 83%, and the volatilization amount of the coating film was 0 μg, but residue and cracks were observed at the edge of the pixel pattern. When the cross section of was observed with the scanning electron microscope (SEM), the undercut was confirmed, and five foreign matters in the liquid were also confirmed.

Example 9

A liquid composition of a radiation sensitive composition (R3) was prepared in the same manner as in Example 1 except that 1,500 parts by weight of a 70/30 (weight ratio) mixture of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate was used as a solvent. .

Subsequently, a red stripe-like pixel was included on the substrate in the same manner as in Example 1 except that the liquid composition (R3) was used instead of the liquid composition (R1) and applied using a slit die coater instead of spin coating. A pixel array was formed and evaluation was performed.

As a result, the developing residue was not confirmed on the unexposed part of the substrate, and no residue or crack was found at the edge of the pixel pattern. In addition, the remaining film ratio of the pixel array was good at 85%, and when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was confirmed. In addition, the volatilization amount of the coating film was 0 μg, and no foreign matter was found in the liquid.

Thus, this composition can suppress the contamination of a kiln, a photomask, etc. by sublimation of a radiation sensitive polymerization initiator component, and also has the advantage that a foreign material does not produce in a liquid, and is excellent also in developability and a pattern shape.

Claims (3)

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer or a combination of monofunctional compound, and (D) the compound represented by following formula (1), and used for formation of a colored layer, It is characterized by the above-mentioned. A radiation sensitive resin composition. <Formula 1> In formula (1), R ¹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and R ² and R ³ are each independently a hydrogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; Or a benzyl group, R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently a hydrogen atom; Halogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; Or a linear or branched alkoxyl group having 1 to 4 carbon atoms, R ⁶ is a halogen atom; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; Linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms substituted with a substituent selected from the group consisting of a hydroxyl group and a linear or branched alkoxyl group having 1 to 4 carbon atoms; Linear or branched alkoxyl groups having 1 to 4 carbon atoms; Or a straight or branched alkoxyl group having 2 to 4 carbon atoms substituted with a substituent selected from the group consisting of a hydroxyl group and a straight or branched alkoxyl group having 1 to 4 carbon atoms. The color filter provided with the colored layer formed from the radiation sensitive composition of Claim 1. The liquid crystal display panel provided with the color filter of Claim 2.