KR100850170B1 - Radiation Sensitive Composition for Forming a Colored Layer, Color Filter and Color Liquid Crystal Display Panel - Google Patents

Abstract

This invention relates to the radiation sensitive composition for colored layer formation containing a coloring agent, alkali-soluble resin, a polyfunctional monomer, and a 0-acyl oxime type photoradical generator. This composition forms a colored layer of a color filter because it does not leave undissolved matters at the time of development or foreign matters on the pattern edges and provides pixels and black matrices in which the pattern edges are not broken and undercut even at low exposure doses. Used to.

Colored layer, radiation sensitive composition, color filter, color liquid crystal display panel

Description

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

[Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Document 2] Japanese Unexamined Patent Publication No. 3-53201

[Document 3] Japanese Unexamined Patent Publication No. 8-259876

The present invention relates to a radiation sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display panel. In more detail, the radiation sensitive composition used for formation of the colored layer used for manufacture of the color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, etc., for example, a pixel and / or a black matrix, and The color filter provided with the colored layer formed from the radiation sensitive composition, and the color 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 which previously formed the light shielding layer of a predetermined pattern, and drying, a dry coating film is prescribed | regulated. The method of obtaining the pixel of each color is known by irradiating a pattern shape with radiation (henceforth "exposure"), and it is known (Japanese Unexamined-Japanese-Patent No. 2-144502 and Japanese Unexamined-Japanese-Patent No. 3-). 5353).

In addition, in the technical field of the color filter, the movement of shortening the tact time by reducing the exposure amount has become mainstream, but in the conventional colored radiation-sensitive composition, it is easy to cause cracking or undercut of the pattern edge during development. For this reason, it was difficult to obtain satisfactory patterned pixels and black matrices while shortening the tact time.

An object of the present invention is a radiation-sensitive composition for forming a colored layer that exhibits excellent developability, more specifically, no cosmetic debris remains or foreign substances are generated at the pattern edge during development, and the pattern edge is not broken or undercut even at a low exposure amount. It is to provide a novel radiation-sensitive composition for forming a colored layer capable of providing a pixel and a black matrix which does not occur.

Another object of the present invention is to provide a color filter having a colored layer formed from the composition and a color liquid crystal display panel having the same.

Further objects and advantages of the invention will be apparent from the following description.

First, according to the present invention, the above object and advantages of the present invention are photoradical generation including (A) colorant, (B) alkali soluble resin, (C) polyfunctional monomer and (D) a compound represented by the following formula (1): It is achieved by the radiation sensitive composition for colored layer formation characterized by containing an agent.

Wherein one of R ¹ and R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (this phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and May be substituted with one or more substituents selected from the group consisting of halogen atoms), alicyclic groups having 7 to 20 carbon atoms (excluding the cycloalkyl group), oxygen-containing heterocyclic groups having 4 to 20 carbon atoms, nitrogen having 4 to 20 carbon atoms Containing heterocyclic group or a sulfur containing heterocyclic group having 4 to 20 carbon atoms, and another one of R ¹ and R ² is an alkyl group having 13 to 20 carbon atoms, an alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), and 4 carbon atoms An oxygen-containing heterocyclic group having from 20 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and R ³ is a hydrogen atom or a straight chain having 1 to 12 carbon atoms; , Branched or cyclic alkyl group, and R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

Secondly, according to the present invention, the above objects and advantages of the present invention are achieved by a color filter comprising a colored layer formed from the radiation-sensitive composition for forming a colored layer of the present invention.

Finally, according to the present invention, the above objects and advantages of the present invention are achieved by a color liquid crystal display panel comprising the color filter of the present invention.

Preferred Embodiments of the Invention

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

Radiation-sensitive composition for colored layer formation

-(A) colorant-

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

Since the color filter requires high color development and heat resistance, as the colorant of the present invention, a colorant having high color development and high heat resistance, in particular, a colorant having high thermal decomposition resistance, is preferably used, and pigments are usually used, particularly preferably organic. Pigments, carbon blacks are used.

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

CI Pigment Yellow 1, CI Pigment Yellow 3, CI 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 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, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment 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 CI 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 Red 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 CI Pigment Red 114, 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 Pigman Red 202, CI Pigment 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.

These organic pigments can be used, for example, by refining the sulfuric acid recrystallization method, solvent washing method or a combination thereof.

In addition, examples of the inorganic pigment 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 blue, and chromium oxide. Rust, cobalt rust, amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

As carbon black used for formation of a black matrix, for example, SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRF, Furnace blacks such as SRF-LM, SRF-LS, GPF, ECF, N-339, N-351 and the like; Thermal blacks such as FT, MT and the like; Acetylene black and the like.

In this invention, the said 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. It is preferable to use one or more organic pigments when forming a pixel, and it is preferable to use two or more organic pigments and / or carbon black when forming a black matrix.

Each pigment in the present invention can be used by modifying its particle surface with a polymer according to the purpose. 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, or oligomer etc. which are commercially available are mentioned, for example.

In addition, the coloring agent in this invention can be used with a dispersing agent according to the objective.

Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, silicone, fluorine and the like.

As said surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyesters; Tertiary amine modified polyurethanes; In addition to polyethyleneimine, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and Mega Pack (Dain Nippon Ink) Kagaku Kogyo Co., Ltd.), Flowride (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), Disperbyk-101, -103, -107, -110, -111, -115, -130, -160, -161, -162, -163, -164, -165, -166, -170, -180, -182, -2000, -2001 (Above, Big Chemi Japan Co., Ltd.), Sol Spas S5000, -S12000, -S13240, -S13940, -S17000, -S20000, -S22000, -S24000, -S24000GR, -S26000, -S27000, -S28000 (Above, Avecia Co., Ltd.), EFKA46, -47, -48, -745, -4540, -4550, -6750, EFKA LP4008, -4009, -4010, -4015, -4050, -4055,- 4560, -4800, EFKA polymer 400, -401, -402, -403, -450, -451, -453 (above, Efka Chemicals Corporation make), etc. are mentioned.

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

The amount of the surfactant 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, if it acts as a binder with respect to (A) coloring agent, and when it has solubility with respect to the developing solution used for the developing process, Preferably an alkaline developing solution, when manufacturing a color filter, it will be specifically limited. It is not. Among them, alkali-soluble resins having a carboxyl group are preferred, and ethylenically unsaturated monomers (hereinafter, "copolymerizable unsaturated") copolymerizable with other ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomers") in particular Preferred are copolymers (hereinafter referred to as "carboxyl group-containing copolymers") with " monomers ".

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 monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, 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;

Indene, such as indene, 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 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;

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;

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;

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

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

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

As a carboxyl group-containing copolymer of this invention, (meth) acrylic acid is an essential component, and it consists of monosuccinate mono [2- (meth) acryloyloxyethyl] and (omega) -carboxypolycaprolactone mono (meth) acrylate as the case may be. Carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) Copolymers with one or more selected from the group consisting of acrylates, glycerol mono (meth) acrylates, N-phenylmaleimide, polystyrene macromonomers and polymethylmethacrylate macromonomers (hereinafter, "carboxyl group-containing copolymers ( B1) ").

As a specific example of a carboxyl group-containing copolymer (B1),

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

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

(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 / polymethylmethacrylate macromonomer copolymer,

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

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

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

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

Methacrylic 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 / mono succinate 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 and the like.

5-50 weight% is preferable and, as for the copolymerization ratio of the carboxyl group-containing unsaturated monomer in a carboxyl group-containing copolymer, 10-40 weight% is more preferable. In this case, when the said copolymerization ratio is less than 5 weight%, the solubility with respect to the alkaline developing solution of the radiation sensitive composition obtained tends to fall, while when it exceeds 50 weight%, the solubility with respect to an alkaline developing solution will become large too much, and it develops with alkaline developing solution. When it does, there exists a tendency which becomes easy to cause the fall of the colored layer from the board | substrate and the film | membrane roughness of the colored layer surface.

As for the polystyrene conversion weight average molecular weight (henceforth "Mw") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin in this invention, 3,000-300,000 are preferable, 5,000-100,000 This is more preferable.

In addition, as for 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, 3,000-60,000 are preferable, 5,000-25,000 are more preferable.

In the present invention, by using an alkali-soluble resin having such specific Mw and Mn, a radiation-sensitive composition excellent in developability is obtained, whereby a pixel and a black matrix having a distinct pattern edge can be formed, and at the same time Residues, ground contamination, film residues, etc., are hardly generated on the substrate and the light shielding layer of the unexposed portion.

Moreover, 1-5 are preferable and, as for ratio (Mw / Mn) of Mw of alkali-soluble resin in this invention, 1-4 are especially preferable.

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. In this case, when the usage-amount of alkali-soluble resin is less than 10 weight part, alkali developability may fall, for example, there exists a possibility that a ground contamination or a film residue may arise on the board | substrate or the light shielding layer of an unexposed part, When the amount exceeds 00 parts by weight, the colorant concentration is relatively lowered, so that there is a fear that it is difficult to achieve the desired concentration as the thin film.

-(C) polyfunctional monomer-

The multifunctional monomer of the present invention includes a monomer having two or more polymerizable unsaturated bonds.

As a polyfunctional monomer, for example

Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, or modified dicarboxylic acids thereof;

Oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, spiran resins and the like;

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

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 trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol tree Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate,

The compound represented by following formula (2) or (3) is 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 produce background contamination, film residue, and the like.

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

The use amount of the multifunctional monomer of the present invention 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. In this case, 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, and when it exceeds 500 weight part, for example, alkali developability falls or the board | substrate of an unexposed part exists. Background contamination, film residues, etc., tend to occur on the phase or the light shielding layer.

Moreover, in this invention, the monofunctional monomer which has one polymerizable unsaturated bond can be used together with a polyfunctional monomer.

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

These monofunctional monomers can be used individually or in mixture of 2 or more types. The use ratio of the monofunctional monomer is preferably 90% by weight or less, and more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

The total amount of the polyfunctional monomer and the monofunctional monomer of the present invention 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. In this case, when the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, when the total amount exceeds 500 parts by weight, for example, alkali developability is lowered. Background contamination or film residues are likely to occur on the light shielding layer.

(D) photo-radical generator-

Component (D) of the present invention is an essential component of an O-acyl oxime optical radical generator, in particular, a compound represented by Chemical Formula 1 (hereinafter referred to as an "photo radical generator (D1)"), And (C) a component that generates radicals capable of initiating the polymerization of (C) the polyfunctional monomer and optionally the monofunctional monomer used by exposure to radiation such as ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays, or the like. .

In formula (1), one of R ¹ and R ² is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, a phenyl group (this phenyl group is an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms) , May be substituted with at least one substituent selected from the group consisting of a phenyl group and a halogen atom), an alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group), an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, 4 to A nitrogen-containing heterocyclic group of 20 or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and another one of R ¹ and R ² is an alkyl group having 13 to 20 carbon atoms and an alicyclic group having 7 to 20 carbon atoms (excluding the cycloalkyl group) ), An oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and R ³ is a hydrogen atom or 1 carbon atom Branched, straight, branched or cyclic alkyl group, and R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

As a C7-20 alicyclic group (except the said cycloalkyl group), a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a ter-cycloalkyl group, a terpene skeleton containing group, an adamantyl skeleton containing group, etc. are mentioned, for example. Can be.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms include, for example, thioranyl, azepinyl, dihydroazinyl, and dioxolanyl. , Triazinyl, oxathinyl, thiazolyl, oxadiazolyl, dioxadinyl, dihyaphthalenyl, furanyl, thiophenyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyra Zolyl, furazinyl, pyranyl, pyridinyl, pyridazinyl, pyrimidyl, pyrazinyl, pyrrolinyl, morphonyl, piperazinyl, quinuclidinyl, indolyl, isoindoleyl, benzofuranyl, benzothio Phenyl, indolidinyl, chromenyl, quinolinyl, isoquinolinyl, furinyl, quinazolinyl, cinnolinyl, phthalazinyl, pterridinyl, carbazolyl, acridinyl, phenantridinyl, thi Oxanthenyl, phenadidinyl, phenocyanidinyl, phenoxatiinyl, phenoxadidinyl, thianthrenyl, etc. The can.

In general formula (1), as a C1-C12 linear, branched or cyclic alkyl group of R <^3> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-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, cyclo Hexyl group etc. are mentioned.

Moreover, as a C1-C6 linear, branched or cyclic alkyl group of R <^4> , R <^5> and R <^6> , it is a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-, for example. A butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

As a specific example of these compounds (D),

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptylmethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -morphonylmethane-1-one oxime-O-benzoate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -morphonylmethane-1-one oxime-O-acetate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-bicycloheptancarboxylate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-tricyclodecanecarboxylate,

1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantanecarboxylate and the like.

These (D) optical radical generating agents can also use 2 or more types simultaneously.

(D) As an optical radical generating agent, O-acyl oxime type optical radical generating agent (henceforth "photo radical generating agent (D2)") other than the said General formula (1) can also be used together.

Specific examples of these photoradical generators (D2) include 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and 1,2-butanedione-1- [4 -(Phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octa Dione-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O- (4- Methyl benzoyl oxime)) etc. are mentioned. Among them, 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable.

Moreover, in this invention, another optical radical generating agent can also be used together with an O-acyl oxime optical radical generating agent.

As said other radical photo-radical generating agent, the biimidazole type compound, benzoin type compound, acetophenone type compound, benzophenone type compound, (alpha)-which has 1 or more types of main skeleton represented by following General formula (4a), (4b) or (4c), Diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, triazine compounds and the like.

As said biimidazole type compound, it is, for example

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, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole is particularly preferred.

The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved products, precipitates, and the like, and is also highly sensitive and sufficiently proceeds the curing reaction by exposure of a small amount of energy, and at the same time, contrast. Is high and does not cause a curing reaction in the unexposed portion, the coating film after exposure is clearly divided into a hardened portion insoluble in the developer and an uncured portion having high solubility in the developer, whereby the undercut The pixel pattern and the black matrix pattern which are absent can form a highly precise pattern array arranged according to a predetermined sequence.

Hydrogen donor

Moreover, in this invention, when using a biimidazole type compound together as an optical radical generating agent, using the hydrogen donor mentioned below together is preferable at the point which can improve a sensitivity further.

The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to radicals generated from a biimidazole compound due to exposure.

As such a hydrogen donor, a mercaptan compound, an amine compound, etc. which are defined below are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, " Mercaptan-based hydrogen donors ".

In addition, the amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, &Quot; amine-based hydrogen donors ").

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

The hydrogen donor will be described in more detail below.

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

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with alkyl, aralkyl or aryl groups. In addition, as long as at least one 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 bound in the form of disulfide.

In addition, 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 a portion other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2 Mercapto-2,5-dimethylaminopyridine and the like.

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

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

In addition, the amine-based hydrogen donor may be substituted with one or more amino groups by an alkyl group or a substituted alkyl group, and further substituted by a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like in a portion other than the amino group. May be

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminoaminopropiope. Non-methyl, 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) benzophenone This is particularly preferred. In addition, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone can act independently as a radical photoinitiator even when a biimidazole type compound does not exist.

The hydrogen donor in this invention can be used individually or in mixture of 2 or more types. It is preferable to use a combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in that the formed colored layer is hardly eliminated from the substrate at the time of development, and the strength and sensitivity of the colored layer are also high.

Specific examples of preferred combinations of mercaptan-based hydrogen donors with 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, A more preferable combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (diethyl Amino) benzophenone and a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

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

As the acetophenone-based compound, for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2- Morpholino-1-propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

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

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

Moreover, as said multinuclear quinone type compound, anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1, 4- naphthoquinone etc. are mentioned, for example.

Moreover, as said xanthone type compound, xanthone, thioxanthone, 2-chloro thioxanthone, etc. are mentioned, for example.

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

Moreover, as said triazine type compound, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2, for example -[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-tri Azine, 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,

The compound etc. which have halomethyl group, such as the compound represented by following formula (5) and (6), are mentioned.

The other photoradical generators may be used alone or in combination of two or more thereof.

The use ratio of the other optical radical generator is preferably 50% by weight or less, and more preferably 1 to 30% by weight, based on the sum of the O-acyl oxime type optical radical generator (D1) and the other optical radical generator. . In this case, when the use ratio of another optical radical generating agent exceeds 50 weight%, the desired effect of this invention may be impaired.

The total amount of optical radical generating agent used in the present invention is preferably 0.01 to 200 parts by weight, more preferably 1, based on 100 parts by weight in total of (C) the polyfunctional monomer and the monofunctional monomer used in some cases. To 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, when the total amount of the optical radical generating agent is less than 0.01 part by weight, curing due to exposure is insufficient, and it may be difficult to obtain a pattern array in which the pixel pattern or the black matrix pattern is arranged in accordance with a predetermined sequence. On the other hand, if it exceeds 200 parts by weight, the formed colored layer is likely to fall off from the substrate during development, and it is easy to generate background contamination, film residue, etc. on the substrate or the light shielding layer of the unexposed part.

In the present invention, one or more kinds of a sensitizer, a curing accelerator, or a polymer photocrosslinker and a sensitizer may be used in combination with the optical radical generator.

-additive-

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

As said additive, the organic acid or organic amino compound (except the said hydrogen donor) etc. which show the effect which further improves the dissolution characteristic with respect to the alkaline developing solution of a radiation sensitive composition, and further suppresses the remainder of the undissolved matter after image development, etc. Can be mentioned.

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 the aliphatic carboxylic acid, for example

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, sperinic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;

And tricarboxylic acids such as 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 whose carboxyl group was couple | bonded with the phenyl group via 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, aliphatic dicarboxylic acids are preferable as the aliphatic carboxylic acid from the viewpoint of alkali solubility, solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residue. 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 to be used is preferably 15% by weight or less, more preferably 10% by weight or less based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed 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- Mono (cyclo) alkylamines such as ethylcyclohexylamine, 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-butanol amine, 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-propaniline, 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 and 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 (cyclo) s are used as aliphatic amines from the viewpoints of solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residues. Alkanediols are preferred, in particular 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol , 4-amino-1,2-butanediol and the like are 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, More preferably, it is 10 weight% or less with respect to the whole radiation sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as additives other than the said organic acid and an organic amino compound, For example, Dispersion adjuvant, such as a blue pigment derivative, such as a copper phthalocyanine derivative, a yellow pigment derivative, etc .; Fillers such as glass, alumina and the like;

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

Surfactants such as nonionic, cationic, anionic and the like;

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, 3-mercaptopropyltrimethoxysilane, and the like ;

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

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

Anti-aggregation agents such as sodium polyacrylate;

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

menstruum

The radiation sensitive composition for forming a colored layer of the present invention contains the above components (A) to (D) as essential components and optionally contains the additive component, but is usually prepared as a liquid composition by blending a solvent.

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

As such a solvent, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

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

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

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

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

Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

And amides such as N, N-dimethylformamide, N, N-dimethylacetoamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, di, etc. from the viewpoint of solubility, pigment dispersibility, coating properties, and the like. Ethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methyl-3 Methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate desirable.

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

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate and ethyl benzoate together with the solvent And high boiling point solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

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

Color filter

The color filter of this invention is equipped with the colored layer formed from the radiation sensitive composition for colored layer formation of this invention.

The method of forming the color filter of this invention is demonstrated below.

First, if necessary, a light shielding layer is formed on the surface of the substrate so as to partition a portion forming a pixel as necessary, and a liquid composition of the radiation-sensitive composition in which, for example, a red pigment is dispersed, is provided on the substrate. After coating, prebaking is carried out to evaporate the solvent to form a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and then post-fires to form the pixel array in which the red pixel pattern was arrange | positioned at the predetermined sequence. do.

Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, it is carried out as described above, and the coating, preliminary firing, exposure, development and post-firing of each liquid composition are carried out to produce a green pixel array and a blue color. By sequentially forming pixel arrays 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 a substrate. However, in the present invention, the order of forming the pixel array of each color is not limited to the above.

In addition, the black matrix can be formed in the same manner as in the case of the pixel formation using the radiation-sensitive composition for forming a colored layer of the present invention.

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

In addition, these substrates can be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like according to the purpose.

When applying the liquid composition of the radiation-sensitive composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating, ink jet, or the like can be used. Among these, the spin coating method and the slit die coating method are particularly preferable.

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

As radiation used for forming the pixel and / or black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. may be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. Do.

The exposure dose of radiation is preferably 10 to 10,000 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 and the like are preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer, for example. In addition, after alkali development, water washing is normally performed.

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, 5 to 300 second is preferable at normal temperature.

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

Color liquid crystal display panel

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

Further, as one embodiment of the color liquid crystal display panel of the present invention, the pixel and / or the black matrix are formed on the thin film transistor substrate array as described above on the thin film transistor substrate array, using the radiation-sensitive composition for forming the colored layer of the present invention. By forming, the color liquid crystal display panel which has especially the outstanding characteristic can be manufactured.

The radiation sensitive composition for colored layer formation of this invention contains the said (A)-(D) component as an essential component, and especially a preferable composition is as follows (a)-(d).

(A) The radiation sensitive composition for colored layer formation in which (B) alkali-soluble resin contains a carboxyl group-containing copolymer (B1).

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

(C) O-acyl oxime type photoradical generator (D1) is 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptylmethane- 1-onoxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-onoxime-O- Acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-one oxime-O-benzoate, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-onoxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl)- 9.H.-Carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carr Bazol-3-yl] -thiophenylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl]- Thiophenylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H.-carbazol-3-yl] -morphonylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole- 3-yl] -morphonylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane- 1-onoxime-O-bicycloheptancarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime- O-tricyclodecanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantane The radiation sensitive composition for colored layer formation of said (b) containing 1 or more types chosen from the group of carboxylates.

(D) The radiation sensitive composition for forming a colored layer of said (A), (B) or (C) in which (A) coloring agent contains an organic pigment and / or carbon black.

In addition, the preferred color filter of the present invention

(E) The pixel and / or black matrix formed from the radiation sensitive composition for colored layer formation of said (a), (b), (c) or (d) are provided.

In addition, the preferred color liquid crystal display panel of the present invention

(F) comprising the color filter of (e) above,

More preferred color liquid crystal display panel of the present invention

(G) The thin film transistor substrate array is provided with the pixel and / or black matrix formed from the radiation sensitive composition for colored layer formation of said (A), (B), (C) or (D).

As described above, the radiation-sensitive composition for forming a colored layer of the present invention uses a photoradical generator having an O-acyl oxime type optical radical generator (D1) having high sensitivity to radiation as an essential component, thereby providing a pigment. Even when it is included in high concentration, undissolved matters remain on the substrate and the light shielding layer of the unexposed part at the time of development, and foreign matter does not occur at the edges of the pixel pattern and the black matrix pattern, and at the low exposure dose, the pattern edge is broken or undercut. It is possible to form a good pixel pattern and a black matrix pattern without.

Moreover, the pixel and black matrix formed using the radiation sensitive composition for colored layer formation of this invention have high surface smoothness, and are excellent also in adhesiveness with a board | substrate.

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

<Example>

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

Where parts and% are based on weight.

<(B) Production of Alkali Soluble Resin>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid and 15 parts of styrene, 35 parts of benzyl methacrylate, 10 parts of glycerol monomethacrylate, 25 parts of N-phenylmaleimide, and 2.5 parts of chain transfer agent α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gradually stirring to raise the reaction solution to 80 ° C. The polymerization was carried out for 3 hours while maintaining this temperature. Then, the reaction solution was heated up at 100 degreeC, 0.5 part of 2,2'- azobis (2, 4- dimethylvaleronitrile) was added, and it further superposed | polymerized for 1 hour, and obtained the resin solution (solid content concentration = 33.0%).

Obtained resin was Mw = 17,000 and Mn = 8,000. This resin was referred to as "resin (B-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid and 15 parts of styrene, 30 parts of benzyl methacrylate, 15 parts of glycerol monomethacrylate, 25 parts of N-phenylmaleimide, and 2.5 parts of chain transfer agent α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gradually stirring to raise the reaction solution to 80 ° C. The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was further carried out for 1 hour to obtain a resin solution (solid content concentration = 32.9%). .

Obtained resin was Mw = 19,000 and Mn = 9,000. This resin was referred to as "resin (B-2)".

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid and 15 parts of styrene, 30 parts of benzyl methacrylate, 10 parts of glycerol monomethacrylate, 30 parts of N-phenylmaleimide, and 2.5 parts of chain transfer agent α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gradually stirring to raise the reaction solution to 80 ° C. The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the resin solution (solid content concentration = 33.2%) was obtained by further polymerizing for 1 hour. .

Obtained resin was Mw = 15,000 and Mn = 7,000. This resin was referred to as "resin (B-3)".

Synthesis Example 4

To a flask equipped with a cooling tube and a stirrer, 3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were added, followed by 15 parts of methacrylic acid and acenaphthylene 30 Part, 35 parts of benzyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of ω-carboxypolycaprolactone monoacrylate and 5 parts of a chain transfer agent α-methylstyrene dimer were substituted with nitrogen, and then stirred slowly. The reaction solution was heated to 80 ° C. and maintained at this temperature for polymerization for 3 hours. Thereafter, the reaction solution was heated to 100 ° C, 0.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and further polymerized for 1 hour to obtain a resin solution (solid content concentration = 31.0%). .

Obtained resin was Mw = 10,000 and Mn = 6,000. This resin was referred to as "resin (B-4)".

<Example 1>

<Production of Liquid Composition>

(A) 85 parts of 80/20 (weight ratio) mixture of CI pigment red 254 and CI pigment red 177 as a coloring agent, (B) 80 parts of resin (B-1) as alkali-soluble resin, (C) polyfunctional monomer Dipentaerythritol hexaacrylate as 80 parts, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicyclo as photoradical generator 10 parts of heptyl-1-onoxime-O-acetate and 1,000 parts of a 70/30 (weight ratio) mixture of ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate as a solvent are mixed to form a liquid composition of a radiation-sensitive composition (R1) was prepared.

In addition, the liquid composition (R1) was prepared in the following order.

First, (A) 15 parts by weight of the CI Pigment Red 254 / CI Pigment Red 177 = 80/20 (weight ratio) mixture as the colorant, 4 parts by weight of Disperbik-2001 as the dispersant (solid content conversion), (B) alkali 6 parts by weight of (B-1) as the soluble resin and 75 parts by weight of ethyl 3-ethoxypropionate as the solvent (E) were treated with a beads mill to prepare a preliminary dispersion (R1-1).

Then, 567 parts by weight of the preliminary dispersion (R1-1), (B) 46 parts by weight of the resin (B-1) as the alkali-soluble resin, (C) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D 10 parts by weight of 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate as a photoradical generator And (E) 275 parts by weight of ethyl 3-ethoxypropionate and 300 parts by weight of propylene glycol monomethyl ether acetate as a solvent to prepare a liquid composition (R1).

<Formation of Colored Layer>

The liquid composition (R1) a, was applied using a spin coating on a soda glass substrate formed film is SiO ₂ for preventing the elution of sodium ions on the surface, is performed for 2 minutes prebaked on a hot plate at 90 ℃, thickness 1.7 ㎛ The coating film of was formed.

Subsequently, after cooling the substrate to room temperature, an ultraviolet light containing each wavelength of 365 nm, 405 nm and 436 nm was exposed to the coating film through a photomask (slit width 30 m) using a high pressure mercury lamp. The exposure amount at this time was 400 J / m <2>. Then, the board | substrate was immersed in 23 degreeC 0.04% potassium hydroxide aqueous solution for 1 minute, and developed, and it wash | cleaned with ultrapure water and air-dried. Subsequently, post-firing was performed for 30 minutes in a 220 degreeC clean oven, and the pixel array in which the red striped pixel pattern was arranged on the board | substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

Comparative Example 1

<Production of Liquid Composition and Formation of Colored Layer>

A radiation sensitive composition (r1) was produced in the same manner as in Example 1 except that the component (D) was changed to 30 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. It was.

Subsequently, except for using the liquid composition (r1) instead of the liquid composition (R1), a pixel array in which red striped pixel patterns were arranged on a substrate was formed in the same manner as in Example 1.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no development residue was observed on the substrate of the unexposed portion, but cracking of the edge of the pixel pattern was confirmed.

Moreover, the undercut was confirmed as a result of observing the cross section of a pixel pattern with a scanning electron microscope (SEM).

<Example 2>

<Production of Liquid Composition and Formation of Colored Layer>

(A) 95 parts of 60/40 (weight ratio) mixture of CI pigment green 36 and CI pigment yellow 150 as a coloring agent, (B) 70 parts of resin (B-2) as alkali-soluble resin, (C) polyfunctional monomer Dipentaerythritol hexaacrylate as 80 parts, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydro as an optical radical generating agent 12 parts of furanylmethane-1-one oxime-O-acetate, 1 part of malonic acid as an additive, and 900 parts of a 50/50 (weight ratio) mixture of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate as a solvent To prepare a liquid composition (G1) of the radiation-sensitive composition.

Subsequently, except for using the liquid composition (G1) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which green stripe pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 3>

<Production of Liquid Composition and Formation of Colored Layer>

(A) 70 parts of 95/5 (weight ratio) mixture of CI pigment blue 15: 6 and CI pigment violet 23 as a coloring agent, (B) 60 parts of resin (B-3) as alkali-soluble resin, (C) polytube 90 parts of dipentaerythritol hexaacrylate as the functional monomer, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl]-as an optical radical generator 20 parts of ethane-1-one oxime-O-bicycloheptancarboxylate, 5 parts of A-60 (trade name, nonionic surfactant manufactured by KAO Co., Ltd.) as an additive, and ethyl 3-ethoxypropionate as a solvent 900 parts by weight of a 60/40 (weight ratio) mixture with propylene glycol monomethyl ether acetate was mixed to prepare a liquid composition (B1) of the radiation-sensitive composition.

Subsequently, except for using the liquid composition (B1) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which blue striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 4>

<Production of Liquid Composition and Formation of Colored Layer>

(A) 250 parts of carbon black (made by Mikuni Sekiso Co., Ltd.) as a coloring agent, (B) 75 parts of resin (B-4) as alkali-soluble resin, (C) dipentaerythritol hexaacrylate as a polyfunctional monomer 75 parts, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O as photoradical generator 10 parts of acetate and 1,000 parts 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 (BK1) of the radiation sensitive composition.

Subsequently, except for using the liquid composition (BK1) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black stripe pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 5>

<Production of Liquid Composition and Formation of Colored Layer>

(D) component to 10 parts of 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-onoxime-O-acetate A radiation sensitive composition (BK2) was produced in the same manner as in Example 4 except for the change.

Subsequently, except for using the liquid composition (BK2) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 6>

<Production of Liquid Composition and Formation of Colored Layer>

(D) component to 10 parts of 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-bicycloheptancarboxylate A radiation sensitive composition (BK3) was produced in the same manner as in Example 4 except for the change.

Subsequently, except for using the liquid composition (BK3) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 7>

<Production of Liquid Composition and Formation of Colored Layer>

(D) component 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-tricyclodecanecarboxylate 10 A radiation sensitive composition (BK4) was produced in the same manner as in Example 4 except for changing to negative.

Subsequently, except for using the liquid composition (BK4) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 8>

<Production of Liquid Composition and Formation of Colored Layer>

(D) component 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantanecarboxylate 10 A radiation sensitive composition (BK5) was produced in the same manner as in Example 4 except for changing to negative.

Subsequently, except for using the liquid composition (BK5) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

Example 9

<Production of Liquid Composition and Formation of Colored Layer>

(D) component 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-bicycloheptane Except having changed into 10 parts of carboxylates, it carried out similarly to Example 4, and manufactured the radiation sensitive composition (BK6).

Subsequently, except for using the liquid composition (BK6) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 10>

<Production of Liquid Composition and Formation of Colored Layer>

A radiation sensitive composition (R2) 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, except that the liquid composition (R2) was used instead of the liquid composition (R1) and applied using a slit die coater instead of spin coating, a red striped pixel pattern was formed on the substrate in the same manner as in Example 1. An array of pixel arrays was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

Moreover, as a result of observing the cross section of a pixel pattern with the scanning electron microscope (SEM), undercut was not confirmed.

<Example 11>

<Production of Liquid Composition and Formation of Colored Layer>

(A) 600 parts of titanium black (titanium nitride) (made by JAMCO) as a coloring agent, (B) 75 parts of resin (B-4) as alkali-soluble resin, (C) dipentaerythritol hexaacryl as a polyfunctional monomer Rate 75 parts, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.ylcarbazol-3-yl] -ethane-1-onoxime-O- as an optical radical generator Ten parts of adamantane carboxylate and 1,000 parts 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 (BK7) of a radiation sensitive composition.

Subsequently, except for using the liquid composition (BK7) instead of the liquid composition (R1), in the same manner as in Example 1, a pixel array in which black striped pixel patterns were arranged on a substrate was formed.

<Evaluation>

As a result of observing the pixel array on the substrate with an optical microscope, no developing residue was observed on the substrate of the unexposed portion, and no foreign matter and cracks were observed at the edge of the pixel pattern.

In addition, when the cross section of the pixel pattern was observed with the scanning electron microscope (SEM), the undercut was not confirmed.

In the radiation-sensitive composition for forming a colored layer of the present invention, even when a pigment is contained at a high concentration, undissolved matters remain on the substrate and the light shielding layer of the unexposed part during development, or foreign matters are generated at the edges of the pixel pattern and the black matrix pattern. In addition, it is possible to form a good pixel pattern and a black matrix pattern without cracks or undercuts of the pattern edge even at a low exposure amount.

Moreover, the pixel and black matrix formed using the radiation sensitive composition for colored layer formation of this invention have high surface smoothness, and are excellent also in adhesiveness with a board | substrate.

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

Claims (3)

(A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer and (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -Bicycloheptyl-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1 -Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-bicycloheptancar Voxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-tricyclodecanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-adamantanecarboxylate and 1- [9-ethyl- 6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-bicycloheptancarboxylate at least one selected from the group consisting of An optical radiation generating agent, The radiation sensitive composition for colored layer formation characterized by the above-mentioned. The color filter provided with the colored layer formed from the radiation sensitive composition for colored layer formation of Claim 1. A color liquid crystal display panel comprising the color filter according to claim 2.