CN1800885A - Radiation sensitive composition for forming coat of colour, color filter and chromatic liquid crystal screen - Google Patents

Abstract

Provided is a radiation sensitive composition, which comprises a colorant, an alkali-soluble resin, a polyfunctional monomer and combination with the simple function group and o-acyl oxime type light free radical generating agent, for forming a colored layer free of remaining of undissolved matter and generation of scum on a pattern edge in developing, causing neither chip nor undercut of a pattern edge even under small exposure energy, and giving pixels and a black matrix.

Description

Be used to form radiation-ray sensitive composition, color filter and the chromatic liquid crystal screen of dyed layer

Technical field

The present invention relates to be used to form radiation-ray sensitive composition, color filter and the chromatic liquid crystal screen of dyed layer.More specifically, the present invention relates to be used to form the radiation-ray sensitive composition of dyed layer (pixel and/or black matrix"), this dyed layer is useful for making the color filter that uses in transmission-type or Reflexible color LCD, the colour pick-up tube element etc., also relates to color filter that possesses the dyed layer that is formed by this radiation-ray sensitive composition and the chromatic liquid crystal screen that possesses this color filter.

Background technology

In the past, make color filter for using colored radiation-sensitive composition, known method as described below: on the substrate or be pre-formed on the substrate of light shield layer of expected pattern and be coated with colored radiation-sensitive composition, after the drying, with the pattern form irradiation dry coating (hereinafter referred to as " exposure ") of radioactive ray by expection, and develop, thereby make each color pixel (opening flat 2-144502 communique and the spy opens flat 3-53201 communique) with reference to the spy.

And, in recent years, in the technical field of color filter, becoming main flow by the practice that reduces the exposure shortening productive temp time, but, colored radiation-sensitive composition in the past is easy to generate the shortcoming or the undercut of pattern edge when developing, therefore, be difficult to make pixel and the black matrix" (black matrix) with good pattern form when shortening the productive temp time.

Summary of the invention

The object of the invention is to provide the radiation-ray sensitive composition that is used to form dyed layer that shows excellent development, more specifically, providing when developing not can residual not dissolved matter, can not produce scum silica frost, even and under low exposure, can produce shortcoming and the pixel of undercut and the novel radiation-ray sensitive composition that is used to form dyed layer of black matrix" that pattern edge do not occur at image edge yet yet.

Other purposes of the present invention and advantage can become clear by following description.

According to the present invention, above-mentioned first purpose of the present invention and advantage are to reach by a kind of radiation-ray sensitive composition that is used to form dyed layer, and said composition is characterised in that: contain (A) colorant, (B) alkali soluble resins, (C) polyfunctional monomer or it and the combination of simple function group monomer and the optical free radical generation agent of (D) being made up of the compound of following formula (1) or (2) expression.

What is called among the present invention " dyed layer " is meant the layer that is made of pixel that is used for color filter and/or black matrix".

In formula (1) or (2), R ₁Be the alkyl of carbon number 1～20, the naphthenic base or the phenyl of carbon number 3～8, R ₂, R ₃The alkyl, the naphthenic base of carbon number 3～8, the phenyl that are hydrogen atom, carbon number 1～20 respectively (but also can be replaced by the alkoxy of the alkyl of the carbon number more than 1 1～6, carbon number 1～6, phenyl or halogen atom.) or the alicyclic group (not comprising above-mentioned naphthenic base) of carbon number 7～20, R ₄Be the oxygen-containing heterocycle of carbon number 4～20, the nitrogen heterocycle of carbon number 4～20 or the sulfur heterocyclic ring base of carbon number 4～20, R ₅Be the alkyl of hydrogen atom, carbon number 1～12 or the alkoxy of carbon number 1～12, and n is 1～5 integer, m is 0～5 integer, n+m≤5, and l is 0～6 integer.

According to the present invention, second purpose of the present invention and advantage are reached by a kind of color filter, and this color filter is characterised in that: possess the dyed layer of being made up of the above-mentioned radiation-ray sensitive composition that is used to form dyed layer.

According to the present invention, the 3rd purpose of the present invention and advantage are reached by a kind of chromatic liquid crystal screen, and this display screen is characterised in that: possess above-mentioned color filter.

Embodiment

Below, the present invention is described in detail.

Be used to form the radiation-ray sensitive composition of dyed layer

-(A) colorant-

The tone of colorant of the present invention is not particularly limited, can suitably select according to the purposes of the color filter that is obtained, and can be any pigment, dyestuff or natural colouring matter.

For color filter, requiring has high-precision colour developing and thermotolerance, therefore, as colorant of the present invention, preferred colour rendering height, and the high colorant of thermotolerance, the high colorant of preferred especially heat-resisting decomposability.The preferred pigment that uses especially preferably uses organic pigment, carbon black.

As above-mentioned organic pigment, for example, can be set forth in color index (C.I.; The distribution of dyers and colourist association) is classified as the compound of pigment (Pigment) in, can enumerates compound particularly with color index as described below (C.I.) numbering.

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

C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. 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;

C.I. paratonere 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. pigment Red 8, C.I. Pigment Red 9, C.I. paratonere 10, C.I. paratonere 11, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. paratonere 18, C.I. paratonere 19, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 30, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 40, C.I. pigment red 41, C.I. pigment red 42, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 53:1, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 57:2, C.I. paratonere 58:2, C.I. paratonere 58:4, C.I. paratonere 60:1, C.I. paratonere 63:1, C.I. paratonere 63:2, C.I. paratonere 64:1, C.I. pigment red 81: 1, C.I. pigment Red 83, C.I. pigment Red 88, C.I. Pigment Red 9 0:1, C.I. Pigment Red 97, C.I. paratonere 101, C.I. paratonere 102, C.I. paratonere 104, C.I. paratonere 105, C.I. paratonere 106, C.I. paratonere 108, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 172, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. paratonere 194, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 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. bistre 23, C.I. bistre 25;

C.I. pigment black 1, C.I. pigment black 7.

These organic pigments for example can be made with extra care by sulfuric acid recrystallization method, solvent wash method or their combination etc. and use.

In addition, as inorganic pigment, for example, can enumerate titanium dioxide, barium sulphate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, dark purple, chrome oxide green, cobalt green, umber, black, the synthetic iron oxide black of titanium, carbon black etc.

In the present invention, above-mentioned organic pigment and inorganic pigment can use separately separately or mix more than 2 kinds and use, and in addition, can and use organic pigment and inorganic pigment.When forming pixel, preferably use the organic pigment more than a kind, in addition, when forming black matrix", preferably use organic pigment and/or carbon black more than 2 kinds.

In the present invention, above-mentioned each pigment can utilize polymkeric substance that its particle surface is carried out modification according to expectation to use.As the polymkeric substance that the particle surface of pigment is carried out modification, for example, can enumerate the spy and open the polymkeric substance of record such as flat 8-259876 communique or commercially available various pigment dispersing with polymkeric substance or oligomer etc.

In addition, in the present invention, colorant can use jointly according to expectation and spreading agent.As above-mentioned spreading agent, for example, can enumerate surfactants such as cationic, anionic species, nonionic class, both sexes class, silicone based, fluorine class.

As above-mentioned surfactant, for example, can enumerate polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, the such polyethylene oxide alkyl ethers of polyoxyethylene oleyl ether; Polyoxyethylene n-octyl phenyl ether, the such polyoxyethylene alkyl phenyl ether of polyoxyethylene n-nonyl phenyl ether; Polyethylene glycol dilaurate, the such polyethylene glycol di of polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polyethyleneimine: amine etc., also have following KP (SHIN-ETSU HANTOTAI's chemical industry (strain) productions), Port リ Off ロ-(common prosperity society chemistry (strain) productions of representing with trade name), エ Off ト Star プ (ト-ケ system プ ロ ダ Network Star company produces), メ ガ Off ア Star Network (big Japanese イ Application キ chemical industry (strain) productions), Off ロ ラ-De (Sumitomo ス リ-エ system (strain) production), ア サ ヒ ガ-De, サ-Off ロ Application (more than, Asahi Glass (strain) production), Disperbyk (PVC Star Network ケ ミ-ジ ヤ パ Application (strain) production), ソ Le ス パ-ス (セ ネ カ (strain) production) etc. in addition.

These surfactants may be used singly or as a mixture of two or more.

The consumption of surfactant is preferably below 50 weight portions, more preferably 0～30 weight portion with respect to the colorant of 100 weight portions.

-(B) alkali soluble resins-

As alkali soluble resins of the present invention, so long as (A) colorant is played the effect of bonding agent and is the developer solution that uses in to this development treatment operation when making color filter, the especially preferably material that alkaline-based developer is had solubility, just not restriction especially.Wherein, preferably have the alkali soluble resins of carboxyl, especially preferably have the carboxyl more than 1 ethylene unsaturated monomer (below, be called " carboxylic unsaturated monomer ".) and other can copolymerization the multipolymer (below, be called " carboxylic multipolymer ") of ethylene unsaturated monomer (below, be called " copolymerization unsaturated monomer ").

As carboxylic unsaturated monomer, for example, can enumerate (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, the such unsaturated monocarboxylic acid of cinnamic acid; Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, such unsaturated dicarboxylic acid or its acid anhydrides of mesaconic acid;

Unsaturated polybasic carboxylic acid more than 3 yuan or its acid anhydrides;

List [(methyl) acryloyloxyalkyl] ester of polybasic carboxylic acid more than 2 yuan that mono succinate [2-(methyl) acryloyl-oxy ethyl ester], phthalic acid list [2-(methyl) acryloyl-oxy ethyl ester] are such;

ω-two such ends of carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.

In these carboxylic unsaturated monomers, mono succinate (2-acryloyl-oxy ethyl ester) and phthalic acid list (2-acryloyl-oxy ethyl ester) are sold on market with the trade name of M-5300 and M-5400 (East Asia synthetic (strain) produces) respectively.

Above-mentioned carboxylic unsaturated monomer may be used singly or as a mixture of two or more.

In addition, as the copolymerization unsaturated monomer, for example, can enumerate styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, the aromatic ethenyl compound such to the vinyl benzyl glycidol ether;

Indenes such as indenes, 1-methyl indenes;

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl binaryglycol ester, (methyl) acrylic acid methoxyl triglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentadienyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, the such esters of unsaturated carboxylic acids of single (methyl) acrylic acid glyceride;

(methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, the such unsaturated carboxylic acid aminoalkyl ester of (methyl) acrylic acid 3-dimethylamino propyl ester;

The unsaturated carboxylic acid ethylene oxidic ester that (methyl) glycidyl acrylate is such;

(methyl) vinyl cyanide, α-Lv Bingxijing, the such acrylonitrile based compound of acrylonitrile;

(methyl) acrylamide, α-chloropropene acid amides, the such unsaturated amides of N-2-hydroxyethyl (methyl) acrylamide;

Maleimide, N-phenylmaleimide, the such unsaturated acyl imines of N-cyclohexyl maleimide;

Vinyl acetate, propionate, vinyl butyrate, the such vinyl carboxylates of benzoic acid vinyl acetate;

Vinyl methyl ether, EVE, the such unsaturated ethers of allyl glycidyl ether;

1,3-butadiene, isoprene, the such aliphatics conjugated diolefine of chlorbutadiene;

Polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, the such end at polymer molecular chain of polysiloxane have the macromonomer of list (methyl) acryloyl group etc.

These copolymerization unsaturated monomers may be used singly or as a mixture of two or more.

As carboxylic multipolymer of the present invention, be essential composition preferably with (methyl) acrylic acid, according to circumstances, the carboxylic unsaturated monomer composition that further contains at least a kind of compound that is selected from mono succinate [2-(methyl) acryloxy ethyl ester] and ω-carboxyl polycaprolactone list (methyl) acrylate, with be selected from styrene, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, N-phenylmaleimide, the multipolymer of at least a kind of formation of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (below, be called " carboxylic multipolymer (B1) ".)。

As the object lesson of carboxylic multipolymer (B1), can enumerate

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

(methyl) acrylic acid/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) methyl acrylate/polymethylmethacrylate macromonomer multipolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer,

(methyl) acrylic acid/styrene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl ester]/styrene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl ester]/styrene/(methyl) allyl acrylate/N-phenylmaleimide multipolymer,

(methyl) acrylic acid/styrene/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/N-phenylmaleimide multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/styrene/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/N-phenylmaleimide multipolymer etc.

The copolymerization ratio of the carboxylic unsaturated monomer in the carboxylic multipolymer is preferably 5～50 weight %, more preferably 10～40 weight %.If this copolymerization ratio is lower than 5 weight %, then the dissolubility of the relative alkaline developer of gained radiation-ray sensitive composition has downward trend, on the other hand, if surpass 50 weight %, then the dissolubility of alkaline developer is excessive relatively, when utilizing alkaline developer to develop, exist cause easily dyed layer from substrate come off or the film on dyed layer surface coarse.

By gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) weight-average molecular weight that is converted into polystyrene of the alkali soluble resins among the present invention of Ce Dinging (below, be called " Mw ".) be preferably 3,000～300,000, more preferably 5,000～100,000.

In addition, by gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) alkali soluble resins among the present invention of Ce Dinging be converted into the polystyrene number-average molecular weight (below, be called " Mn ".) be preferably 3,000～60,000, more preferably 5,000～25,000.

In the present invention, have this specific Mw and the alkali soluble resins of Mn by use, can obtain the radiation-ray sensitive composition of development property excellence, thereby can form pixel and black matrix" with clear pattern edge, and, when developing, be difficult on the substrate at unexposed portion and produce residue, scum, residual film etc. on the light shield layer.

In addition, the ratio (Mw/Mn) of the Mw of the alkali soluble resins among the present invention and Mn is preferably 1～5, and more preferably 1～4.

In the present invention, alkali soluble resins can separately or mix use more than 2 kinds.

Relative 100 weight portions of the consumption of the alkali soluble resins among the present invention (A) colorant is preferably 10～1,000 weight portion, more preferably 20～500 weight portions.At this moment, if the consumption of alkali soluble resins is lower than 10 weight portions, for example, alkali-developable is descended, produce scum or residual film on the substrate of unexposed portion or on the light shield layer, on the other hand, if surpass 1,000 weight portion, then colorant concentration reduces relatively, therefore, as film, probably be difficult to reach aim colour concentration.

-(C) polyfunctional monomer-

Polyfunctional monomer of the present invention is made of the monomer with the polymerism unsaturated link more than 2.

As polyfunctional monomer, for example, can enumerate two (methyl) acrylate of the such aklylene glycol of ethylene glycol, propylene glycol;

Two (methyl) acrylate of the poly alkylene glycol that polyglycol, polypropylene glycol are such;

Poly-(methyl) acrylate and the dicarboxylic acid modifier thereof of the polyvalent alcohol more than 3 yuan that glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol are such;

Polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, such oligomeric (methyl) acrylate of spirane resin;

Two terminal hydroxyls are poly--two (methyl) acrylate of the such two terminal hydroxyl fluidized polymers of 1,3-butadiene, two terminal hydroxyl polyisoamylenes, two terminal hydroxyl polycaprolactones and

Tricresyl phosphate [2-(methyl) acryloxy ethyl] ester etc.

In these polyfunctional monomers, poly-(methyl) acrylate and their the dicarboxylic acid modifier of preferred polyvalent alcohol more than 3 yuan, preferred particularly trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate,

The compound of following formula (3) expression,

The compound of following formula (4) expression etc.,

Especially, because the intensity height of dyed layer, the surface smoothing excellence of dyed layer, and be difficult to producing scum, residual film etc. on the substrate at unexposed position and on the light shield layer preferred trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol acrylate.

Above-mentioned polyfunctional monomer may be used singly or as a mixture of two or more.

(B) alkali soluble resins of relative 100 weight portions of the consumption of polyfunctional monomer of the present invention is preferably 5～500 weight portions, more preferably 20～300 weight portions.When the consumption of polyfunctional monomer is lower than 5 weight portions, exist the intensity or the surface smoothing downward trend of chromatograph, on the other hand, if surpass 500 weight portions, for example, exist alkali-developable descend, easily on the substrate at unexposed position or produce the trend of scum, residual film etc. on the light shield layer.

In addition, in the present invention, can also use simple function group monomer with polyfunctional monomer with 1 polymerism unsaturated link.

As above-mentioned simple function group monomer; for example, can enumerate compound identical or N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-epsilon-caprolactams and as the M-5600 (trade name, East Asia synthetic (strain) are produced) of commercially available product etc. with above-mentioned carboxylic unsaturated monomer of listing for (B) alkali soluble resins or copolymerization unsaturated monomer.

These simple function group monomers may be used singly or as a mixture of two or more.The total amount of relative polyfunctional monomer of the usage ratio of simple function group monomer and simple function group monomer is preferably below the 90 weight %, more preferably below the 50 weight %.At this moment, if the usage ratio of simple function group monomer greater than 90 weight %, the intensity of gained dyed layer or surface smoothing may be not enough.

The consumption of polyfunctional monomer of the present invention or be preferably 5～500 weight portions with respect to (B) alkali soluble resinss of 100 weight portions, more preferably 20～300 weight portions with total use amount of the combination of simple function group monomer.If above-mentioned total use amount is lower than 5 weight portions, exist the intensity or the surface smoothing downward trend of chromatograph, on the other hand, if surpass 500 weight portions, for example, exist alkali-developable descend, easily on the substrate of unexposed portion or produce the trend of scum, residual film etc. on the light shield layer.

-(D) optical free radical generation agent-

Optical free radical of the present invention produces agent and is made of O-acyl oxime type Photoepolymerizationinitiater initiater, especially with the compound of following formula (1) or (2) expression (below, be called " optical free radical produce agent [D1] ") as essential composition, the composition of the free radical of the simple function group monomer polymerization that can cause (C) polyfunctional monomer and according to circumstances use that is produced by the exposure by visible light, ultraviolet ray, far ultraviolet, charged particle ray, X ray isoradial constitutes.

In " optical free radical produces agent (D1) " of above-mentioned formula (1) or (2) expression, R ₁Be carbon atom uncle 1～20 alkyl, the naphthenic base or the phenyl of carbon number 3～8.R ₂, R ₃It is respectively the alicyclic group (not comprising above-mentioned naphthenic base) of naphthenic base, phenyl (but can also be replaced) or the carbon number 7～20 of alkyl, the carbon number 3～8 of hydrogen atom, carbon number 1～20 by the alkoxy of the alkyl of the carbon number more than 1 1～6, carbon number 1～6, phenyl or halogen atom.R ₄Be the oxygen-containing heterocycle of carbon number 4～20, the nitrogen heterocycle of carbon number 4～20 or the sulfur heterocyclic ring base of carbon number 4～20, R ₅Be the alkyl of hydrogen atom, carbon number 1～12 or the alkoxy of carbon number 1～12, and n is 1～5 integer, m is 0～5 integer, n+m≤5, and l is 0～6 integer.

R in formula (1) or (2) ₁The alkyl of carbon number 1～20 can be the straight or branched alkyl, as its object lesson, for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.As the naphthenic base of carbon number 3～8, for example, can enumerate cyclopentyl, cyclohexyl etc.

In addition, R ₂, R ₃The alkyl of carbon number 1～20 can be a straight chain shape or a chain, as its object lesson, for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.As the naphthenic base of carbon number 3～8, for example, can enumerate cyclopentyl, cyclohexyl etc.

As R ₂, R ₃The alkyl of substituent carbon number 1～6 of phenyl can be the alkyl of straight chain shape, a chain, ring-type, for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.

In addition, the alkoxy of carbon number 1～6 can be straight chain shape, a chain, cyclic alkoxy, for example, can enumerate methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc.As halogen atom, for example, can enumerate fluorine atom, chlorine atom etc.

As the alicyclic group (not comprising above-mentioned naphthenic base) of carbon number 7～20, for example, can enumerate bicyclic alkyl, tricyclic alkyl, spirane base, tricyclic alkyl, contain the terpenes skeleton group, contain the group of diamantane skeleton etc.

As R ₄The nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the sulfur heterocyclic ring base of carbon number 4～20, for example, can enumerate tetrahydro-thienyl, the azepines base, dihydro azepines base, dioxolanyl (ジ オ キ ソ ラ ニ Le), triazinyl, the thioxane base, thiazolyl oxadiazine base, the dioxy indanyl, two thianaphthenyls, furyl, thienyl, pyrrole radicals oxazolyl isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, the furazan base, pyranose, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, pyrrolinyl, morpholinyl, piperazinyl, quininuclidinyl, indyl, isoindolyl, benzofuranyl, benzothienyl, the indolizine base, the chromene base, quinolyl, isoquinolyl, purine radicals, quinazolyl, the cinnolines base, phthalazinyl, pteridyl, carbazyl, acridinyl, phenanthridinyl, the thioxanthene base, phenazinyl, phenothiazinyl phenoxthine base (Off エ ノ キ サ ジ ニ Le) phenoxazine group, thianthrene group, tetrahydrofuran base, THP trtrahydropyranyl etc.Wherein, preferred especially tetrahydrofuran base, THP trtrahydropyranyl etc.

R ₅The alkyl of carbon number 1～12 can be the alkyl of straight chain shape, a chain or ring-type, for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc.

In addition, the alkoxy of carbon number 1～12 can be the alkoxy of straight chain shape, a chain or ring-type, for example, can enumerate methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy etc.

Wherein, special preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, methoxyl, ethoxy.

N is 1～5 integer, preferred 1.M is 0～5 integer, and any is preferred especially 1 in preferred 0,1,2, and in addition, l is 0～6, is preferably in 0,1,2 any, preferred especially 1.

As the object lesson of described compound (D1),

Can enumerate 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H ,-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,,

1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,,

1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,,

1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,,

1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxo benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl oximido) ethyl ketone,

1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone etc.

Wherein, preferred especially 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl oximido) ethyl ketone), 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl oximido) ethyl ketone and 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone.

These optical free radicals produce agent (D1) and can also use simultaneously more than 2 kinds.

Produce agent (D) as optical free radical, can and with above-mentioned formula (1) or (2) O-acyl oxime type optical free radical in addition produce agent (below, be called " optical free radical generation agent (D2) ".)。

Produce the object lesson of agent (D2) as these optical free radicals, can enumerate 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime); 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime); 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl oxime); 1,2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oxime); And 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-toluyl oxime)) etc.Wherein, preferred especially 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime).

In addition, in the present invention, can also produce agent with O-acyl oxime type optical free radical and also produce agent with other optical free radical.

Produce agent as above-mentioned other optical free radical, for example, can enumerate have at least a kind of following formula (4-1), formula (4-2) or (4-3) the bisglyoxaline compounds, styrax compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear benzoquinone compound, xanthone compounds, phosphine compound, compound in triazine class etc. of the main skeleton of expression.

As above-mentioned bisglyoxaline compounds, for example, can enumerate

2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,

2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,

2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In these bisglyoxaline compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline and 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, preferred especially 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.

Above-mentioned bisglyoxaline compounds is for the dissolubility excellence of solvent, can not produce impurity such as insolubles, precipitate, and it is highly sensitive, just can be cured reaction fully by low-energy exposure, and, the contrast height, at unexposed position curing reaction can not take place, therefore, filming after the exposure obviously divided into the cured portion that is insoluble to developer solution and had the uncured portion of highly dissoluble for developer solution, thereby the orientation configuration that can form does not according to the rules have the pattern of pixels of undercut and the patterns of high precision array of black matrix pattern.

-hydrogen donor-

In addition, in the present invention, when also using the bisglyoxaline compounds to produce agent,, therefore preferably also use following hydrogen donor owing to can further improve sensitivity as optical free radical.

Here so-called " hydrogen donor " is meant the compound that hydrogen atom can be provided to the free radical that is produced by the bisglyoxaline compounds by exposure.

As such hydrogen donor, be preferably as follows the sulfur alcohol compound of definition, as the aminated compounds of giving a definition etc.

Above-mentioned sulfur alcohol compound is by serving as female ring with phenyl ring or heterocycle, have more than 1, preferred 1～3, further preferred 1～2 encircle the compound of the sulfydryl that directly links to each other (hereinafter referred to as " thio-alcohol hydrogen donor " with this mother.) constitute.

In addition, above-mentioned aminated compounds is by serving as female ring with phenyl ring or heterocycle, have more than 1, preferred 1～3, further preferred 1～2 encircle the compound of the amino that directly links to each other (hereinafter referred to as " amine hydrogen donor " with this mother.) constitute.

In addition, these hydrogen donors also can have sulfydryl and amino simultaneously.

Below, hydrogen donor is illustrated in greater detail.

The thio-alcohol hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, can also have phenyl ring and heterocycle simultaneously.These whens ring when having more than 2 can form condensed ring, also can not form condensed ring.

In addition, when the thio-alcohol hydrogen donor has 2 above sulfydryls, if residual at least 1 free sulfhydryl groups, just can be replaced more than 1 in the then residual sulfydryl by alkyl, aralkyl or aryl.In addition, as long as residual at least 1 free sulfhydryl groups, then can have by divalent organic groups such as alkylidenes in conjunction with the structural unit of 2 sulphur atoms or with the form of disulfide structural unit in conjunction with 2 sulphur atoms.

In addition, the place of thio-alcohol hydrogen donor beyond sulfydryl can also be by carboxyl, replacement or unsubstituted alkoxy carbonyl group, replacement or replacements such as unsubstituted carbobenzoxy, nitro.

As the object lesson of such thio-alcohol hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.

In these thio-alcohol hydrogen donors, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.

The amine hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, also can have phenyl ring and heterocycle simultaneously.These whens ring when having more than 2 can form condensed ring, also can not form condensed ring.

In addition, can be replaced by alkyl or substituted alkyl more than 1 in the amino of amine hydrogen donor,, other positions beyond amino can also be by carboxyl, replacement or unsubstituted alkoxy carbonyl group, replacement or replacements such as unsubstituted carbobenzoxy, nitro.

Object lesson as such amine hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, 4-dimethylamino rest in peace acid, 4-dimethylamino cyanobenzene etc.

In these amine hydrogen donors, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.In addition, even there is not the bisglyoxaline compounds, 4,4 '-two (dimethylamino) benzophenone or 4,4 '-two (diethylamino) benzophenone can also play the optical free radical action of evocating separately.

In the present invention, hydrogen donor may be used singly or as a mixture of two or more, can also be used in combination thio-alcohol hydrogen donor more than a kind and the amine hydrogen donor more than a kind, because the dyed layer that forms is difficult to come off from substrate when developing, and the intensity of dyed layer and sensitivity are all high, thereby be preferred.

Object lesson as the preferred compositions of thio-alcohol hydrogen donor and amine hydrogen donor, can enumerate 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone etc., preferred combination is 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone, particularly preferred combination is 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone.

The thio-alcohol hydrogen donor in the combination of thio-alcohol hydrogen donor and amine hydrogen donor and the weight ratio of amine hydrogen donor be preferably 1: 1～and 1: 4, more preferably 1: 1～1: 3.

In addition, as above-mentioned styrax compounds, for example, can enumerate styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-benzoyl benzoic acid methyl esters etc.

In addition, as above-mentioned acetophenone compounds, for example, can enumerate 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl-(4-methyl mercapto phenyl)-2-morpholinyl-1-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 1-hydroxy-cyclohexyl benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.

In addition, as above-mentioned benzophenone compound, for example, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone etc.

In addition, as above-mentioned α-cyclohexadione compounds, for example, can enumerate diacetyl, dibenzoyl, toluyl formic ether etc.

In addition, as above-mentioned multinuclear benzoquinone compound, for example, can enumerate anthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1,4-naphthoquinones etc.

In addition, as above-mentioned xanthone compounds, for example, can enumerate xanthone, thioxanthones, 2-clopenthixal ketone etc.

In addition, as above-mentioned phosphine compound, for example, can enumerate two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

In addition, as above-mentioned compound in triazine class, for example, can enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine of 6-;

The compound of following formula (6) expression

, following formula (7) expression compound

Deng compound with halomethyl etc.

Above-mentioned other optical free radical produces agent and may be used singly or as a mixture of two or more.

Other optical free radical produces the usage ratio of agent and is preferably below the 50 weight % with respect to the total amount that O-acyl oxime type optical free radical produces agent (D1) and other optical free radicals generation agent, more preferably 1～30 weight %.At this moment, surpass 50 weight %, may damage the effect of the present invention's expectation if other optical free radical produces the consumption of agent.

Optical free radical of the present invention produces total consumption of agent and is preferably 0.01～200 weight portion with respect to (C) polyfunctional monomer of 100 weight portions or with the simple function group monomer total amount of using with it, more preferably 1～120 weight portion is preferably 1～100 weight portion especially.When total consumption of optical free radical generation agent is lower than 0.01 weight portion, the curing that exposure causes may become insufficient, and be difficult to obtain the pattern of pixels of orientation configuration according to the rules or the pattern array of black matrix pattern, on the other hand, if surpass 200 weight portions, the dyed layer that forms comes off from substrate when developing easily, in addition, is producing scum, residual film etc. on the substrate of unexposed portion or on the light shield layer easily.

In addition, in the present invention, can also produce agent with above-mentioned optical free radical in case of necessity and use sensitizer, curing accelerator or high-molecular optical crosslinking sensitizer more than a kind simultaneously.

-adjuvant-

In case of necessity, the radiation-ray sensitive composition that is used to form dyed layer of the present invention can also contain various adjuvants.

As above-mentioned adjuvant, can enumerate and demonstrate the dissolution characteristics of further improvement for the alkaline developer of radiation-ray sensitive composition, and the organic acid or the organic amino compounds of the effect that the insolubles after further suppressing to develop is residual etc. (wherein, do not comprise above-mentioned hydrogen donor.) etc.

As above-mentioned organic acid, have the aliphatic carboxylic acid of the carboxyl more than 1 in the preferred molecule or contain the carboxylic acid of phenyl.

As above-mentioned aliphatic carboxylic acid, for example, can enumerate

Formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, sad such monocarboxylic acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brazilic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, the such dicarboxylic acids of mesaconic acid;

Tricarboxylic acid that the third three acid, aconitic acid, camphoronic acid are such etc.

As the above-mentioned carboxylic acid that contains phenyl, for example, can enumerate the compound that carboxyl directly is connected with phenyl, carboxylic acid that carboxyl links to each other with phenyl by carbochain etc.

As the carboxylic acid that contains phenyl, for example, can enumerate benzoic acid, toluic acid, cumidic acid, 2,3-mesitylenic acid (ヘ メ リ Star ト acid), the such aromatic series monocarboxylic acid of Lay woods acid;

Phthalic acid, m-phthalic acid, the such aromatic dicarboxylic acid of terephthalic acid (TPA);

The aromatic series polybasic carboxylic acid more than 3 yuan that trihemellitic acid, trimesic acid, mellophanic acid, pyromellitic acid are such and

Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, inferior cinnamic acid, coumaric acid, 2,4-dihydroxycinnamic acid etc.

In these organic acids, from alkali solubility, for the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or light shield layer produces viewpoints such as scum or residual film, as aliphatic carboxylic acid, the preferred aliphat dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.In addition, as the carboxylic acid that contains phenyl, optimization aromatic dicarboxylic acid, preferred especially phthalic acid.

Above-mentioned organic acid may be used singly or as a mixture of two or more.

Organic acid consumption relatively all radiation-ray sensitive composition is preferably below the 15 weight %, more preferably below the 10 weight %.At this moment, if the organic acid consumption surpasses 15 weight %, exist the adaptation downward trend of the dyed layer of formation to substrate.

In addition, as above-mentioned organic amino compounds, have fatty amine amino more than 1 in the preferred molecule or contain the amine of phenyl.

As above-mentioned fatty amine, for example, can enumerate n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, positive lauryl amine, cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, 4-methyl cyclohexylamine, 2-ethyl cyclohexylamine, 3-ethyl cyclohexylamine, such list (ring) alkyl amine of 4-ethyl cyclohexylamine;

Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, two n-amylamines, two n-hexylamines, methyl cyclohexylamine, ethyl cyclohexylamine, such two (ring) alkyl amine of dicyclohexyl amine;

Dimethylamino ethylamine, methyl-diethyl-amine, triethylamine, dimethyl n propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dimethyl cyclohexyl amine, diethyl cyclohexylamine, methyl bicyclic hexylamine, ethyl dicyclohexyl amine, such three (ring) alkyl amine of tricyclohexyltin amine;

The 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, such list (ring) alkanolamine of 4-amino-1-cyclohexanol;

Diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, such two (ring) alkanolamine of two n-hexyl alcohol amine, two (4-cyclohexanol) amine;

Triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, such three (ring) alkanolamine of three n-hexyl alcohol amine, three (4-cyclohexanol) amine;

3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3 butylene glycol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino (ring) the alkane glycol that ammediol is such;

1-Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, the such cycloalkanes methyl alcohol that contains amino of 4-diethylamino cyclohexane methanol;

Amino carboxylic acid that Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-1-aminocyclopropane-1-carboxylic acid, 1-aminocyclohexane carboxylic acid, 4-1-aminocyclopropane-1-carboxylic acid are such etc.

In addition, as the above-mentioned amine that contains phenyl, for example, can enumerate the compound that amino is direct and phenyl is continuous, the compound that amino is connected with phenyl by carbochain etc.

As the amine that contains phenyl, for example, can enumerate

Aniline, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-pro-pyl aniline, 4-isopropyl aniline, 4-n-butyl aniline, 4-tert-butyl group aniline, naphthalidine, 2-naphthylamines, N, accelerine, N, N-diethylaniline, 4-methyl-N, the aromatic amine that accelerine is such;

2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylamino benzyl alcohol, the such aminobenzyl alcohol of 4-diethylamino benzyl alcohol;

Amino-phenol that 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol are such etc.

In these organic amino compounds, from for the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or light shield layer produces viewpoints such as scum or residual film, as fatty amine, preferred single (ring) alkanolamine, amino (ring) alkane glycol, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol etc.In addition, as the amine that contains phenyl, preferred amino phenols, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.

Above-mentioned organic amino compounds may be used singly or as a mixture of two or more.

The consumption of organic amino compounds relatively all radiation-ray sensitive composition is preferably 15 weight %, more preferably below the 10 weight %.If the consumption of organic amino compounds is greater than 15 weight %, the adaptation of the relative substrate of dyed layer of formation may descend.

In addition, as the adjuvant beyond above-mentioned organic acid and the organic amino compounds, for example, can enumerate blue pigment derivant such as copper phthalocyanine derivative thing or yellow uitramarine derivant etc. and disperse auxiliary agent;

Filler such as glass, alumina;

Macromolecular compounds such as polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ethers, poly-(fluoroalkyl acrylate) class;

Surfactants such as anionic species, cationic, nonionic class;

Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-glycidyl ether propyl trimethoxy silicane, 3-glycidyl ether propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, driving fit promoter such as 3-sulfydryl propyl trimethoxy silicane;

2, antioxidants such as 2 '-sulphur two (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol;

2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone class ultraviolet light absorber;

Anticoalescents such as sodium polyacrylate;

1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2-phenylazos-4-methoxyl-2, hot radicals such as 4-methyl pentane nitrile produce agent etc.

Solvent

The radiation-ray sensitive composition that is used to form dyed layer of the present invention as essential composition, contains above-mentioned additive component with above-mentioned (A)～(D) composition in case of necessity, preferably sneaks into solvent and is modulated into fluid composition.

As above-mentioned solvent, can suitably select to use to disperse or dissolve (A)～(D) composition or the additive component that constitutes radiation-ray sensitive composition, and not react with these compositions, have appropriate volatile solvent.

As such solvent, for example, can enumerate

The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, the single n-propyl ether of dipropylene glycol, the single n-butyl ether of dipropylene glycol, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers that tripropylene glycol list ethylether is such;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, TC acetate, propylene glycol monomethyl ether acetate, such (gathering) the alkylene glycol monoalkyl ethers acetate of propylene glycol list ethylether acetate;

Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other such ethers of tetrahydrofuran;

MEK, cyclohexanone, 2-heptanone, the such ketone of 3-heptanone;

Methyl lactate, the such lactic acid alkyl ester of ethyl lactate;

2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-Methoxy acetic acid butyl ester, 3-methyl-3-methoxy propyl acid butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other esters that 2-ketobutyric acid ethyl ester is such;

Toluene, the such aromatic hydrocarbon of dimethylbenzene;

N, the acid amides that dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone are such or lactams etc.

In these solvents, from dissolubility, pigment-dispersing, viewpoints such as coating, preferred propylene glycol monomethyl ether, the ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol list ethylether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxy propyl acid butyl ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.

Above-mentioned solvent may be used singly or as a mixture of two or more.

In addition, with above-mentioned solvent, can also and with high boiling solvents such as benzylisoeugenol, two-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, glycol monomethyl phenyl ether acetates.

These high boiling solvents may be used singly or as a mixture of two or more.

The consumption of solvent is restriction especially, but from viewpoints such as the coating of gained radiation-ray sensitive composition, stability, and the total concentration of each composition of removing the solvent of said composition is preferably 5～50 weight %, more preferably 10～40 weight %.

Color filter

Color filter of the present invention possesses the dyed layer that is formed by the radiation-ray sensitive composition that is used to form dyed layer of the present invention.

Below, the method that forms color filter of the present invention is described.

At first, on the surface of substrate, as required, form light shield layer in order to divide the part that forms pixel, on this substrate, for example, after coating is dispersed with the fluid composition of radiation-ray sensitive composition of red pigment, carry out prebake, make solvent evaporation, formation is filmed.Then, Jie is filmed to this by mask and exposes, and uses alkaline developer to develop then, and the unexposed portion of filming is removed in dissolving, bakes after carrying out then, thereby forms the pel array of red pixel pattern with the orientation configuration of regulation.

Afterwards, use is dispersed with the fluid composition of each radiation-ray sensitive composition of green or blue pigment, with aforesaid way similarly carry out each fluid composition coating, bake in advance, expose, develop and after bake, on same substrate, form green pel array and blue pixels array successively, thereby obtained on substrate, to dispose the color filter of red, green and blue trichromatic pel array.But in the present invention, the order that forms each color pixel is not limited to said sequence.

In addition, black matrix" can use the radiation-ray sensitive composition that is used to form dyed layer of the present invention, forms by the mode identical with the situation that forms above-mentioned pixel.

As the substrate that when forming pixel and/or black matrix", uses, for example, can enumerate glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.

In addition, for these substrates,, can also implement to utilize the suitable pre-service such as chemical treatment, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc. in advance according to hope.

When on substrate, being coated with the fluid composition of radiation-ray sensitive composition, can adopt spraying process, roll coating process, spin-coating method (spin coat), slit die rubbing method, rod to be coated with suitable rubbing methods such as method, ink-jet method.Preferred especially spin-coating method, slit die rubbing method.

When coating thickness is dried thickness, be preferably 0.1～10 μ m, more preferably 0.2～8.0 μ m is preferably 0.2～6.0 μ m especially.

Radioactive ray as using when forming pixel and/or black matrix" for example, can use visible light, ultraviolet ray, far ultraviolet, electronics line, X ray.The radioactive ray of optimal wavelength in 190～450nm scope.

The exposure of radioactive ray is preferably 10～10,000J/m ²

In addition, as above-mentioned alkaline developer, for example, preferred sodium carbonate, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5,4,0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4,3,0]-5-nonene etc.

Can also in above-mentioned alkaline developer, add an amount of water-miscible organic solvent such as for example methyl alcohol, ethanol etc. or surfactant etc.In addition, alkali is generally washed after developing.

As the development treatment method, can use spray development method, spray development method, immersion development method, the development method etc. of striking.Development conditions is preferably 5～300 seconds at normal temperatures.

The color filter of the present invention that makes like this is for example very useful for transmission-type or Reflexible color LCD, colour pick-up tube element, color photo sensors etc.

Chromatic liquid crystal screen

Chromatic liquid crystal screen of the present invention possesses color filter of the present invention.

In addition, 1 embodiment as LCDs of the present invention, use the radiation-ray sensitive composition that is used to form dyed layer of the present invention, on the thin film transistor base plate array, according to above-mentioned such pixel and/or black matrix" of forming, thereby can make chromatic liquid crystal screen with utmost point excellent specific property.

The radiation-ray sensitive composition that is used to form dyed layer of the present invention contains above-mentioned (A)～(D) composition as essential composition, and following (I)～(IV) enumerates particularly preferred composition particularly.

(I) (B) alkali soluble resins comprises the radiation-ray sensitive composition that is used to form dyed layer of carboxylic multipolymer (B1).

(II) (C) polyfunctional monomer by the radiation-ray sensitive composition that is used to form dyed layer of at least a kind that is selected from trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate above-mentioned (I) that forms.

(III) O-acyl oxime type optical free radical produces agent by being selected from 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl oximido) ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl oximido) ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl oximido) ethyl ketone, and 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, the radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (II) of at least a kind of composition of 1-(O-acetyl oximido) ethyl ketone.

(IV) (A) colorant comprises above-mentioned (I), (II) or the radiation-ray sensitive composition that is used to form dyed layer (III) of organic pigment and/or carbon black.

In addition, the preferred color filter of the present invention

(V) possess pixel and/or the black matrix" that forms by above-mentioned (I), (II), (III) or the radiation-ray sensitive composition that is used to form dyed layer (IV).

In addition, the preferred chromatic liquid crystal screen of the present invention

(VI) possess the color filter of above-mentioned (V),

The further preferred chromatic liquid crystal screen of the present invention

(VII) on the thin film transistor base plate array, possess the pixel and/or the black matrix" that form by above-mentioned (I), (II), (III) or the radiation-ray sensitive composition that is used to form dyed layer (IV).

As mentioned above, the radiation-ray sensitive composition of dyed layer that is used to form of the present invention is by using by the highly sensitive O-acyl oxime type optical free radical of radioactive ray being produced the optical free radical generation agent that agent (D1) is formed, even contain under the situation of pigment on high concentration ground, can be even also can form when developing not, can not produce scum silica frost at the edge of pattern of pixels and black matrix pattern and under low exposure, also not have the good pixel pattern and the black matrix pattern of pattern edge shortcoming and undercut at residual insolubles on the substrate at unexposed position and on the light shield layer.

In addition, use pixel and the black matrix" that is used to form the radiation-ray sensitive composition of dyed layer and forms of the present invention, its surface smoothing height, the adaptation with substrate is also excellent in addition.

Therefore, can extremely to be fit to be applied to make in the electronics industry be the various color filters of representative with the chromatic liquid crystal screen color filter to the radiation-ray sensitive composition that is used to form dyed layer of the present invention.

Embodiment

Below, by enumerating embodiment, embodiments of the present invention are described particularly further.But the present invention is not limited to following embodiment.

Here, part and % are weight standards.

＜(B) manufacturing of alkali soluble resins 〉

Synthesis example 1

In the flask that condenser pipe and stirrer are housed, add 1 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 parts propylene glycol monomethyl ether acetate, continue to add 15 parts methacrylic acid, 15 parts styrene, 35 parts benzyl acrylate, 10 parts glycerin monomethyl acrylic ester, 25 parts N-phenylmaleimide and 2.5 parts chain-transferring agent α-Jia Jibenyixierjuwu, and with behind the nitrogen replacement, slowly stir, reaction solution is warming up to 80 ℃, keep this temperature, carry out 3 hours polymerization.Afterwards, reaction solution is warming up to 100 ℃, add 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) carries out 1 hour polymerization again, thereby makes resin solution (solid concentration=33.0%).

The Mw=17 of gained resin, 000, Mn=8,000.This resin as " resin (B-1) ".

Synthesis example 2

In the flask that condenser pipe and stirrer are housed, add 1 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 parts propylene glycol monomethyl ether acetate, continue to add 15 parts methacrylic acid, 15 parts styrene, 30 parts benzyl acrylate, 15 parts glycerin monomethyl acrylic ester, 25 parts N-phenylmaleimide and 2.5 parts chain-transferring agent α-Jia Jibenyixierjuwu, and with behind the nitrogen replacement, slowly stir, reaction solution is warming up to 80 ℃, keep this temperature, carry out 3 hours polymerization.Afterwards, reaction solution is warming up to 100 ℃, add 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) carries out 1 hour polymerization again, thereby makes resin solution (solid concentration=32.9%).

The Mw=19 of gained resin, 000, Mn=9,000.This resin as " resin (B-2) ".

Synthesis example 3

In the flask that condenser pipe and stirrer are housed, add 1 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 parts propylene glycol monomethyl ether acetate, continue to add 15 parts methacrylic acid, 15 parts styrene, 30 parts benzyl acrylate, 10 parts glycerin monomethyl acrylic ester, 30 parts N-phenylmaleimide and 2.5 parts chain-transferring agent α-Jia Jibenyixierjuwu, and with behind the nitrogen replacement, slowly stir, reaction solution is warming up to 80 ℃, keep this temperature, carry out 3 hours polymerization.Afterwards, reaction solution is warming up to 100 ℃, add 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) carries out 1 hour polymerization again, thereby makes resin solution (solid concentration=33.2%).

The Mw=15 of gained resin, 000, Mn=7,000.This resin as " resin (B-3) ".

Synthesis example 4

In the flask that condenser pipe and stirrer are housed, add 3 parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 parts propylene glycol monomethyl ether acetate, continue to add 15 parts methacrylic acid, 30 parts acenaphthylene, 35 parts benzyl acrylate, 10 parts 2-hydroxyethyl methacrylate, ω-carboxyl polycaprolactone single-acrylate of 10 parts and 5 parts chain-transferring agent α-Jia Jibenyixierjuwu, and with behind the nitrogen replacement, slowly stir, reaction solution is warming up to 80 ℃, keep this temperature, carry out 3 hours polymerization.Afterwards, reaction solution is warming up to 100 ℃, add 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) carries out 1 hour polymerization again, thereby makes resin solution (solid concentration=31.0%).

The Mw=10 of gained resin, 000, Mn=6,000.This resin as " resin (B-4) ".

Embodiment 1

The preparation of＜fluid composition 〉

Mix following composition: 80/20 (weight ratio) potpourri of the C.I. paratonere 254 of 85 parts conduct (A) colorant and C.I. paratonere 177; the resin (B-1) of 80 parts conduct (B) alkali soluble resins; the dipentaerythritol acrylate of 80 parts conduct (C) polyfunctional monomer; 10 parts conduct (D) optical free radical produces 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxo the benzoyl)-9.H.-carbazole-3-yl of agent]-; 1-(O-acetyl oximido) ethyl ketone; and 1; 000 part as the 3-ethoxyl ethyl propionate of solvent and 70/30 (weight ratio) potpourri of propylene glycol monomethyl ether acetate, the preparation radiation-ray sensitive composition fluid composition (R1).

The formation of＜dyed layer 〉

Use spinner, be formed with the SiO that prevents surperficial precipitated sodium ion ₂Be coated with fluid composition (R1) on the soda-lime glass substrate of film afterwards, on 90 ℃ hot plate, carry out 2 hours bake in advance, form filming of thickness 1.7 μ m.

Then, substrate is cooled to after the room temperature, uses high-pressure mercury-vapor lamp, be situated between by mask (slit width 30 μ m), exposure comprises the ultraviolet ray of each wavelength of 365nm, 405nm and 436nm on filming.The exposure of this moment is 400J/m ²Afterwards, substrate was flooded 1 minute in 23 ℃ 0.04% potassium hydroxide aqueous solution, after the development, utilize ultrapure water to wash, air-dry.Then, in 220 ℃ purification stove, carry out 30 minutes after bake, be formed on the pel array that is arranged with red strip pattern of pixels on the substrate.

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, and on the edge of pattern of pixels, do not find scum silica frost and shortcoming.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, do not find undercut.The live width of the pattern that can form is 10 μ m.

Comparative example 1

The preparation of＜fluid composition and the formation of dyed layer 〉

(D) composition changed into beyond 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone of 30 parts, prepare radiation-ray sensitive composition (r1) similarly to Example 1.

Then, substitute the fluid composition (R1), on substrate, form the pel array that is arranged with red strip pattern of pixels similarly to Example 1 except using fluid composition (r1).

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, still, found the shortcoming at the edge of pattern of pixels.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, found undercut.The live width of the pattern that can form is 15 μ m.

Embodiment 2

The preparation of＜fluid composition and the formation of dyed layer 〉

Mix following composition: 60/40 (weight ratio) potpourri of the C.I. pigment green 36 of 95 parts conduct (A) colorant and C.I. pigment yellow 150; the resin (B-2) of 70 parts conduct (B) alkali soluble resins; the dipentaerythritol acrylate of 80 parts conduct (C) polyfunctional monomer; 12 parts conduct (D) optical free radical produces 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl the base)-9.H.-carbazole-3-yl of agent]-; 1-(O-acetyl oximido) ethyl ketone; 1 part as the malonic acid of adjuvant and 900 parts as the acetate 3-methoxyl butyl ester of solvent and 50/50 (weight ratio) potpourri of propylene glycol monomethyl ether acetate, the fluid composition (G1) of preparation radiation-ray sensitive composition.

Then, except using the alternative fluid composition (R1) of fluid composition (G1), on substrate, form the pel array that is arranged with green strip pattern of pixels similarly to Example 1.

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, and on the edge of pattern of pixels, do not find scum silica frost and shortcoming.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, do not find undercut.The live width of the pattern that can form is 10 μ m.

Embodiment 3

The preparation of＜fluid composition and the formation of dyed layer 〉

Mix following composition: the C.I. pigment blue 15 of 70 parts conduct (A) colorant: 6 and 95/5 (weight ratio) potpourri of C.I. pigment Violet 23; the resin (B-3) of 60 parts conduct (B) alkali soluble resins; the dipentaerythritol acrylate of 90 parts conduct (C) polyfunctional monomer; 20 parts conduct (D) optical free radical produces neat 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl oximido) ethyl ketone; 5 parts A-60 (trade name as adjuvant; the non-ionic surfactant that flower king (strain) makes) and 900 parts as the 3-ethoxyl ethyl propionate of solvent and 60/40 (weight ratio) potpourri of propylene glycol monomethyl ether acetate, the fluid composition (B1) of preparation radiation-ray sensitive composition.

Then, except using the alternative fluid composition (R1) of fluid composition (B1), on substrate, form the pel array that is arranged with blue strip pattern of pixels similarly to Example 1.

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, and on the edge of pattern of pixels, do not find scum silica frost and shortcoming.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, do not find undercut.The live width of the pattern that can form is 10 μ m.

Embodiment 4

The preparation of＜fluid composition and the formation of dyed layer 〉

Mix following composition: the carbon black of 250 parts conduct (A) colorant (driving state's pigment (strain) manufacturing); the resin (B-4) of 75 parts conduct (B) alkali soluble resins; the dipentaerythritol acrylate of 75 parts conduct (C) polyfunctional monomer; 10 parts conduct (D) optical free radical produces 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl the base)-9.H.-carbazole-3-yl of agent]-; 1-(O-acetyl oximido) ethyl ketone; and 1; 000 part as the propylene glycol monomethyl ether acetate of solvent and 50/50 (weight ratio) potpourri of cyclohexanone, the preparation radiation-ray sensitive composition fluid composition (BK1).

Then, except using the alternative fluid composition (R1) of fluid composition (BK1), on substrate, form the pel array that is arranged with black strip pattern of pixels similarly to Example 1.

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, and on the edge of pattern of pixels, do not find scum silica frost and shortcoming.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, do not find undercut.The live width of the pattern that can form is 10 μ m.

Embodiment 5

The preparation of＜fluid composition and the formation of dyed layer 〉

Except using 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, beyond 1-(the O-acetyl oximido) ethyl ketone, prepare the fluid composition (BK2) of radiation-ray sensitive composition similarly to Example 4.

＜estimate

Use the pel array on the observation by light microscope substrate, on the substrate at unexposed position, do not find the development image retention, and on the edge of pattern of pixels, do not find scum silica frost and shortcoming.

In addition, use scanning electron microscope (SEM) to observe the cross section of pattern of pixels, do not find undercut.The live width of the pattern that can form is 9 μ m.

Claims (3)

1. be used to form the radiation-ray sensitive composition of dyed layer, it is characterized in that: contain the combination of (A) colorant, (B) alkali soluble resins, (C) polyfunctional monomer or itself and simple function group monomer and (D) serve as the optical free radical generation agent of essential composition with the compound of following formula (1) or (2) expression

In formula (1) or (2), R ₁Be the alkyl of carbon number 1～20, the naphthenic base or the phenyl of carbon number 3～8, R ₂, R ₃The alkyl, the naphthenic base of carbon number 3～8, the phenyl that are hydrogen atom, carbon number 1～20 respectively (but also can be replaced by the alkoxy of the alkyl of the carbon number more than 1 1～6, carbon number 1～6, phenyl or halogen atom.) or the alicyclic group (not comprising above-mentioned naphthenic base) of carbon number 7～20, R ₄Be the oxygen-containing heterocycle of carbon number 4～20, the nitrogen heterocycle of carbon number 4～20 or the sulfur heterocyclic ring base of carbon number 4～20, R ₅Be the alkyl of hydrogen atom, carbon number 1～12 or the alkoxy of carbon number 1～12, and n is 1～5 integer, m is 0～5 integer, n+m≤5, and l is 0～6 integer.

2, color filter is characterized in that: possess the dyed layer that is formed by the described radiation-ray sensitive composition that is used to form dyed layer of claim 1.

3, the chromatic liquid crystal screen that possesses the described color filter of claim 2.