CN1690735A - Dyed layer forming radiation linear combination, colour filter and liquid crystal display screen - Google Patents

Abstract

A dyed layer forming used sense radiating linear composition includes a colorant, an alkali-soluble resin, a polyfunctional monomer and the sense radiating linear polymerization initiator of 2-(4-methy benzyl)-2-(dimethylamino)-1-(4-mrpholine phenyl)butane-1-ketone kind of mrpholine phenyl compound. The composition can restrain the pollution to the sintering furnace and photomask which is caused by the sublimation of the sense radiating linear polymerization initiator component, furthermore, the liquid is not generated with impurity and the imaging property and pattern shape are excellent.

Description

Dyed layer forms with radiation sensitive compositions, colored filter and LCDs

Technical field

The present invention relates to dyed layer forms with radiation sensitive compositions, colored filter and LCDs, the dyed layer of colored filter that relates to the uses such as color liquid crystal display arrangement, colour pick-up tube element of transmission-type or reflection-type in more detail forms the radiation sensitive compositions of usefulness, has the colored filter of the dyed layer that is made of this radiation sensitive compositions, and the LCDs with this colored filter.

Background technology

In the past, when using painted radiation sensitive compositions to make colored filter, known have on the substrate or be pre-formed the painted radiation sensitive compositions of coating on the substrate of light shield layer of predetermined pattern, dry back is facing to the pattern form irradiation radioactive ray (hereinafter referred to as exposure) of filming to regulation, obtains the formation method (opening flat 2-144502 communique and the spy opens flat 3-53201 communique with reference to the spy) of each color pixel by video picture.

In addition, in recent years, because the large tracts of landization of LCDs and productive raising etc., the size of female glass substrate maximizes about 1500 * 1800mm from about 680 * 880mm in the past.But maximization along with substrate, when colored colored filter forms, dyed layer forms with the distillation of the radioactivity-sensitive polymerization initiator composition in the radiation sensitive compositions, has the problem of polluting sintering furnace and photomask, has caused the decline of production efficiency and the rising of production cost.

And then, the applicant opens the radioactivity-sensitive polymerization initiator that discloses in the 2001-235617 communique as radiation sensitive compositions the spy, by using the bromine substituted acetophenone based compound of 1-(2-bromo-4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone or 1-(3-bromo-4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone etc., can reduce since the distillation of radioactivity-sensitive polymerization initiator composition to the pollution of sintering furnace and exhaust passage, minimizing is arranged on the obstruction of the ducted filtrator of video picture when using imaging liquid repeatedly etc.

; comprising that the spy opens is put down in writing in the 2001-235617 communique; be used for the radiation sensitive compositions in the past that colored filter forms; the distillation of radioactivity-sensitive polymerization initiator composition preventing owing to can't be said so fully aspect the generation of impurity in to the pollution of sintering furnace and photomask and liquid; therefore, wish to develop the radiation sensitive compositions that has these characteristics concurrently at present consumingly.

Summary of the invention

The object of the present invention is to provide dyed layer to form the radiation sensitive compositions of usefulness, its can suppress since the distillation of radioactivity-sensitive polymerization initiator composition to there not being the generation of impurity in the pollution of sintering furnace and photomask and the liquid, and video picture, pattern form etc. also good, have the colored filter of the dyed layer that forms by this radiation sensitive compositions and have the LCDs of this colored filter.

Other purpose and advantage of the present invention can be clear and definite from the following description.

According to the present invention, above-mentioned purpose of the present invention and advantage, first, finish by using a kind of radiation sensitive compositions, it is characterized in that containing (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer or itself and simple function combination of compounds, and (D) contain the compound of useful following formula (1) expression, and be used for dyed layer and form.

R in the general formula (1) ¹The alkyl of the straight chain shape of expression carbon number 1～12, a chain or ring-type; R ²And R ³Alkyl or the benzyl of representing straight chain shape, a chain or the ring-type of hydrogen atom, carbon number 1～12 independently of each other; R ⁴, R ⁵, R ⁷And R ⁸Represent the straight chain shape of the straight chain shape of hydrogen atom, halogen atom, carbon number 1～12, the alkyl that props up chain or ring-type or carbon number 1～4, the alkoxy of a chain independently of each other; R ⁶The expression halogen atom, the straight chain shape of carbon number 1～12, prop up the alkyl of chain or ring-type, with hydroxyl and be selected from the straight chain shape of the carbon number 1～12 that substituting group in the group that the alkoxy by the straight chain shape of carbon number 1～4 or a chain constitutes replaced, prop up the alkyl of chain or ring-type, the straight chain shape of carbon number 1～4, or the alkoxy of a chain, the perhaps straight chain shape of the carbon number 2～4 that replaced of substituting group in the group that constitutes with the alkoxy that is selected from by the straight chain shape of hydroxyl and carbon number 1～4 or a chain, or the alkoxy of a chain.

Said among the present invention " radioactive ray " are meant and comprise ultraviolet ray, far ultraviolet, X line, electronics line, molecular line, γ line, synchrotron radioactive ray, proton beam etc.

Said among the present invention " dyed layer " is meant the layer that is made of pixel and/or black matrix".

According to the present invention, above-mentioned purpose of the present invention and advantage, the second, be to finish by the colored filter that the dyed layer that the radiation sensitive compositions with the invention described above forms constitutes.

According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, be to finish by LCDs with above-mentioned colored filter.

Below explain the present invention.

(A) colorant

Colorant among the present invention has no particular limits for tone, can suitably select any can the use in pigment, dyestuff or the natural colouring matter according to the purposes of the colored filter that obtains.

In order to make colored filter have high meticulous color development and thermotolerance, colorant of the present invention preferably uses color emissivity 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 organic pigment, for example can enumerate, at Colour Index (C.I.; The Society ofDyers and colourists company distribution) in, be sorted in the compound of pigment (Pigment), concrete is has the pigment of following Colour Index (C.I.) number.

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. paratonere-3, C.I. paratonere-4, C.I. paratonere-5, C.I. paratonere-6, C.I. paratonere-7, C.I. paratonere-8, C.I. paratonere-9, C.I. paratonere-10, C.I. paratonere-11, red-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. paratonere-21, C.I. paratonere-22, C.I. paratonere-23, C.I. paratonere-30, C.I. paratonere-31, C.I. paratonere-32, C.I. paratonere-37, C.I. paratonere-38, C.I. paratonere-40, C.I. paratonere-41, C.I. paratonere-42, C.I. paratonere-48:1, C.I. paratonere-48:2, C.I. paratonere-48:3, C.I. paratonere-48:4, C.I. paratonere-49:1, C.I. paratonere-49:2, 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. paratonere-81:1, C.I. paratonere-83, C.I. paratonere-88, C.I. paratonere-90:1, C.I. paratonere-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. paratonere-112, C.I. paratonere-113, C.I. paratonere-114, C.I. paratonere-122, C.I. paratonere-123, C.I. paratonere-144, C.I. paratonere-146, C.I. paratonere-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, paratonere-190, C.I. paratonere-193, C.I. paratonere-194, C.I. paratonere-202, C.I. paratonere-206, C.I. paratonere-207, C.I. paratonere-208, C.I. paratonere-209, C.I. paratonere-215, C.I. paratonere-216, 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. alizarol saphirol-15, C.I. alizarol saphirol-15:3, C.I. alizarol saphirol-15:4, C.I. alizarol saphirol-15:6, C.I. alizarol saphirol-60;

C.I. naphthol green-7, C.I. naphthol 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 and make up these methods back of purifying and use with for example sulfuric acid recrystallization method, solvent wash method in addition.

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

In the present invention, organic pigment and inorganic pigment can be distinguished individually or mix back use more than 2 kinds, and organic pigment and inorganic pigment also can and be used in addition.When forming pixel, preferably use the organic pigment more than a kind.When forming black matrix", preferably use organic pigment and/or carbon black more than 2 kinds in addition.

In the present invention, above-mentioned each pigment as required can be with using behind this particle surface of polymkeric substance upgrading.As the polymkeric substance of this particle surface of upgrading, for example can enumerate, the spy open record such as flat 8-259876 communique polymkeric substance and, the polymkeric substance used of commercially available various pigment dispersing or oligomer etc.

As required, colorant can use with spreading agent among the present invention.

For example can enumerate the surfactant of kation system, negative ion system, nonionic system, both sexes, silicon-type, fluorine system etc. as above-mentioned spreading agent.

As above-mentioned surfactant, can enumerate the polyoxyethylene alkyl ether of polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether class; The polyoxyethylene alkyl phenyl ether of polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ethers; Polyethylene glycol dilaurate; The polyethylene glycol di of polyglycol distearate class; Sorbitan fatty acid ester; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polyethyleneimine: amine etc., in addition, also have commodity, as KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Port リ Off ロ-(common prosperity chemistry (strain) system), エ Off ト Star プ (ト-ケ system product society system), メ ガ Off ア Star Network (big Japanese ink chemical industry (strain) system), Off ロ ラ-De (Sumitomo three M (strain) system), ア サ ヒ ガ-De, サ-Off ロ Application (above Asahi Glass (strain) system), Disperbyk (color chemistry Japan (strain) system), ソ Le ス パ-ス (セ ネ カ (strain) system) etc. with following trade name.

These surfactants can separately or mix more than 2 kinds and use.

The use amount of surfactant, for 100 weight portion colorants, below preferred 50 weight portions, more preferably 0～30 weight portion.

(B) alkali soluble resin

Alkali soluble resin of the present invention as long as play the cementing agent effect for colorant, and when forming dyed layer, has solubility to the imaging liquid that uses in this video picture operation, preferred alkaline imaging liquid, just has no particular limits.The alkali soluble resin that wherein preferably has carboxyl, especially preferably have more than one carboxyl ethylene unsaturated monomer (hereinafter referred to as " containing the carboxyl unsaturated monomer ") and with other the multipolymer (hereinafter referred to as " containing carboxyl copolymer ") of copolymerization of ethylene unsaturated monomer (hereinafter referred to as " copolymerization unsaturated monomer ").

As the unsaturated monomer that contains carboxyl, for example can enumerate the unsaturated monocarboxylic acid of (methyl) acrylic acid, butenoic acid, α-Lv Bingxisuan, cinnamic acid;

The unsaturated dicarboxylic acid of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid class or its acid anhydrides;

Unsaturated polyprotonic acid or its acid anhydrides that ternary is above;

List [2-(methyl) acrylyl oxy-ethyl] ester of the polybasic carboxylic acid that the binary of mono succinate [2-(methyl) acrylyl oxy-ethyl] ester, phthalic acid list [2-(methyl) acrylyl oxy-ethyl] ester class is above;

Two ends of ω-carboxyl polycaprolactone list (methyl) esters of acrylic acid have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.

In these the unsaturated monomer that contains carboxyl, mono succinate [2-acrylyl oxy-ethyl] ester and phthalic acid list [2-acrylyl oxy-ethyl] ester are being sold on market with the trade name of M-5300 and M-5400 (East Asia synthetic (strain) system) respectively.

The above-mentioned unsaturated monomer that contains carboxyl can individually or mix more than 2 kinds and use.

In addition as the copolymerization unsaturated monomer, for example can enumerate styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to Benzene Chloride ethene, 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 glycidyl ether, a vinyl benzyl glycidyl ether, to the aromatic ethenyl compound of vinyl benzyl glycidyl ethers;

Other polymerism aromatics of indenes, 1-methyl indenes, acenaphthylene class;

(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-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) allyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, 2-methoxy ethyl (methyl) acrylate, 2-phenoxy group ethyl (methyl) acrylate, methoxyl diglycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, MPEG (methyl) acrylate, methoxyl dipropylene glycol (methyl) acrylate, (methyl) acrylic acid norborneol ester, bicyclopentadiene (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, the esters of unsaturated carboxylic acids of glycerine list (methyl) esters of acrylic acid;

The unsaturated carboxylic acid aminoalkyl ester of 2-amino-ethyl (methyl) acrylate, 2-dimethyl aminoethyl (methyl) acrylate, 2-aminopropyl (methyl) acrylate, 2-dimethylaminopropyl (methyl) acrylate, 3-aminopropyl (methyl) acrylate, 3-dimethylaminopropyl (methyl) esters of acrylic acid;

The unsaturated carboxylic acid glycidyl esters of (methyl) acrylic acid glycidyl esters class;

The vinyl carboxylates of vinyl acetate, propionate, vinyl butyrate, vinyl benzoate class;

The unsaturated ethers of vinyl methyl ether, EVE, allyl glycidyl ether class;

The acrylonitrile compound of (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile class;

The unsaturated amides of (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide etc.;

The unsaturated acyl imines of maleimide, N-phenylmaleimide, N-cyclohexyl maleimide etc.;

The aliphatics conjugated diolefine of 1,3-butadiene, isoprene, chlorbutadiene class;

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

These multipolymer unsaturated monomers can individually or mix more than 2 kinds and use.

As the carboxyl copolymer that contains of the present invention, preferably (i) with (methyl) acrylic acid as essential composition, according to circumstances, so can contain at least a compound that is selected from the group that constitutes by mono succinate [2-(methyl) acrylyl oxy-ethyl] ester and ω-carboxyl polycaprolactone list (methyl) acrylate contain carboxyl unsaturated monomer composition and, (ii) be selected from by styrene, acenaphthylene, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, glycerine list (methyl) acrylate, N-phenylmaleimide, at least a multipolymer (hereinafter referred to as " containing carboxyl copolymer (I) ") in the group that the big molecule of polystyrene macromolecular monomer and polymethylmethacrylate constitutes.

The concrete example that contains carboxyl copolymer (I) can be enumerated:

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

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

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate multipolymer,

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

(methyl) acrylic acid/(methyl) methyl acrylate/polyacrylic acid methyl formate 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-hydroxyl ethyl ester/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer,

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

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

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

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

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/styrene/(methyl) benzyl acrylate/glycerine list (methyl) acrylate/N-phenylmaleimide multipolymer,

(methyl) acrylic acid/acenaphthylene/(methyl) benzyl acrylate/(methyl) acrylic acid 2-hydroxyl ethyl ester/ω-carboxyl polycaprolactone list (methyl) acrylate copolymer etc.

The ratio that contains the multipolymer that contains the carboxyl unsaturated monomer in the carboxyl copolymer, preferred 5～50 weight %, more preferably 10～40 weight %.The ratio of multipolymer that contains the carboxyl unsaturated monomer is during less than 5 weight %, and the radiation sensitive compositions that obtains has the tendency of decline to the dissolubility of alkaline imaging liquid.On the other hand, then excessive if surpass 50 weight % to the dissolubility of alkaline imaging liquid, with alkaline imaging liquid video picture the time, cause the tendency that come off with the film on dyed layer surface slightly make of dyed layer easily from substrate.

Alkali soluble resin of the present invention, with gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) the conversion polystyrene weight-average molecular weight of Ce Dinging (below, be called " Mw ".), preferred 3,000～300,000, more preferably 5,000～100,000.

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

In the present invention, the soluble resin that has specific like this Mw and a Mn by use can obtain the good radiation sensitive compositions of video picture.In addition, in the time of by the pixel pattern that uses it to form to have sharp-pointed pattern edge and black matrix pattern, when video picture, be not easy to take place residue, loose colour, residual film etc. on the substrate of unexposed portion and on the light shield layer.

In addition, the ratio (Mw/Mn) of the Mw of soluble resin of the present invention and Mn, preferred 1～5, preferred especially 1～4.

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

The use amount of soluble resin of the present invention, for (A) colorant 100 weight portions, preferred 10～1,000 weight portion, more preferably 20～500 weight portions.During for use amount less than 10 weight portions of alkali soluble resin, for example alkali video picture reduction may occur, loose colour or residual film are taking place on the substrate of unexposed portion or on the light shield layer.On the other hand, if when surpassing 1,000 weight portion, because colorant concentration reduces relatively, so film often is difficult to reach colour saturation as purpose sometimes.

(C) multi-functional monomer or itself and simple function combination of compounds

Multi-functional monomer of the present invention is the monomer with the polymerism unsaturated link more than 2.

As the example of multi-functional monomer, can enumerate two (methyl) acrylate as ethylene glycol, propandiols alkane glycol;

Two (methyl) acrylate of the poly-alkane glycol of polyglycol, polypropylene glycols;

Poly-(methyl) acrylate or their the dicarboxylic acids modifier of the polyvalent alcohol that the ternary of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol class is above;

Oligomeric (methyl) acrylate of polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin etc.;

Two terminal hydroxyls are poly--two (methyl) acrylate of two terminal hydroxyl fluidized polymers of 1,3-butadiene, two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones etc. and,

Three [2-(methyl) acrylyl oxy-ethyl] phosphate etc.

In these multi-functional monomer, poly-(methyl) acrylate or these dicarboxylic acids modifier, the trimethylolpropane triacrylate specifically of preferred polyvalent alcohol more than 3 yuan, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol six acrylate, dipentaerythritol hexamethyl acrylate, with the compound of following formula (2) or formula (3) expression etc.

The intensity height of the dyed layer of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol six acrylate particularly, the surface smoothing of dyed layer is good, and in that to be not easy to take place on loose colour, the residual film etc. be desirable on the substrate of unexposed portion and on the light shield layer.

In the present invention, multi-functional monomer can separately or mix more than 2 kinds and use.

In the present invention, the use amount of multi-functional monomer, for (B) alkali soluble resin 100 weight portions, preferred 5～500 weight portions, more preferably 20～300 weight portions.During for use amount less than 5 weight portions of multi-functional monomer, the intensity or the surface smoothing reduction institute trend of dyed layer is arranged.On the other hand, if when surpassing 500 weight portions, alkali video picture reduction is for example arranged, on the substrate of unexposed portion or the trend of loose colour, residual film takes place on the light shield layer easily.

In addition, in the present invention, also can use multi-functional monomer and combination with simple function monomer of 1 polymerism unsaturated link.

As above-mentioned simple function monomer, for example with above-mentioned (B) alkali soluble resin in exemplify contain outside the identical monomer of carboxyl unsaturated monomer or copolymerization unsaturated monomer, can enumerate N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-epsilon-caprolactams or as the M-5600 (trade name, East Asia synthetic (strain) system) of commercially available product etc.

These simple function monomers can separately or mix more than 2 kinds and use.The usage ratio of above-mentioned simple function monomer is for the summation of multi-functional monomer and simple function monomer, below the preferred 90 weight %, more preferably below the 50 weight %.At this moment, if the usage ratio of simple function monomer surpasses 90 weight %, the intensity or the surface smoothing of possible dyed layer are insufficient.

(D) radioactivity-sensitive polymerization initiator

In the present invention, as the radioactivity-sensitive polymerization initiator, the compound that use is represented with above-mentioned formula (1) (below, be called " polymerization initiator (1) ".)。This compound has the effect that can produce the spike of the simple function monomer polymerization that causes above-mentioned (C) multi-functional monomer and according to circumstances be used by exposure.

In formula (1), as R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸The alkyl of straight chain, side chain or ring-type of carbon number 1～12, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, 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, as R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Halogen atom, for example can enumerate fluorine atom, chlorine atom, bromine atoms etc.

In addition, as R ⁴, R ⁵, R ⁶, R ⁷And R ⁸The straight chain of carbon number 1～4 or the alkoxy of chain, for example can enumerate methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy etc.

In addition, at R ⁶With hydroxyl and be selected from the carbon number 1～12 that the substituting group in the group of being made up of the straight chain shape of carbon number 1～4 or a chain alkoxy replaces the straight chain shape, prop up in chain or the cyclic alkyl, as the alkoxy of the straight chain shape of substituent carbon number 1～4 or a chain, for example can enumerate with for above-mentioned R ⁴, R ⁵, R ⁶, R ⁷And R ⁸The identical group of group that exemplifies as the alkoxy of the straight chain shape of carbon number 1～4 or a chain.

As above-mentioned substituting group, for example preferred hydroxyl, methoxyl etc.

In addition, above-mentioned substituting group can exist more than a kind the latter more than 1.

As R ⁶Straight chain shape, the chain or the cyclic alkyl of carbon number 1～12, for example can enumerate with for above-mentioned R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸The identical group of group that exemplifies of the alkoxy of straight chain shape, chain or ring-type of carbon number 1～12.

In addition, at R ⁶With hydroxyl and be selected from the carbon number 2～4 that the substituting group in the group of being made up of the straight chain shape of carbon number 1～4 or a chain alkoxy replaces the straight chain shape, prop up in chain or the cyclic alkyl, as the alkoxy of the straight chain shape of substituent carbon number 1～4 or a chain, for example can enumerate with for above-mentioned R ⁴, R ⁵, R ⁶, R ⁷And R ⁸The identical group of group that exemplifies as the alkoxy of the straight chain shape of carbon number 1～4 or a chain.

As such substituting group, for example preferred hydroxyl, methoxyl etc.

Such substituting group can the latter exist more than 1 more than a kind.

As R ⁶The straight chain shape of carbon number 1～4 or the alkoxy of chain, for example can enumerate ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy etc.

In formula (1), as R ¹, for example preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl etc.

In addition, as R ²And R ³, for example preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl etc.

In addition, as R ⁴, R ⁵, R ⁷And R ⁸, for example preferred hydrogen atom, methyl, ethyl etc.

And then, as R ⁶, for example preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, dodecyl, hydroxymethyl, 2-hydroxyethyl, methoxy, 2-methoxy ethyl, methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, hydroxyl methoxyl, 2-hydroxyl-oxethyl, methoxymethoxy, 2-methoxy ethoxy etc.

Object lesson as preferred polymerization initiator of the present invention (1) for example has:

2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-Ethylbenzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-isopropyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-normal-butyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-isobutyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-dodecyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(3, the 4-dimethyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-methoxy-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-ethoxy benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-methylol benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-[4-(2-hydroxyl-oxethyl) benzyl]-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-[4-(2-methoxy ethoxy) benzyl]-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-isopropyl benzyl)-2-[(normal-butyl) (methyl) amino]-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-normal-butyl benzyl)-2-[(normal-butyl) (methyl) amino]-1-(4-morpholino phenyl) butane-1-ketone,

2-(4-isopropyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) pentane-1-ketone,

2-(4-isobutyl benzyl)-2-[(normal-butyl) (methyl) amino]-1-(4-morpholino phenyl) pentane-1-ketone,

2-(4-n-butoxy benzyl)-2-[(normal-butyl) (methyl) amino]-1-(4-morpholino phenyl) pentane-1-ketone,

2-(4-methyl-benzyl)-2-[two (n-octyl) amino]-1-(4-morpholino phenyl) hexane-1-ketone,

2-(4-dodecyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) octane-1-ketone etc.

In these polymerization initiators (1), preferred especially 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone, 2-(4-Ethylbenzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone, 2-(4-isopropyl benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone etc.

Among the present invention, polymerization initiator (1) can separately or mix more than 2 kinds and use.

In addition, in the present invention, with polymerization initiator (1) can and with other sensitization radiate linear composition (below, be called " other polymerization initiator ".)。

As other polymerization initiator, for example preferably have the main skeleton of representing respectively with following formula (4), formula (5) and formula (6) at least a kind of di-imidazole compound, acetophenone based compound, benzophenone based compound, benzoin based compound, α-diketone based compound, encircle quinone based compound, xanthone based compound, phosphine based compound, triazine based compound, carbazole based compound etc. more.In these, preferred di-imidazole compound, acetophenone based compound etc.

As the object lesson of above-mentioned di-imidazole compound, can enumerate:

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

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

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

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

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

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

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

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

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

Above-mentioned di-imidazole compound can separately or mix more than 2 kinds and use.

In the present invention, during as other polymerization initiator and with the di-imidazole compound, adding following hydrogen donor, is desirable thereby improve in the sensitivity.At this, said " hydrogen donor " is meant for by the free radical of exposure from the generation of di-imidazole compound, can supplies with the compound of hydrogen atom.

As such hydrogen donor, preferably with the mercapto alcohol based compound of following definitions, the amine compound of usefulness following definitions etc.

Above-mentioned mercapto alcohol based compound be with phenyl ring or heterocycle as parent nucleus, have on this parent nucleus the sulfydryl that directly combines more than 1, preferred 1～3, more preferably 1～2 compound (below, be called " mercapto alcohol is hydrogen donor ".)。

Above-mentioned amine compound be with phenyl ring or heterocycle as parent nucleus, have on this parent nucleus the amido that directly combines more than 1, preferred 1～3, more preferably 1～2 compound (below, be called " amine is hydrogen donor ".)。

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

Below, be described more specifically for hydrogen donor.

Mercapto alcohol is that hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, can have phenyl ring and heterocycle.When these rings that have more than 2, also can form condensed ring or not form condensed ring.

In addition, mercapto alcohol is that hydrogen donor is when having 2 above sulfydryls, as long as during remaining at least 1 free sulfhydryl groups, 1 above sulfydryl in the remaining sulfydryl also can use alkyl, aralkyl or aryl to replace, and then, as long as during remaining at least 1 free sulfhydryl groups, can have structural unit or 2 structural units that sulphur atom combines with the disulfide form that the organic group of 2 sulphur atoms by the divalent of alkylidene etc. combines.

And then mercapto alcohol is hydrogen donor, and the replacements such as carbobenzoxy, itrile group of alkoxy carbonyl, replacement or the non-replacement of carboxyl, replacement or non-replacement also can be used in the position beyond the sulfydryl.

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

At these mercapto alcohol is in the hydrogen donor, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.

Secondly, amine is that hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, can have phenyl ring and complexity is encircled both, when having more than 2 these rings, can form condensed ring, also can not form condensed ring.

In addition, amine is hydrogen donor, and the amino more than 1 can replace with alkyl or substituted alkyl, and in addition, the replacements such as carbobenzoxy, itrile group of alkoxy carbonyl, replacement or the non-replacement of carboxyl, replacement or non-replacement also can be used in the position beyond amino.

As such amine is the object lesson of hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid, 4-dimethylamino benzene nitrile etc.

At these amine is in the hydrogen donor, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.In addition, even when not having the di-imidazole compound, 4,4 '-two (dimethylamino) benzophenone or 4,4 '-two (diethylamino) benzophenone also can be used as radiation sensitive compositions demonstration effect individually.

In the present invention, hydrogen donor can separately or mix more than 2 kinds and use.If with the mercapto alcohol more than a kind is that hydrogen donor and the amine more than a kind are hydrogen donor when being used in combination, the dyed layer of formation is difficult to come off from substrate when video picture, in addition, is desirable from intensity and also high this aspect of sensitivity of dyed layer.

As mercapto alcohol is that hydrogen donor and amine are the object lesson of the preferred compositions of 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.Wherein, 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.

Mercapto alcohol is that hydrogen donor and amine are that the mercapto alcohol of the combination of hydrogen donor is that hydrogen donor and amine are the weight ratio of hydrogen donor, preferred 1: 1～1: 4, more preferably 1: 1～1: 3.

In addition, object lesson as above-mentioned acetophenone based compound, 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, 1-[4-(methyl mercapto) phenyl]-2-methyl-2-morpholino propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone, 1-(2-bromo-4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone, 1-(4-morpholino phenyl)-2-(2-bromobenzyl)-2-dimethylamino butane-1-ketone, 1-(4-morpholino phenyl)-2-(4-bromobenzyl)-2-dimethylamino butane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.

In these acetophenone based compounds, preferred 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone, 1-(2-bromo-4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone, 1-(4-morpholino phenyl)-2-(4-bromination benzyl)-2-dimethylamino butane-1-ketone etc.

In the present invention, and when being used as other the acetophenone based compound of polymerization initiator, also can add the above-mentioned hydrogen donor more than a kind.

In addition, as the object lesson of above-mentioned benzophenone based compound, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone etc.

In addition, as the object lesson of above-mentioned benzoin based compound, can enumerate benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoylbenzoic acid ester etc.

In addition, as the object lesson of above-mentioned α-diketone based compound, can enumerate diacetyl, dibenzoyl, toluyl formic ether etc.

In addition, as the object lesson of above-mentioned multinuclear quinone based compound, can enumerate anthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1,4-naphthoquinones etc.

In addition, as the object lesson of above-mentioned xanthone based compound, can enumerate xanthone, sulfo-xanthone, 2-chlorine sulfo-xanthone etc.

In addition, as the object lesson of above-mentioned phosphine based compound, can enumerate two (2,4,6-trimethylbenzene formyl) phenyl phosphine oxides, 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide etc.

In addition, object lesson as above-mentioned triazine based compound, can enumerate triazine based compound with halomethyl etc., for example 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-lignocaine-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-, compound with following formula (7) expression

With the compound of following formula (8) expression etc.

In addition, concrete example as above-mentioned carbazole based compound, can enumerate 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl] nonane-1,2-nonane-2-oxime-O-benzoic ether, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl] nonane-1,2-nonane-2-oxime-O-acetic acid esters, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl] pentane-1,2-pentane-2-oxime-O-acetic acid esters, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl] octane-1-ketoxime-O-acetic acid esters, 1-[9-ethyl-6-(2-toluyl)-9.H.-carbazole-3-yl] ethane-1-ketoxime-O-benzoic ether, 1-[9-ethyl-6-(2-toluyl)-9.H.-carbazole-3-yl] ethane-1-ketoxime-O-acetic acid esters, 1-[9-ethyl-6-(2,4,6-trimethylbenzene formyl)-9.H.-carbazole-3-yl] ethane-1-ketoxime-O-benzoic ether, 1-[9-normal-butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl] ethane-1-ketoxime-O-benzoic ether etc.

In these carbazole based compounds, preferred 1-[9-ethyl-6-(2-toluyl)-9.H.-carbazole-3-yl] ethane-1-ketoxime-O-acetic acid esters.

These other polymerization initiators can separately or mix more than 2 kinds and use.The usage ratio of other polymerization initiators is for the summation of polymerization initiator (1) and other polymerization initiators, below the preferred 80 weight %, more preferably below the 70 weight %.If when the usage ratio of other polymerization initiators surpasses 80 weight %, may damage the desired effect of the present invention.

The use amount of polymerization initiator of the present invention, for summation 100 weight portions of (C) multi-functional monomer or itself and simple function monomer, preferred 0.01～200 weight portion, more preferably 1～120 weight portion, preferred especially 1～100 weight portion.During use amount less than 0.01 weight portion of polymerization initiator, the curing that may occur exposes causes is insufficient, is difficult to obtain the pattern array of pixel pattern or black matrix pattern orientation configuration according to the rules.On the other hand, if surpass 200 weight portions, the dyed layer of formation comes off from substrate when video picture easily, in addition, loose colour, residual film etc. is taking place easily on the substrate of unexposed portion or on the light shield layer.

And then, in the present invention, when using above-mentioned radioactivity-sensitive polymerization initiator, as required also can and crosslinked with sensitizer, curing accelerator or high-molecular optical.More than a kind of sensitizer.

Adjuvant

Dyed layer of the present invention forms and uses radiation sensitive compositions, can contain various adjuvants as required.

As above-mentioned adjuvant, can enumerate organic acid or organic amine compound (but, remove above-mentioned hydrogen donor.) etc., it can

Further improve for dyed layer and form dissolution characteristics, and show the remaining effect that further suppresses the not dissolved matter after the video picture etc. with the alkali imaging liquid of radiation sensitive compositions.

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

As the example of above-mentioned aliphatic carboxylic acid, can enumerate:

The monocarboxylic acid of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, diethacetic acid, enanthic acid, sad class;

The dicarboxylic acids of oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, Brazilian diacid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic carboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid class;

The tricarboxylic acid of third tricarboxylic acid, aconitic acid, camphoronic acid class etc.

In addition, as the above-mentioned phenyl carboxylic acid that contains, for example can enumerate the compound that carboxyl directly is combined in phenyl, carboxyl is combined in phenyl by carbochain carboxylic acid etc.

As the example that contains the phenyl carboxylic acid, can enumerate:

Benzoic acid, toluic acid, cumfrey, 2,3-mesitylenic acid, 3, the aromatic series monocarboxylic acid of 5-mesitylenic acid class;

The aromatic binary carboxylic acid of phthalic acid, isophthalic acid, terephthalic acids class;

The aromatic series polybasic carboxylic acid more than 3 yuan of trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, Pyromellitic Acid class or phenyl acetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, inferior cinnamic acid, coumaric acid, umbellic acid etc.

In these organic acids, from alkali dissolution, for the dissolubility of solvent described later, prevent on the substrate of unexposed portion or aspect such as the loose colour on the light shield layer and residual film, as aliphatic carboxylic acid, preferred aliphat dicarboxylic acids, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.In addition, as containing the phenyl carboxylic acid, the optimization aromatic dicarboxylic acids, wherein, preferred especially phthalic acid.

Above-mentioned organic acid can separately or mix more than 2 kinds and use.

The organic acid use amount is with respect to radiation sensitive compositions integral body, below the preferred 15 weight %, more preferably below the 10 weight %.If the organic acid use amount surpasses 15 weight %, exist the trend of chromatograph for the adaptation reduction of substrate.

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

As the example of above-mentioned fatty amine, can enumerate:

List (ring) alkyl amine of 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, n-undecane base amine, dodecyl amine, cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, 4-methyl cyclohexylamine, 2-ethyl cyclohexylamine, 3-ethyl cyclohexylamine, 4-ethyl cyclohexylamine class;

Two (ring) alkyl amine of Methylethyl amine, 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, dicyclohexyl amine class;

Three (ring) alkyl amine of dimethylethyl amine, methyl diethylamide, 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, tricyclohexyltin amine class;

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

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

Three (ring) alkanolamine of triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, 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, the amino of ammediol class (ring) alkane glycol;

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, 4-diethylamino cyclohexane methanol class contain amino cycloalkanes methyl alcohol;

The amino carboxylic acid of 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-aminocyclohexane carboxylic acids etc.

In addition, as the above-mentioned phenyl amine that contains, for example can enumerate the amino compound of phenyl, the amino compound that is combined in phenyl by carbochain etc. of directly being combined in.

As the example that contains phenyl amine, 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 of accelerine class;

The aminobenzyl alcohol of 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylamino benzylalcohol, 4-diethylamino benzylalcohol class;

The amino-phenol of 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol etc.

In these organic amine compounds, from for the dissolubility of solvent described later, prevent on the substrate of unexposed portion or viewpoint such as the loose colour on the light shield layer and residual film, as fatty amine, preferred single (ring) alkanol amine and amino (ring) alkane glycol, wherein, 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 containing phenyl amine, preferred amino phenols, wherein, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.

Above-mentioned organic amine compound can separately or mix more than 2 kinds and use.

The use amount of organic amine compound, all for radiation sensitive compositions, below the preferred 15 weight %, more preferably below the 10 weight %.If the use amount of organic amine compound surpasses 15 weight %, exist the trend of chromatograph to the cohesive reduction of substrate.

And then, as the adjuvant beyond above-mentioned, for example can enumerate:

Dispersing aid as the blue pigment derivant of the blue or green derivant class of copper titanium or yellow uitramarine derivant etc.;

The filling agent of glass, aluminium oxide etc.;

The macromolecular compound of polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether, poly-(fluoroalkyl acrylate) etc.;

The surfactant of nonionic system, kation system, negative ion system etc.;

Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl trimethyl silane, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metering system oxygen propyl trimethoxy silicane, the adhesion promotor of 3-sulfydryl propyl trimethoxy silicane etc.;

2, the antioxidant of 2 '-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol etc.;

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

The anti-coagulants of sodium polyacrylate etc.;

1,1 '-azo (cyclohexane-1-nitrile), 2-phenylazo-4-methoxyl-2, the hot radical propellant of 4-methyl pentane nitrile etc. etc.

Solvent

Radiation sensitive compositions of the present invention be with above-mentioned (A)～(D) composition as must composition, according to circumstances contain above-mentioned adjuvant, be mixed with liquid composition after preferably cooperating solvent.

As above-mentioned solvent, so long as disperse or dissolve each composition that constitutes radiation sensitive compositions, and do not react with these compositions, having the volatile of appropriateness, just can suitably select to use.

As such solvent, for example for example can enumerate,

The alcohol of methyl alcohol, ethanol, benzylalcohol class;

The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary n-propyl ether, the diglycol monotertiary n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkane glycol monoalkyl ether of tripropylene glycol list ethyl ethers;

(gathering) alkylene glycols monoalky lether acetic acid esters of ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl n-propyl ether acetic acid esters, glycol monomethyl n-butyl ether acetic acid esters, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary n-propyl ether acetic acid esters, diglycol monotertiary n-butyl ether acetic acid esters, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, 3-methoxyl butylacetic acid ester class;

The ether of other of diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran derivatives;

The ketone of methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one class;

The lactic acid alkyl ester of methyl lactate, ethyl lactate class;

Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, 3-methyl-3-methoxyl butylacetic acid ester, n-butyl propionate, 3-methyl-3-methoxyl butyl propionic ester, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, the hydroxacetic acid ethyl ester, the ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, the ester of 2-ketobutyric acid ethyl ester class;

The aromatic hydrocarbon of toluene, dimethylbenzene;

N-Methyl pyrrolidone, N, the acid amides of dinethylformamide, N,N-dimethylacetamide class etc.

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

Above-mentioned solvent can separately or mix more than 2 kinds and use.

And then, with above-mentioned solvent simultaneously, also can and with the high boiling solvent of benzylisoeugenol, hexyl ether, acetonitrile and acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, acetic acid benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, glycol monomethyl phenyl ether acetic acid esters etc.

Above-mentioned high boiling solvent can separately or mix more than 2 kinds and use.

Use amount for solvent is not particularly limited, but from viewpoints such as the coating of the radiation sensitive compositions that obtains, storage stabilities, the summation concentration of removing each composition of said composition solvent, preferred 5～50 weight %, more preferably 10～40 weight %.

The formation method of dyed layer

Below, for using radiation sensitive compositions of the present invention, the method that forms dyed layer describes.

At first, on the surface of substrate, form light shield layer as required and go out to form the part of pixel with zoning, for example disperseed the liquid composition of radiation sensitive compositions of red pigment in coating on this substrate after, carry out the preroast evaporating solvent and form and film.Then, on filming, this, uses imaging liquid by after the photomask exposure, the video picture of preferred bases imaging liquid, and the unexposed portion of filming is removed in dissolving, then, forms the cell array of red pixel pattern with the orientation configuration of regulation by the back roasting.

Then, use has disperseed the liquid composition of each radiation sensitive compositions of green or blue pigment, carry out coating, preroast, exposure, video picture and the back roasting of each liquid composition same as described abovely, on same substrate, form green cell array and blue cell array successively, can obtain on substrate, disposing the colored filter of red, green and blue trichromatic cell array.But in the present invention, the order that forms cell array of all kinds is not subjected to above-mentioned restriction.

As when forming pixel, using substrate, for example can enumerate glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.

In addition, on these substrates, also can carry out the suitable pre-treatment of the medicine processing, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation etc. of silane coupling agent etc. as required in advance.

When the liquid composition with radiation sensitive compositions is coated on substrate, can adopt spraying process, rolling method, method of spin coating (revolving tumbling barrel process), slit die to be coated with the suitable rubbing method that method, rod are coated with method, ink jet method etc.Wherein, preferred especially method of spin coating, slit die are coated with method.

Coating thickness, as dried thickness, preferred 0.1～10 μ m, more preferably 0.2～8.0 μ m, preferred especially 0.2～6.0 μ m.

The radioactive ray that use during as exposure for example can use luminous ray, ultraviolet ray, far ultraviolet, electronics line, X line etc., but optimal wavelength are at the radioactive ray of 190～450nm.

The exposure of radioactive ray, preferred 10～10,000J/m ²About.

In addition, as above-mentioned alkali imaging liquid, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl-ammonium oxyhydroxide, choline, 1,8-diazonium two ring-[5.4.0]-7-undecylenes, 1, the aqueous solution of 5-diazonium two ring-[4.3.0]-5-nonenes etc.

In above-mentioned alkali imaging liquid, also can add the water-miscible organic solvent of methyl alcohol, ethanol etc. or surfactant etc. in right amount.

As the video picture facture, can use spray visualization method, spray-on process, dipping visualization method, stir hydrorrhea visualization method etc.The video picture condition is preferably at normal temperatures about 5～300 seconds.In addition, after the video picture of alkali imaging liquid, wash usually.

In addition, the formation of black matrix" is also carried out in the same manner with the method that forms above-mentioned cell array.

Colored filter

Colored filter of the present invention is to have a dyed layer of being made up of above-mentioned pixel that forms and/or black matrix", is extremely useful for the color liquid crystal display arrangement of for example transmission-type or reflection-type, color picture tube etc.

LCDs

LCDs of the present invention possesses above-mentioned colored filter.

And then as 1 embodiment of LCDs of the present invention, the radiation sensitive compositions of the application of the invention forms above-mentioned dyed layer on thin film transistor (TFT) (TFT) base plate array, can make the LCDs with special good characteristic.

Radiation sensitive compositions of the present invention, as must composition being to contain above-mentioned (A)～(D) composition, if when more specifically enumerating preferred compositions, the mode of following (1)～(6).

(1) dyed layer forms and uses radiation sensitive compositions, and wherein (B) alkali soluble resin comprises carboxyl copolymer (I).

(2) dyed layer of above-mentioned (1) forms and to use radiation sensitive compositions, and wherein (C) multi-functional monomer is formed by a kind that is selected from the group that trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythrite six acrylate constitute at least.

(3) dyed layer of above-mentioned (1) or (2) forms and uses radiation sensitive compositions, and wherein (D) radioactivity-sensitive polymerization initiator contains 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone.

(4) dyed layer of above-mentioned (1), (2) or (3) forms and to use radiation sensitive compositions, wherein (D) radioactivity-sensitive polymerization initiator and then contain the di-imidazole compound and/or the acetophenone based compound.

(5) dyed layer of above-mentioned (4) forms and to use radiation sensitive compositions, wherein (D) radioactivity-sensitive polymerization initiator and then contain hydrogen donor more than a kind.

(6) dyed layer of above-mentioned (1), (2), (3), (4) or (5) forms and uses radiation sensitive compositions, and wherein (A) colorant contains organic pigment and/or carbon black.

In addition, preferred colored filter of the present invention is made up of the colored filter of following (7).

(7) colored filter, it is to have pixel and/or the black matrix" that the radiation sensitive compositions by above-mentioned (1), (2), (3), (4), (5) or (6) forms.

As above-mentioned, can suppress the pollution of radioactivity-sensitive polymerization initiator composition distillation with radiation sensitive compositions of the present invention to sintering furnace or photomask etc., do not produce impurity in the liquid, and the edge at pixel pattern and black matrix pattern does not produce loose colour, and can form no recessed good pixel pattern and black matrix pattern.

Therefore, radiation sensitive compositions of the present invention extremely is applicable to based on the various colored filters of the chromatic liquid crystal screen colored filter of electronics industry and the manufacturing of LCDs.

Embodiment

Below, by embodiment, further specifically describe embodiments of the present invention.But the present invention is not subjected to the restriction of following embodiment.

Synthesis example 1

In the flask that cooling tube, stirring machine are housed, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 1 weight portion and propylene glycol monomethyl ether 200 weight portions, then, add methacrylic acid 15 weight portions, styrene 15 weight portions, benzyl methacrylate 35 weight portions, glycerin monomethyl acrylic ester 10 weight portions, N-phenylmaleimide 25 weight portions and chain-transferring agent α-Jia Jibenyixierjuwu 2.5 weight portions, behind the nitrogen replacement, slowly stir, the reaction solution temperature is raised to 80 ℃, keeps this temperature to carry out 3 hours polymerization.Then, the temperature of reaction solution is raised to 100 ℃, adds 2, two (2, the 4-methyl pentane nitrile) 0.5 weight portions of 2 '-azo, and then polymerization 1 hour obtains the solution (Gu shape branch concentration=33.0 weight %) of (B) alkali soluble resin.

Mw=17 that should (B) alkali soluble resin, 000, Mn=8,000.Should (B) alkali soluble resin conduct " resin (B-1) ".

Synthesis example 2

In the flask that cooling tube, stirring machine are housed, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 1 weight portion and propylene glycol monomethyl ether 200 weight portions, then, add methacrylic acid 15 weight portions, styrene 15 weight portions, benzyl methacrylate 30 weight portions, glycerin monomethyl acrylic ester 15 weight portions, N-phenylmaleimide 25 weight portions and chain-transferring agent α-Jia Jibenyixierjuwu 2.5 weight portions, behind the nitrogen replacement, slowly stir, the reaction solution temperature is raised to 80 ℃, keeps this temperature to carry out 3 hours polymerization.Then, the temperature of reaction solution is raised to 100 ℃, adds 2, two (2, the 4-methyl pentane nitrile) 0.5 weight portions of 2 '-azo, and then polymerization 1 hour obtains the solution (Gu shape branch concentration=32.9 weight %) of (B) alkali soluble resin.

Mw=19 that should (B) alkali soluble resin, 000, Mn=9,000.Should (B) alkali soluble resin conduct " resin (B-2) ".

Synthesis example 3

In the flask that cooling tube, stirring machine are housed, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 1 weight portion and propylene glycol monomethyl ether 200 weight portions, then, add methacrylic acid 15 weight portions, styrene 15 weight portions, benzyl methacrylate 30 weight portions, glycerin monomethyl acrylic ester 10 weight portions, N-phenylmaleimide 30 weight portions and chain-transferring agent α-Jia Jibenyixierjuwu 2.5 weight portions, behind the nitrogen replacement, slowly stir, the reaction solution temperature is raised to 80 ℃, keeps this temperature to carry out 3 hours polymerization.Then, the temperature of reaction solution is raised to 100 ℃, adds 2, two (2, the 4-methyl pentane nitrile) 0.5 weight portions of 2 '-azo, and then polymerization 1 hour obtains the solution (Gu shape branch concentration=33.2 weight %) of (B) alkali soluble resin.

Mw=15 that should (B) alkali soluble resin, 000, Mn=7,000.Should (B) alkali soluble resin conduct " resin (B-3) ".

Synthesis example 4

Cooling tube is being housed, in the flask of stirring machine, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 3 weight portions and propylene glycol monomethyl ether 200 weight portions, then, add methacrylic acid 15 weight portions, acenaphthylene 30 weight portions, benzyl methacrylate 35 weight portions, 2-hydroxyethyl meth acrylate 10 weight portions, ω-carboxyl polycaprolactone monomethacrylates 10 weight portions and chain-transferring agent α-Jia Jibenyixierjuwu 5 weight portions, behind the nitrogen replacement, slowly stir, the reaction solution temperature is raised to 80 ℃, keeps this temperature to carry out 3 hours polymerization.Then, the temperature of reaction solution is raised to 100 ℃, adds 2, two (2, the 4-methyl pentane nitrile) 0.5 weight portions of 2 '-azo, and then polymerization 1 hour obtains the solution (Gu shape branch concentration=31.0 weight %) of (B) alkali soluble resin.

Mw=10 that should (B) alkali soluble resin, 000, Mn=6,000.Should (B) alkali soluble resin conduct " resin (B-4) ".

Embodiment 1

Mix following composition, promptly mix the C.I. paratonere 254 of conduct (A) colorant and 80/20 (weight ratio) potpourri, 85 weight portions of C.I. paratonere 177, resin (B-1) 70 weight portions of conduct (B) alkali soluble resin, dipentaerythritol six acrylate 80 weight portions of the multi-functional monomer of conduct (C), 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone (trade name IRGACURE 379, the CIBA SPECIALTY CHEMICALS corporate system of conduct (D) radioactivity-sensitive polymerization initiator.Below identical.) 50 weight portions and as the 3-ethoxyl ethyl propionate of solvent and 70/30 (weight ratio) potpourri, 1,000 weight portion of propylene glycol monomethyl ether, the fluid composition (R1) of preparation radiation sensitive compositions.

(formation of colored filter)

With fluid composition (R1), formed the SiO that prevents the sodion stripping from the teeth outwards ₂On the alkali glass substrate of film, after the coating of use spin coater, preroast is 2 minutes on 90 ℃ hot plate.Form filming of thickness 1.7 μ m.

Then, behind this substrate cool to room temperature, use high-pressure mercury-vapor lamp,, use 5000J/m with the ultraviolet ray of each wavelength of containing 365nm, 405nm and 436nm by photomask (30 microns of gap widths) ²Exposure exposure.Then, substrate is immersed in 23 ℃ 0.04 weight % potassium hydroxide aqueous solution 1 minute, after the video picture,, air-dry with the ultrapure water washing.Then in 220 ℃ purification baking oven, carry out 30 minutes back roasting, on substrate, form the cell array that the banded pixel by redness constitutes.

The evaluation of video picture

During with the observation by light microscope cell array, on the substrate of unexposed portion, do not see the remnants of video picture, and do not see loose colour and disappearance at the edge of pixel pattern.In addition, the residual film ratio of cell array is 80%, for well, when observing the section of pixel pattern with scanning electron microscope (SEM), does not see recessed.

The evaluation of sublimability

Fluid composition (R1) is coated on back drying on the substrate, forms filming of 1.7 μ m.Then, film for this, use normal octane (proportion=0.701 as standard substance, injection rate IR=0.02 microlitre), at cleaning condition is under 100 ℃/10 minutes, use JHS-100A (trade name as head-space sampler, Japan's analytical industry (strain) system), as the gas chromatography/mass spectrometry analytical equipment, use JEOLJMS-AX505W type mass spectrophotometry meter (trade name, Japan's analytical industry (strain) system), carry out headspace gas chromatography/mass spectrophotometry, obtain peak area A from (D) radioactivity-sensitive polymerization initiator composition, by following calculating formula, calculate the volatile quantity that is converted into normal octane, volatile quantity is 0 μ g.

(being converted into the calculating formula of the volatile quantity of normal octane)

Volatile quantity (μ g)=A * (amount of normal octane) (μ g)/(peak area of normal octane)

The evaluation of impurity in the liquid

Maintenance is after 7 days down at 5 ℃ with fluid composition (R1), and whether visual observations (D) radioactivity-sensitive polymerization initiator composition exists recrystallization compound.In addition, with the temperature of the fluid composition (R1) after preserving when 5 ℃ are brought up to 23 ℃, use particle detector (trade name KS-28B in the light scattering formula liquid, リ オ Application (strain) system), be determined in 1 milliliter of fluid composition (R1) not dissolving again and during the number of the solid content (impurity in the liquid) of the remaining above size of 0.5 μ m, do not see solid content.

Embodiment 2

Use 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 20 weight portions, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (trade name IRGACURE 907, CIBASPECIALTY CHEMICALS corporate system as (D) radioactivity-sensitive polymerization initiator.Below identical.) 20 weight portions and be 4,4 ' of hydrogen donor-two (diethylamine) benzophenone 4 weight portions as amine, in addition, other and embodiment 1 prepare the fluid composition (R2) of radiation sensitive compositions in the same manner.

Then, replace the fluid composition (R1), on substrate, form the cell array that the striated pixel by redness constitutes in the same manner, estimate with embodiment 1 except using fluid composition (R2).

Its result does not see the remnants of video picture on the substrate of unexposed portion, and does not see loose colour and disappearance at the edge of pixel.In addition, the residual film ratio of cell array is 85%, for well.And when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM).In addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Comparative example 1

Except use 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions as the radioactivity-sensitive polymerization initiator.Prepare the fluid composition (r1) of radiation sensitive compositions in the same manner with embodiment 1.

Then, replace the fluid composition (R1) except using fluid composition (r1), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by redness constitutes, estimate.

Its result, on the substrate of unexposed portion, do not see the remnants of video picture, the residual film ratio of cell array is 79%, and when observing the section of pixel pattern,, perhaps do not see the impurity in the liquid though do not see recessedly with scanning electron microscope (SEM), but, see loose colour and disappearance at the edge of pixel pattern, in addition, the volatile quantity of filming is 1.0 μ g.

Embodiment 3

Mix following composition, promptly mix as the C.I. pigment green 36 of (A) colorant and 60/40 (weight ratio) potpourri, 95 weight portions of C.I. pigment yellow 150, resin (B-2) 70 weight portions as (B) alkali soluble resin, dipentaerythritol six acrylate 80 weight portions as (C) multi-functional monomer, as 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions of (D) radioactivity-sensitive polymerization initiator and as malonic acid 1 weight portion of adjuvant and as the 3-methoxyl butylacetic acid ester of solvent and 50/50 (weight ratio) potpourri, 900 weight portions of propylene glycol monomethyl ether, be mixed with the fluid composition (G1) of radiation sensitive compositions.

Then, replace the fluid composition (R1) except using fluid composition (G1), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by green constitutes, estimate.

Its result does not see the remnants of video picture on the substrate of unexposed portion, and does not see loose colour and disappearance at the edge of pixel.In addition, the residual film ratio of cell array is 80%, for well.And when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM).In addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Embodiment 4

Use 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 20 weight portions, 2 as (D) radioactivity-sensitive initiating agent, 2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-di-imidazoles, 12 weight portions and be 4 of hydrogen donor as amine, 4 '-two (diethylamine) benzophenone 12 weight portions and be hydrogen donor 2-mercaptobenzothiazole 6 weight portions as mercaptan, in addition, other and embodiment 3 are mixed with the fluid composition (G2) of radiation sensitive compositions in the same manner.

Then, replace the fluid composition (R1) except using fluid composition (G2), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by green constitutes, estimate.

Its result does not see the remnants of video picture on the substrate of unexposed portion, and does not see loose colour and disappearance at the edge of pixel.In addition, the residual film ratio of cell array is 87%, for well.And when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM).In addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Comparative example 2

Except use 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions as the radioactivity-sensitive polymerization initiator.Prepare the fluid composition (g1) of radiation sensitive compositions in the same manner with embodiment 3.

Then, replace the fluid composition (R1) except using fluid composition (g1), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by green constitutes, estimate.

Its result, on the substrate of unexposed portion, do not see the remnants of video picture, the residual film ratio of cell array is 79%, and when observing the section of pixel pattern with scanning electron microscope (SEM), though do not see the impurity in recessed or the liquid,, see loose colour and disappearance at the edge of pixel pattern, the volatile quantity of filming in addition, is 1.0 μ g.

Embodiment 5

Mix following composition, promptly mix C.I. pigment blue 15: 6 and 95/5 (weight ratio) potpourri, 70 weight portions of C.I. pigment Violet 23 as (A) colorant, resin (B-3) 60 weight portions as (B) alkali soluble resin, dipentaerythritol six acrylate 90 weight portions as (C) multi-functional monomer, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions as (D) radioactivity-sensitive polymerization initiator, nonionic as adjuvant is surfactant A-a 60 (trade name, flower king (strain) system) 5 weight portions and as the 3-ethoxyl ethyl propionate of solvent and 60/40 (weight ratio) potpourri, 900 weight portions of propylene glycol monomethyl ether are mixed with the fluid composition (B1) of radiation sensitive compositions.

Then, replace the fluid composition (R1) except using fluid composition (B1), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by blueness constitutes, estimate.

Its result does not see the remnants of video picture on the substrate of unexposed portion, and does not see loose colour and disappearance at the edge of pixel.In addition, the residual film ratio of cell array is 85%, for well.And when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM).In addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Embodiment 6

Use 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 15 weight portions as (D) radioactivity-sensitive initiating agent, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-di-imidazoles, 6 weight portions, as amine is 4 of hydrogen donor, 4 '-two (diethylamine) benzophenone 9 weight portions, as mercaptan is hydrogen donor 2-mercaptobenzothiazole 3 weight portions and 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone 15 weight portions, in addition, other and embodiment 5 prepare the fluid composition (B2) of radiation sensitive compositions in the same manner.

Then, replace the fluid composition (R1) except using fluid composition (B2), with embodiment 1 in the same manner, on substrate, form the cell array that the striated pixel by blueness constitutes, estimate.

Its result does not see the remnants of video picture on the substrate of unexposed portion, and does not see loose colour and disappearance at the edge of pixel, and in addition, the residual film ratio of cell array is 90%, for well.And when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM).In addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Comparative example 3

Except use 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions as the radioactivity-sensitive polymerization initiator, prepare the fluid composition (b1) of radiation sensitive compositions in the same manner with embodiment 5.

Then, replace the fluid composition (R1), on substrate, form the cell array that the pixel by blueness constitutes in the same manner, estimate with embodiment except using fluid composition (b1).

Its result, on the substrate of unexposed portion, do not see video picture remnants, and, loose colour and disappearance are not seen in edge at pixel, and the residual film ratio of pixel ground array is 84%, 0 μ g on the volatile quantity of filming, in addition, though in liquid, do not see impurity, when observing the section of pixel pattern, seen recessed with scanning electron microscope (SEM).

Embodiment 7

Mix carbon black 250 weight portions (driving state's pigment (strain) system) as (A) colorant, (B-4) 75 weight portions as (B) alkali soluble resin, dipentaerythritol six acrylate 75 weight portions as (C) multi-functional monomer, as 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 50 weight portions of (D) radiation polymerization initiator and as the propylene glycol monomethyl ether of solvent and 50/50 (weight ratio) potpourri 1 of cyclohexanone, 000 weight portion is mixed with the fluid composition (BKI) of radiation sensitive compositions.

Then, replace the fluid composition (R1), on substrate, form the cell array that the pixel by black lines constitutes in the same manner, estimate with embodiment 1 except using fluid composition (BKI).

Its result does not see the remnants of video picture on the substrate of unexposed portion, and, do not see loose colour and disappearance at the edge of pixel pattern.The residual film ratio of cell array is 80% for good in addition, when observing the pixel pattern section with scanning electron microscope (SEM), does not see recessed.In addition, the volatile quantity of filming is 0 μ g, does not see impurity in liquid.And the cohesive of pixel and substrate is also good.

Embodiment 8

Mix carbon black 250 weight portions (driving state's pigment (strain) system) as (A) colorant, (B-4) 75 weight portions as (B) alkali soluble resin, dipentaerythritol six acrylate 75 weight portions as (C) multi-functional monomer, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone 20 weight portions and 1-[9-ethyl-6-(2-toluyl)-9.H.-carbazole-3-yl as (D) radiation polymerization initiator] ethane-1-ketoxime-O-acetic acid esters (trade name CGI-242, CIBA SPECIALTYCHEMICALS society system) 20 weight portions and as the propylene glycol monomethyl ether of solvent and 50/50 (weight ratio) potpourri 1 of cyclohexanone, 000 weight portion is mixed with the fluid composition (BK2) of radiation sensitive compositions.

Then, replace the fluid composition (R1) except using fluid composition (BK2), the strip pixel that forms on substrate in the same manner by black with embodiment 1 constitutes the ground cell array, estimates.

Its result does not see the remnants of video picture on the substrate of unexposed portion, and, do not see loose colour and disappearance at the pixel pattern edge.In addition, the residual film ratio of cell array is 85% for good, when observing the section of pixel pattern with scanning electron microscope (SEM), does not see recessed.In addition, the volatile quantity of filming is 0 μ g, does not see impurity in liquid.And the cohesive of pixel and substrate is also good.

Comparative example 4

Except using 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone 30 weight portions, 2 as (D) radioactivity-sensitive polymerization initiator, 2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-di-imidazoles, 12 weight portions, be 4 of hydrogen donor as amine, 4 '-two (diethylamine) benzophenone 12 weight portions and be that other and embodiment 7 are mixed with the fluid composition (bk1) of radiation sensitive compositions in the same manner beyond 2-mercaptobenzothiazole 6 weight portions of hydrogen donor as mercaptan.

Then, replace the fluid composition (BK1), on substrate, form the cell array that the striated pixel by black constitutes in the same manner, estimate with embodiment 7 except using fluid composition (bk1).

Its result, on the substrate of unexposed portion, do not see the remnants of video picture, the residual film ratio of cell array is 83%, in addition, though the volatile quantity of filming is 0 μ g, see loose colour and disappearance at the edge of pixel pattern, when observing the section of pixel pattern with scanning electron microscope (SEM), see recessed, and, in liquid, see 5 impurity.

Embodiment 9

Except using beyond 70/30 (weight ratio) potpourri, 1,500 weight portion as the 3-ethoxyl ethyl propionate of solvent and propylene glycol monomethyl ether, other and embodiment 1 are mixed with the fluid composition (R3) of radiation sensitive compositions in the same manner.

Then, replace fluid composition (R1), replace spin coater is coated with the gap coating device except using fluid composition (R3), with embodiment 1 in the same manner on substrate formation estimate by the cell array that the striated pixel of redness constitutes.

Its result, on the substrate of unexposed portion, do not see the remnants of video picture, and loose colour and disappearance are not seen in the edge of pixel pattern, the residual film ratio of cell array is 85% in addition, be good, when observing the section of pixel pattern, do not see recessed with scanning electron microscope (SEM), in addition, the volatile quantity of filming is 0 μ g, and, in liquid, do not see impurity.

Claims (3)

1. radiation sensitive compositions, it is characterized in that, contain (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer or itself and simple function combination of compounds, and (D) with the compound of following formula (1) expression, and be used for the formation of dyed layer

In the formula (1), R ¹The alkyl of the straight chain shape of expression carbon number 1～12, a chain or ring-type; R ²And R ³Represent hydrogen atom independently of each other, the alkyl of the straight chain shape of carbon number 1～12, a chain or ring-type, perhaps benzyl; R ⁴, R ⁵, R ⁷And R ⁸Represent hydrogen atom independently of each other, halogen atom, the alkyl of the straight chain shape of carbon number 1～12, a chain or ring-type, the perhaps alkoxy of the straight chain shape of carbon number 1～4 or a chain; R ⁶The expression halogen atom, the alkyl of the straight chain shape of carbon number 1～12, a chain or ring-type, with hydroxyl and be selected from the carbon number 1～12 that substituting group in the group of being made up of the alkoxy of the straight chain shape of carbon number 1～4 or a chain replaced the straight chain shape, prop up the alkyl of chain or ring-type, the alkoxy of the straight chain shape of carbon number 1～4, chain is perhaps with hydroxyl and be selected from the straight chain shape of the carbon number 2～4 that substituting group in the group of being made up of the alkoxy of the straight chain shape of carbon number 1～4 or a chain replaced or prop up the alkoxy of chain.

2. colored filter, it has the dyed layer that is formed by the described radiation sensitive compositions of claim 1.

3. LCDs, it has the described colored filter of claim 2.