CN102213916A - Coloring composition, color filter and color liquid crystal display element - Google Patents

Abstract

The invention relates to a coloring composition, a color filter and a color liquid crystal display element. The coloring composition for the color filter is excellent in colority characteristic, alkali developability and storage stability. The coloring composition is characterized by comprising (A) a colorant containing a pigment; (B) a block copolymer containing a block A and a block B. The amine value of the block copolymer is 50 mg KOG / g to 80 mg KOG / g. The block A contains a repeated unit derived from an ethylenically unsaturated monomer with the mass percentages more than 60%. The block B contains a repeated unit derived from an alkylene glycol chain having ethylenically unsaturated monomer; (C) a solvent.

Description

Coloured composition, color filter and color liquid crystal display device

Technical field

The present invention relates to coloured composition, color filter and color liquid crystal display device.

Background technology

When using colored radiation-sensitive composition to make color filter, known following method: at the colored radiation-sensitive composition of coating pigment decentralized on the substrate and after carrying out drying, by desired pattern form dry coating is shone radioactive ray (hereinafter referred to as " exposure "), and develop, obtain each color pixel (patent documentation 1～2) thus.In addition, also know the method (patent documentation 3) of utilizing the optical polymerism composition that is dispersed with carbon black to form black matrix.And then the colored resin composition of also known use pigment-dispersing type obtains the method (patent documentation 4) of each color pixel by ink-jetting style.

But, in the field of the color filter that is used for liquid crystal display cells or solid-state imager, follow the requirement of high brightnessization and high-contrastization, the pigment of use has more and more micronized tendency.In order to realize the stable and good dispersiveness of so micronized pigment, known use spreading agent is effective.And, a kind of scheme has been proposed in the patent documentation 5, for a spot of addition effectively with highly micronized pigment dispersing, use the amine value as the segmented copolymer of 80mgKOH/g～150mgKOH/g as spreading agent.

The prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 2-144502 communique

Patent documentation 2: Japanese kokai publication hei 3-53201 communique

Patent documentation 3: Japanese kokai publication hei 6-35188 communique

Patent documentation 4: TOHKEMY 2000-310706 communique

Patent documentation 5: TOHKEMY 2009-25813 communique

Summary of the invention

But when using the high segmented copolymer of the amine value that proposes in the patent documentation 5 as spreading agent, the alkali-developable variation of coloured composition is so bring obstacle for the batch process of color filter.When particularly making up pigment and dyestuff and using as colorant, it is remarkable that the deterioration of alkali-developable becomes.Therefore, strong hope is developed: the realization high-contrastization in recent years and the requirement and the also excellent color composition for color filter of alkali-developable of high brightnessization.

Therefore, problem of the present invention is to provide the coloured composition of colorimetric properties, alkali-developable and excellent storage stability.And then problem of the present invention is to provide color filter that possesses the dyed layer that is formed by above-mentioned coloured composition and the color liquid crystal display device that possesses this color filter.

In view of described truth, the inventor furthers investigate, and found that, by using specific segmented copolymer, can solve above-mentioned problem, has finished the present invention.

That is, the invention provides a kind of coloured composition, it is characterized in that, contain: the colorant that (A) comprises pigment; (B) comprise A block and B block, the amine value is the segmented copolymer (below be also referred to as " (B) multipolymer ") of the above and not enough 80mgKOH/g of 50mgKOH/g, described A block has the above repetitive (1) with following formula (1) expression of 60 quality %, and described B block has the repetitive with following formula (2) expression; (C) solvent.

(in the formula (1), X represents divalent linking group, R ¹Expression hydrogen atom or methyl, R ²And R ³Represent that independently of each other hydrogen atom maybe can have the alkyl of substituent chain or ring-type, R ²And R ³Can mutually combine and form ring texture.)

(in the formula (2), R ⁴Represent that independently of each other carbon number is 2～4 alkylidene, R ⁵The expression carbon number is 1～6 alkyl, R ⁶Expression hydrogen atom or methyl, n represents 1～150 integer.)

In addition, the invention provides color filter that possesses the dyed layer that uses this coloured composition and form and the color liquid crystal display device that possesses this color filter.Herein, " dyed layer " means each color pixel that uses, black matrix, black separator etc. in color filter.

Use coloured composition of the present invention, can access the color filter of each color pixel with colorimetric properties excellence.In addition, coloured composition of the present invention is also excellent aspect alkali-developable and storage stability.

Therefore, coloured composition of the present invention can extremely be suitable for making with the color separation color filter of color liquid crystal display device color filter, solid-state imager, organic EL display element color filter, the various color filters of Electronic Paper headed by the color filter.And then coloured composition of the present invention also can be suitable as electrophoresis coloured composition used in electrophoretic display device.

Embodiment

Below, describe the present invention in detail.

Coloured composition

Below, describe for the constituent of coloured composition of the present invention.

-(A) colorant-

Coloured composition of the present invention contains pigment as (A) colorant.As pigment, be not particularly limited, can be in organic pigment, the inorganic pigment any.Among the present invention, pigment can use separately or mix more than 2 kinds and use.Certainly, also organic pigment and inorganic pigment can be mixed use.

As above-mentioned organic pigment, can enumerate for example anthraquione pigmentss, amino anthraquinones series pigments, quinacridone pigment, quinacridone quinone pigment, diketopyrrolopyrrolecocrystals series pigments, perylene pigment, purple cyclic ketones (ペ リ ノ Application) series pigments, anthrone buttress anthrone series pigments, benzimidazolone series pigments, disazo condensation system pigment, azo pigment, thioindigo series pigments, pyranthrone series pigments, two Piperazine series pigments, Kui phthalein ketone series pigments, isoindoline series pigments, phthualocyanine pigment etc.

In addition, as above-mentioned inorganic pigment, for example can enumerate titanium dioxide, barium sulphate, lime carbonate, zinc paste, lead sulfate, chrome yellow, zinc yellow, colcother (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, black, the synthetic iron oxide black of titanium, carbon black etc.

(B) multipolymer can the stable and dispersion well with the particularly phthualocyanine pigment in these pigment.In the phthualocyanine pigment,, can enumerate for example CuPc as blue pigment.More particularly, can enumerate at pigment index (C.I.; The Society 0f Dyers and Colourists society distribution) classifies as the compound of pigment in, promptly has a compound of following such pigment index (C.I.) name.

C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6.

(B) to be particularly suitable for disperseing these phthalocyanines be C.I. pigment blue 15 in the blue pigment to multipolymer: 6.

In addition, in the phthualocyanine pigment, as viridine green, can enumerate the metal phthalocyanine of for example chlorination and/or bromination, more specifically can enumerate CuPc, Phthalocyanine Zinc, magnesium phthalocyanine, aluminum phthalocyanine, phthalocyanine titanium, phthalocyanine vanadium, manganese phthalocyanine, FePC, phthalocyanine cobalt, phthalocyanine nickel, phthalocyanine tin, phthalocyanine germanium etc.

(B) to be suitable for disperseing these phthalocyanines be chlorination CuPc, chlorination bromination CuPc, bromination CuPc, chlorination bromination Phthalocyanine Zinc, bromination Phthalocyanine Zinc in the viridine green to multipolymer, particularly chlorination bromination Phthalocyanine Zinc.Chlorination bromination Phthalocyanine Zinc is preferably the structure of following formula (I) expression.

(in the formula (I), Y represents hydrogen atom, chlorine atom or bromine atoms independently of each other, and 10～15 is that bromine atoms, 1～6 are the chlorine atom among whole Y.)

Need to prove that in pigment index (C.I.) name, the chlorination CuPc is the pigment that classifies as the C.I. pigment Green 7, chlorination bromination CuPc is the pigment that classifies as the C.I. pigment green 36, and chlorination bromination Phthalocyanine Zinc is the pigment that classifies as C.I. naphthol green 58.

Among the present invention, also can pass through recrystallization method, reprecipitation method, solvent cleaning method, sublimed method, vaccum heating method or their combination the refining back of pigment is used.In addition, pigment also can be as required uses after with its particle surface modification with resin.As resin, can enumerate vector resin that TOHKEMY 2001-108817 communique for example put down in writing or the commercially available various resins that are used for pigment dispersing with the particle surface modification of pigment.As the resin-coated method of carbon blacksurface, the method that can adopt for example Japanese kokai publication hei 9-71733 communique, Japanese kokai publication hei 9-95625 communique, Japanese kokai publication hei 9-124969 communique etc. to be put down in writing.In addition, organic pigment is preferably handled and will be used after the primary particle miniaturization by so-called salt mill.As the method that salt mill is handled, for example can adopt disclosed method in the Japanese kokai publication hei 08-179111 communique.

, in the color composition for color filter,, can realize high brightnessization and the high-contrastization that to reach with pigment separately by using dyestuff as colorant.But, when using dyestuff as colorant, the remarkable variation of the alkali-developable of coloured composition.In the coloured composition of the present invention,,, also can access the good coloured composition of alkali-developable even combination pigment and dyestuff use as colorant by using (B) multipolymer as pigment dispersing agent.As dyestuff, can enumerate the compound that for example has following such pigment index (C.I.) name.

C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. direct yellow 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. mordant rouge 7, C.I. mordant yellow 5, C.I. 7 based dyes such as azo such as grade are deceived in mordant dyeing;

C.I. anthraquinone based dyes such as Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60;

C.I. vat blue (パ Star De Block Le one) 5 based dyes such as phthalocyanine such as grade;

C.I. quinone imines based dye such as alkali blue 3, C.I. alkali blue 9;

C.I. quinoline based dyes such as solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64;

C.I. nitro based dyes such as Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42;

Disperse yellow 201 based dyes such as methine such as grade.

Among the present invention, when using dyestuff as colorant, dyestuff can use separately or mix more than 2 kinds and use.

Consider that from the aspect of the black matrix of the pixel that forms brightness height and excitation excellence or light-proofness excellence (A) colorant contains proportional to be 5～70 quality % usually, to be preferably 5～60 quality % in the solid constituent of coloured composition.At this, solid constituent is meant the composition beyond the aftermentioned solvent.

-(B) multipolymer-

Among the present invention, (B) multipolymer is the composition as pigment dispersing agent performance function, be comprise A block and B block, the amine value is the segmented copolymer of the above and not enough 80mgKOH/g of 50mgKOH/g, wherein the A block has the above repetitive (1) with above-mentioned formula (1) expression of 60 quality %, and the B block has the repetitive (2) with above-mentioned formula (2) expression.Need to prove, " having the above repetitives of 60 quality % (1) " be meant repetitive (1) in the A block to contain proportional be more than the 60 quality %.

In the above-mentioned formula (1), as divalent linking group X, can enumerate for example methylene, carbon number and be 2～10 alkylidene, arlydene ,-CONH-R ⁷-(*) base ,-COO-R ⁸-(*) base (wherein, R ⁷And R ⁸Represent that independently of each other methylene, carbon number are that 2～10 alkylidene or carbon number are 2～10 alkylidene oxyalkylene (ア Le キ レ Application オ キ シ ア Le キ レ Application base), (*) the binding site (Knot that combines with N of expression closes hand)) etc.Wherein, as X, preferred-COO-R ⁸-Ji is as R ⁸, preferred carbon number is 2～6 alkylidene.

In addition, above-mentioned formula (1)-NR ²R ³In, R ²And R ³Representing that independently of each other hydrogen atom maybe can have the alkyl of substituent chain or ring-type, is 1～4 alkyl as the preferred carbon number of alkyl, special preferable methyl, ethyl, propyl group, butyl.In the substituting group on the alkyl,, can enumerate halogen atom, alkoxy, benzoyl etc. as the substituting group on the chain alkyl.In addition, as the substituting group on the cyclic hydrocarbon group, can enumerate alkyl, halogen atom, alkoxy of chain etc.Need to prove R ²And R ³Represented chain alkyl comprises any alkyl of a straight chain shape and a chain.

In addition, R ²And R ³Also can mutually combine and form ring texture,, can enumerate for example nitrogen heterocyclic ring monocycle or 2 condensed ring that these monocycle condensations form of 5～7 yuan of rings as ring texture.Nitrogen heterocyclic ring does not preferably have aromaticity, more preferably saturated rings.Specifically can enumerate for example following example.

These ring texturees also can further have substituting group.

In the above-mentioned formula (2), as R ⁴, preferred ethylidene, methyl ethylidene.In addition, as R ⁵, preferable methyl, ethyl, propyl group, butyl.In addition, the integer of n preferred 1～20, more preferably 1～10 integer, preferred especially 1～5 integer.

(B) the A block of multipolymer can have above-mentioned repetitive (1) and the repetitive except that repetitive (1).As the example of such repetitive, can enumerate derive from have pyridine radicals, the ethylenically unsaturated monomers of nitrogen heterocycle such as imidazole radicals, pyrazolyl, triazolyl, tetrazole radical, imidazolinyl, tetrahydro-pyrimidine base; Repetitive etc. with ethylenically unsaturated monomers of quaternary ammonium base.

(B) the B block of multipolymer preferably has the repetitive (3) of above-mentioned repetitive (2) and following formula (3) expression.

(in the formula (3), R ⁹Expression can have substituent chain or ring-type alkyl, can have substituent aryl, maybe can have substituent aralkyl, R ¹⁰Expression hydrogen atom or methyl.)

In the above-mentioned formula (3), as R ⁹, preferred carbon number is that 1～8 chain-like alkyl, carbon number are that 6～14 aryl, carbon number are 7～16 aralkyl, special preferable methyl, ethyl, propyl group, butyl, 2-ethylhexyl, phenyl, benzyl, phenethyl.In addition, as R ⁹Substituting group on the represented alkyl can be enumerated halogen atom, alkoxy etc.In addition, as the substituting group on the aryl or aralkyl, can enumerate alkyl, halogen atom, alkoxy of chain etc.In addition, R ⁹Represented chain-like alkyl comprises any alkyl of a straight chain shape and a chain.

(B) the B block of multipolymer also can have other repetitives except that above-mentioned repetitive (2) and repetitive (3).As the example of such repetitive, can enumerate styrenic monomers such as deriving from styrene; (methyl) acrylamide monomers such as (methyl) acrylamide; Vinyl acetate; The repetitive of monomers such as vinyl cyanide.

(B) structure of multipolymer so long as comprise has the A block of the above repetitive (1) of 60 quality % and has the segmented copolymer of the B block of repetitive (2), just is not particularly limited, but is preferably A-B segmented copolymer or B-A-B segmented copolymer.

(B) in 1 of multipolymer A block, also can contain repetitive more than 2 kinds (1).At this moment, the repetitive more than 2 kinds (1) can be contained in the A block in arbitrary mode of random copolymerization, block copolymerization.In addition, the repetitive (1) in the A block contain proportional be preferably 75 quality % above, be preferably more than the 90 quality % especially.

(B) in 1 of multipolymer B block, also can contain repetitive more than 2 kinds (2).At this moment, the repetitive more than 2 kinds (2) can be contained in the B block in arbitrary mode of random copolymerization, block copolymerization.In addition, when having repetitive (3) and other repetitive in the B block, these repetitives can contain more than 2 kinds in 1 B block respectively.At this moment, each repetitive can be contained in the B block in arbitrary mode of random copolymerization, block copolymerization.Repetitive (2), repetitive (3) and other repetitive also can be contained in the B block in arbitrary mode of random copolymerization, block copolymerization.

When the B block had repetitive (2) and repetitive (3) both sides, the copolymerization ratio (mass ratio) of the repetitive in the B block (2)/repetitive (3) was preferably 1/99～50/50, more preferably 1/99～30/70.

(B) the amine value of multipolymer is the above and not enough 80mgKOH/g of 50mgKOH/g, but is preferably 52mgKOH/g～79mgKOH/g.Herein, the alkali number in amine value representation and the every 1g spreading agent solid constituent is the mg number of the KOH of equivalent.

In addition, (B) in the multipolymer, repetitive (2) contain proportional 1～30 quality %, 1～25 quality % more preferably of in whole repetitives, being preferably.

By (B) multipolymer is set at such mode, can access the coloured composition of dispersed and alkali-developable excellence.

(B) molecular weight of multipolymer is with gel permeation chromatography (GPC, eluting solvent: the DMF) weight-average molecular weight that is scaled polymethylmethacrylate of Ce Dinging (below be also referred to as " Mw "), be preferably 1,000～30,000, be preferably 5 especially, 000～15,000.In addition, (B) Mw of multipolymer with (eluting solvent: DMF) ratio (Mw/Mn) of the number-average molecular weight that is scaled polymethylmethacrylate of Ce Dinging (hereinafter referred to as " Mn ") is preferably 1.0～2.0, more preferably 1.0～1.8 with GPC.By (B) multipolymer is set at such mode, can access the coloured composition of dispersed and alkali-developable excellence.

(B) multipolymer can for example, can carry out living polymerization and make by the known method manufacturing by the monomer that above-mentioned each repetitive will be provided.As the living polymerization method, can adopt Japanese kokai publication hei 9-62002 communique, TOHKEMY 2002-31713 communique, P.Lutz, P.Masson et al, Polym.Bull., 12,79 (1984); B.C.Anderson, G.D.Andrews et al, Macromolecules, 14,1601 (1981); K.Hatada, K.Ute, et al, Polym.J., 17,977 (1985); K.Hatada, K.Ute, et al, Polym.J., 18,1037 (1986), the great Yi ， of right hand field Tagayasu Den one, Process Technology of Polymer, 36,366 (1987); East Village is quick to be prolonged, pool this light man, macromolecule collection of thesis, 46,189 (1989); M.Kuroki, T.Aida, J.Am.Chem.Soc., 109,4737 (1987); Phase Tian Zhuosan, aboveground auspicious flat, Synthetic Organic Chemistry, 43,300 (1985); D.Y.Sogoh, W.R.Hertler et al, Macromolecules, the known method of record in 20,1473 (1987) etc.

As the monomer that repetitive (1) is provided, for example can enumerate (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) acrylic acid dimethylamino propyl ester, (methyl) acrylic acid lignocaine propyl ester etc.

As the monomer that repetitive (2) are provided, can enumerate for example polyglycol (n=1～5) methyl ethers (methyl) acrylate, polyglycol (n=1～5) ether (methyl) acrylate, polyglycol (n=1～5) propyl ether (methyl) acrylate, polypropylene glycol (n=1～5) methyl ethers (methyl) acrylate, polypropylene glycol (n=1～5) ether (methyl) acrylate, polypropylene glycol (n=1～5) propyl ether (methyl) acrylate etc.

As the monomer that repetitive (3) are provided, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tetrahydro-dicyclopentadiene ester (dicyclopentanyl (meth) acrylate), (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid phenyl chlorocarbonate etc.

In addition; as the monomer that copolymerization can take place with the monomer that repetitive (1) is provided in the A block, for example can enumerate the monomer that (methyl) acrylamido oxypropyl trimethyl ammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) acrylyl oxy-ethyl triethyl ammonium chloride, (methyl) acrylyl oxy-ethyl (4-benzoyl benzyl) dimethyl ammonium bromide, (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, (methyl) acrylyl oxy-ethyl benzyl diethyl ammonium chloride and following formula are represented.

(monomer 1) (monomer 2)

(monomer 3) (monomer 4)

(monomer 5)

(monomer 6)

(monomer 7) (monomer 8)

(monomer 9) (monomer 10)

(monomer 11) (monomer 12)

(monomer 13) (monomer 14)

(B) multipolymer can use separately or mix more than 2 kinds and use.(B) content of multipolymer with respect to 100 mass parts pigment be generally 1～100 mass parts, be preferably 5～70 mass parts, 10～50 mass parts more preferably.When (B) content of multipolymer was too much, development might be impaired.

Among the present invention,, also can further contain known spreading agent in order to improve dispersiveness.As known spreading agent, for example can enumerating, carbamate is that spreading agent, polyethyleneimine are that spreading agent, polyoxyethylene alkyl ether are that spreading agent, polyoxyethylene alkyl phenyl ether are that spreading agent, polyethylene glycol di are that spreading agent, sorbitan fatty acid ester are that spreading agent, fatty acid modified polyester are spreading agent, acrylic acid series spreading agent, pigment derivative etc.

As the concrete example of such spreading agent, can enumerate commodity EFKA (manufacturing of EFKAChemicals BV (EFKA) society) by name, Disperbyk (manufacturing of Bi Ke chemistry (BYK) society), Supreme Being Si Balong (nanmu originally changes into Co., Ltd. and makes), Solsperse (manufacturing of Lubrizol society), KP (Shin-Etsu Chemial Co., Ltd's manufacturing), Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacturing), EFTOP (manufacturing of Tochem Products society), MEGAFAC (Dainippon Ink. ﹠ Chemicals Inc's manufacturing), FLUORAD (manufacturing of Sumitomo 3M Co., Ltd.), ASAHI GUARD, SURFLON (above make for Asahi Glass Co., Ltd) etc.In addition, as the concrete example of pigment derivative, can enumerate the sulfonic acid of CuPc, diketopyrrolopyrrolecocrystals, Kui phthalein ketone etc.

-(C) solvent-

Coloured composition of the present invention is prepared as follows usually: at first, colorant other compositions with (B) multipolymer and interpolation as required in (C) solvent that will comprise pigment use for example pulverizing such as ball mill, roller mill and mixing, disperse, and make dispersible pigment dispersion.Then, when giving curable and alkali-developable to coloured composition of the present invention, (C) solvent and the adjuvant that add (D)～(F) composition described later and further append as required in this dispersible pigment dispersion mix.As (C) solvent, so long as will constitute composition (A) composition of coloured composition and (B) composition, other compositions described later disperse or dissolve, and do not react with these compositions, have volatile solvent of appropriateness, just can suit to select use.

As such solvent, for example can enumerate:

Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, the diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, acetate 3-methoxyl butyl ester, acetate-3-methyl-(gathering) alkylene glycol monoalkyl ethers acetate esters such as 3-methoxyl butyl ester;

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

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

Propylene-glycol diacetate, 1,3 butylene glycol diacetate esters, 1, diacetate esters classes such as 6-hexanediol diacetate esters;

3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-alkoxyl carboxylate classes such as 3-methoxyl butyl propionic ester;

Other ester class such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid ethyl ester;

Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;

Lactic acid alkyl ester such as methyl lactate, ethyl lactate class;

(ring) alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutyl alcohol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol;

Ketols such as diacetone alcohol;

N, acid amides such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or lactams etc.

Among the present invention, solvent can use separately or mix more than 2 kinds and use.

In these solvents, in modulation during above-mentioned dispersible pigment dispersion, the preferred use is selected from least a in (gathering) alkylene glycol monoalkyl ethers class, (gathering) alkylene glycol monoalkyl ethers acetate esters, diacetate esters class and the alkoxyl carboxylate class.Its contain proportionally in whole solvents that dispersible pigment dispersion contained, be preferably more than the 80 quality %, more preferably more than the 90 quality %.

In addition, (gathering) alkylene glycol monoalkyl ethers class, (gathering) alkylene glycol monoalkyl ethers acetate esters, in diacetate esters class and the alkoxyl carboxylate class, preferred especially propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl butyl ester, the dipropylene glycol monomethyl ether acetic acid esters, propylene-glycol diacetate, 1,3-butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate.

Content to solvent is not particularly limited, but preferably the total concentration of removing each composition after desolvating of this coloured composition becomes the amount of 5～50 quality %, and preferred especially described total concentration becomes the amount of 10～40 quality %.By being set at such mode, can access dispersiveness, stability, coloured composition that coating is good.

-(D) crosslinking chemical-

Can make coloured composition of the present invention contain (D) crosslinking chemical.Thus, can give coloured composition Thermocurable or radiation-curable.Herein, (D) crosslinking chemical is meant the compound with the polymerizable groups more than 2.As polymerizable groups, can enumerate for example ethylenic unsaturated group, epoxy ethyl, oxa-cyclobutyl, N-alkoxyl-methyl amino etc.Among the present invention,, preferably have the compound of (methyl) acryloyl group more than 2 or have the compound of 2 above N-alkoxyl-methyl amino as (D) crosslinking chemical.

As above-mentioned concrete example, can enumerate multifunctional (methyl) acrylate that aliphatic polyhydroxy compound is obtained with the reaction of (methyl) acrylic acid with compound of (methyl) acryloyl group more than 2; multifunctional (methyl) acrylate through caprolactone modification; multifunctional (methyl) acrylate through the alkylene oxide modification; polyfunctional carbamate (methyl) acrylate that makes (methyl) acrylate with hydroxyl and polyfunctional isocyanate reaction and obtain; multifunctional (methyl) acrylate that makes (methyl) acrylate with hydroxyl and anhydride reaction and obtain etc. with carboxyl.

Herein, as above-mentioned aliphatic polyhydroxy compound, can enumerate for example ethylene glycol, propylene glycol, polyglycol, 2 yuan such aliphatic polyhydroxy compound of polypropylene glycol, glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol, the such aliphatic polyhydroxy compound more than 3 yuan of tripentaerythritol.As above-mentioned (methyl) acrylate, for example can enumerate (methyl) acrylic acid 2-hydroxyl ethyl ester, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine dimethylacrylate etc. with hydroxyl.As above-mentioned polyfunctional isocyanate, can enumerate for example toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.As acid anhydrides, can enumerate the such tetra-atomic acid dianhydride of acid anhydrides, pyromellitic acid dianhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic acid dianhydride of the such dibasic acid of succinic anhydride for example, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride.

In addition, as above-mentioned multifunctional (methyl) acrylate, can enumerate for example compound of the middle record in the paragraph of TOHKEMY 11-44955 communique (0015)～(0018) through caprolactone modification.As above-mentioned multifunctional (methyl) acrylate, can enumerate the oxirane and/or epoxy pronane modification two (methyl) acrylate of bisphenol-A through the alkylene oxide modification, the oxirane of isocyanuric acid and/or epoxy pronane modification three (methyl) acrylate, the oxirane of trimethylolpropane and/or epoxy pronane modification three (methyl) acrylate, the oxirane of pentaerythrite and/or epoxy pronane modification three (methyl) acrylate, the oxirane of pentaerythrite and/or epoxy pronane modification four (methyl) acrylate, the oxirane of dipentaerythritol and/or epoxy pronane modification five (methyl) acrylate, the oxirane of dipentaerythritol and/or epoxy pronane modification six (methyl) acrylate etc.

In addition, as above-mentioned compound with 2 above N-alkoxyl-methyl amino, can enumerate for example have the melamine structure, the compound of benzoguanamine structure, urea structure etc.Need to prove that triazine ring or phenyl that melamine structure, benzoguanamine structure refer to have more than 1 replace the chemical constitution of triazine ring as basic framework, are the notions that also comprises melamine compound, benzoguanamine compound or their condensation product.As the concrete example of compound, can enumerate N, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-four (alkoxy methyl) benzoguanamine, N, N, N, N-four (alkoxy methyl) glycoluril etc. with 2 above N-alkoxyl-methyl amino.

In these multi-functional monomers, preferably make aliphatic polyhydroxy compound and (methyl) acrylic acid reaction more than 3 yuan and multifunctional (methyl) acrylate, multifunctional (methyl) acrylate through caprolactone modification, polyfunctional carbamate (methyl) acrylate that obtains, multifunctional (methyl) acrylate, N with carboxyl, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-four (alkoxy methyl) benzoguanamine.Intensity height at dyed layer, the surface smoothing excellence of dyed layer, and be difficult to producing scum (Di れ on the substrate of unexposed portion and on the light shield layer), aspects such as film is residual, in multifunctional (methyl) acrylate that the aliphatic polyhydroxy compound that makes more than 3 yuan obtains with the reaction of (methyl) acrylic acid, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, in having multifunctional (methyl) acrylate of carboxyl, especially preferably make the reaction of pentaerythritol triacrylate and succinic anhydride and the compound that obtains, the compound that makes the reaction of dipentaerythritol five acrylate and succinic anhydride and obtain.

Among the present invention, (D) crosslinking chemical can use separately or mix more than 2 kinds and use.

With respect to 100 mass parts (A) colorant, the content of (D) crosslinking chemical among the present invention is preferably 10～1,000 mass parts, preferred especially 20～500 mass parts.At this moment, if the content of crosslinking chemical is very few, then might can not get sufficient curable.On the other hand, if the content of crosslinking chemical is too much, when then giving coloured composition alkali-developable of the present invention, has alkali-developable and reduce, be easy to generate tendencies such as scum, film be residual on the substrate of unexposed portion or on the light shield layer.

-(E) resin glue-

Can make coloured composition of the present invention contain (E) resin glue.Thus, can give the coloured composition alkali-developable and with the cohesiveness of substrate.Resin glue as such is not particularly limited, but be preferably have carboxyl, the resin of acidic functionality such as phenolic hydroxyl group.Wherein, the polymkeric substance (hereinafter referred to as " carbonyl bearing polymer ") that preferably has carboxyl, can enumerate the ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (e1) ") that for example has 1 above carboxyl but with the multipolymer of the ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (e2) ") of other copolymerization.

As above-mentioned unsaturated monomer (e1), for example can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate (2-(methyl) acryloxy ethyl) ester, ω-carboxyl polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.

These unsaturated monomers (e1) can use separately or mix more than 2 kinds and use.

In addition, as above-mentioned unsaturated monomer (e2), for example can enumerate:

N-phenylmaleimide, the such N-position substituted maleimide amine of N-cyclohexyl maleimide;

Styrene, α-Jia Jibenyixi, para hydroxybenzene ethene, to hydroxyl-α-Jia Jibenyixi, to vinyl benzyl glycidol ether, the such aromatic ethenyl compound of acenaphthylene;

(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyethylene glycol (n=2～10) methyl ethers (methyl) acrylate, polypropylene glycol (n=2～10) methyl ethers (methyl) acrylate, single (methyl) acrylate of polyglycol (n=2～10), single (methyl) acrylate of polypropylene glycol (n=2～10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, (methyl) acrylic acid dihydro DCPA (dicyclopentenyl (meth) acrylate), glycerine list (methyl) acrylate, (methyl) acrylic acid 4-hydroxylphenyl ester, to oxirane modification (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3 of cumyl phenol, 4-epoxycyclohexyl methyl esters, 3-((methyl) acryloyl-oxy ylmethyl) oxetanes, 3-((methyl) acryloyl-oxy ylmethyl)-such (methyl) acrylate of 3-ethyl oxetanes;

Cyclohexyl vinyl ether, isobornyl vinyl ether, three ring [5.2.1.0 ^2,6] decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(ethyleneoxy the methyl)-such vinyl ether of 3-ethyl oxetanes;

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

These unsaturated monomers (e2) can use separately or mix more than 2 kinds and use.

In the multipolymer of unsaturated monomer (e1) and unsaturated monomer (e2), the copolymerization ratio of the unsaturated monomer in this multipolymer (e1) is preferably 5～50 quality %, 10～40 quality % more preferably.By make unsaturated monomer (e1) copolymerization with such scope, can access the coloured composition of alkali-developable and excellent storage stability.

As the concrete example of the multipolymer of unsaturated monomer (e1) and unsaturated monomer (e2), for example can enumerate disclosed multipolymer among Japanese kokai publication hei 7-140654 communique, Japanese kokai publication hei 8-259876 communique, Japanese kokai publication hei 10-31308 communique, Japanese kokai publication hei 10-300922 communique, Japanese kokai publication hei 11-174224 communique, Japanese kokai publication hei 11-258415 communique, TOHKEMY 2000-56118 communique, the TOHKEMY 2004-101728 etc.

In addition; among the present invention; for example as Japanese kokai publication hei 5-19467 communique, Japanese kokai publication hei 6-230212 communique, Japanese kokai publication hei 7-207211 communique, Japanese kokai publication hei 09-325494 communique, Japanese kokai publication hei 11-140144 communique, TOHKEMY 2008-181095 communique etc. are disclosed, also can use the carbonyl bearing polymer that has polymerism unsaturated links such as (methyl) acryloyl group at side chain as resin glue.

Resin glue among the present invention utilize GPC (eluting solvent: tetrahydrofuran) weight-average molecular weight by polystyrene conversion of Ce Dinging is generally 1,000～100,000, be preferably 3,000～50,000.If this weight-average molecular weight is too small, the then reductions such as residual film ratio of resulting overlay film, perhaps pattern form, thermotolerance etc. are impaired, and electrical characteristics might worsen, on the other hand, if weight-average molecular weight is excessive, then resolution reduces, perhaps pattern form is impaired, and might be easy to generate dry foreign matter when utilizing the gap nozzle mode to be coated with.

In addition, (eluting solvent: the ratio of tetrahydrofuran) measuring by the number-average molecular weight of polystyrene conversion is preferably 1.0～5.0, more preferably 1.0～3.0 to the weight-average molecular weight of the resin glue among the present invention with utilizing GPC.

Resin glue among the present invention can be by the known method manufacturing, can also control its structure, molecular weight, molecular weight distribution by TOHKEMY 2003-222717 communique for example, TOHKEMY 2006-259680 communique, the international middle disclosed method such as No. 07/029871 pamphlet that disclose.

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

Among the present invention, with respect to (A) colorant of 100 mass parts, the content of resin glue is generally 10～1,000 mass parts, is preferably 20～500 mass parts.If the content of resin glue is very few, then for example alkali-developable reduces, perhaps the storage stability of resulting coloured composition reduces, on the other hand, if the content of resin glue is too much, then colorant concentration reduces relatively, so might be difficult to reach the aim colour concentration as film.

-(F) Photoepolymerizationinitiater initiater-

Can make coloured composition of the present invention contain (F) Photoepolymerizationinitiater initiater.Thus, can give the coloured composition radiation-sensitive.Being used for (F) of the present invention Photoepolymerizationinitiater initiater is the compound that produces the spike that can cause the polymerization of above-mentioned (D) crosslinking chemical by the exposure of luminous ray, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial.

As such Photoepolymerizationinitiater initiater, for example can enumerate thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound,

Salt based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, encircle quinone based compound, diazonium based compound, acid imide sulphonic acid ester based compound etc. more.

Among the present invention, Photoepolymerizationinitiater initiater can use separately or mix more than 2 kinds and use.As Photoepolymerizationinitiater initiater, be preferably selected from least a in thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, the O-acyl group oxime compound.

Among the present invention in the preferred Photoepolymerizationinitiater initiater, concrete example as the thioxanthones based compound, can enumerate thioxanthones, 2-clopenthixal ketone, 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.

In addition, as the concrete example of above-mentioned acetophenone based compound, can enumerate 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone etc.

In addition, as the concrete example of above-mentioned bisglyoxaline based compound, can enumerate 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ' 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In addition, when using the bisglyoxaline based compound as Photoepolymerizationinitiater initiater, can improve sensitivity aspect preferably share hydrogen donor.Said herein " hydrogen donor " means the compound that hydrogen atom can be provided the free radical that is produced by the bisglyoxaline based compound by exposure.As hydrogen donor, can enumerate for example 2-mercaptobenzothiazole, 2-sulfydryl benzo

Mercaptan such as azoles are hydrogen donor, 4, and amine such as 4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone are hydrogen donor.Among the present invention, hydrogen donor can use separately or mix more than 2 kinds and to use, can further improve sensitivity aspect, preferably be with mercaptan more than a kind hydrogen donor and more than a kind amine be that hydrogen donor is used in combination.

In addition, concrete example as above-mentioned triazine based compound, can enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(5-methylfuran-2-yl) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(furans-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-(3 for 2-, 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 etc. of 6-have the triazine based compound of halogenated methyl.

In addition; concrete example as O-acyl group oxime compound; can enumerate 1; 2-octane diketone-1-(4-(thiophenyl) phenyl)-2-(O-benzoyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl)-1-(O-acetyl oxime), ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9H-carbazole-3-yl)-1-(O-acetyl oxime) etc.

Among the present invention, during Photoepolymerizationinitiater initiater beyond using the bisglyoxaline based compound of acetophenone based compound etc., also can share sensitizer.As such sensitizer; for example can enumerate 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2, two (the 4-lignocaine benzylidene) cyclohexanone of 5-, 7-lignocaine-3-(4-lignocaine benzoyl) cumarin, 4-(lignocaine) chalcone etc.

Among the present invention, with respect to 100 mass parts (D) crosslinking chemical, the content of Photoepolymerizationinitiater initiater is preferably 0.01～120 mass parts, preferred especially 1～100 mass parts.At this moment, if the content of Photoepolymerizationinitiater initiater is very few, then may be insufficient by being solidified with of carrying out of exposure, on the other hand,, then have the tendency that formed dyed layer comes off from substrate easily when developing if this content is too much.

-adjuvant-

Coloured composition of the present invention also can contain various adjuvants as required.

As adjuvant, can enumerate for example filling agent such as glass, aluminium oxide; Macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl acrylate) class; Fluorine is that surfactant, silicon are surfactants such as surfactant; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, driving fit promoter such as 3-sulfydryl propyl trimethoxy silicane; 2, antioxidants such as 2-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone class; Anti flocculants such as sodium polyacrylate; Malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1, residue improvers such as 2-butylene glycol; Mono succinate (2-(methyl) acryloxy ethyl) ester, phthalic acid list (2-(methyl) acryloxy ethyl) ester, ω-development property improvement agent such as carboxyl polycaprolactone list (methyl) acrylate etc.

Color filter and manufacture method thereof

Color filter of the present invention possesses the dyed layer that uses coloured composition of the present invention and form.

As the method for making color filter, first can enumerate following method.At first, on the surface of substrate, form light shield layer (black matrix) in the mode that the part that forms pixel is divided as required.Next, be dispersed with the fluid composition of the radiation-ray sensitive composition of the present invention of red stain for example in coating on this substrate after, carry out prebake, make solvent evaporation, formation is filmed.Then, to this exposure of filming, then, use alkaline developer to develop, unexposed the dissolving of filming removed across photomask.Thereafter, by after cure, form the red pixel pattern pel array that is configured to of sequence in accordance with regulations.

Next, use green or each blue colored radiation-sensitive composition, with the above-mentioned coating of similarly carrying out each colored radiation-sensitive composition, prebake, exposure, development and after cure, on same substrate, form green pixel array and blue pixel array successively.Thus, can obtain on substrate, disposing the color filter of redness, green and blue three primary colors pel array.But among the present invention, the order that forms each color pixel is not limited to said sequence.

In addition, black matrix can form in the following way, promptly, to utilize photoetching process to make desired pattern by the metallic films such as chromium that sputter or evaporation form forms, but also can use the colored radiation-sensitive composition that is dispersed with black colorant, similarly form during with the above-mentioned pixel of formation.

The substrate that uses during as the formation color filter can be enumerated for example glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.

In addition, as required, can also implement the pre-treatment that suits in advance, as utilize chemicals processing that silane coupling agent etc. carries out, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation etc. these substrates.

When colored radiation-sensitive composition is coated substrate, can adopt suitable rubbing method such as spray-on process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, scraper rubbing method, but especially preferably adopt spin-coating method, slit die rubbing method.

Prebake makes up drying under reduced pressure and heat drying usually carries out.Drying under reduced pressure is carrying out until reaching 50～200Pa usually.In addition, the condition of heat drying is normally 70～110 ℃ of dryings about 1～10 minute.

Coating thickness is generally 0.6～8.0 μ m, is preferably 1.2～5.0 μ m with dried film thickness gauge.

The light source of the radioactive ray that use during as formation pixel and/or black matrix, for example can enumerate LASER Light Source such as lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp or Argon ion laser, YAG laser instrument, XeCl quasi-molecule laser, nitrogen laser etc., but optimal wavelength is at the radioactive ray of 190～450mm scope.

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

In addition, as above-mentioned alkaline developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.

In above-mentioned alkaline developer, also can add for example water-miscible organic solvent such as methyl alcohol, ethanol, surfactant etc. in right amount.Need to prove that alkali is washed after developing usually.

As the development treatment method, can use spray development method, spray development method, immersion development method, soak and put (puddle) development method etc.Development conditions was preferably carried out 5～300 seconds at normal temperature.

After the condition of curing be generally at 180～280 ℃ and carry out about 10～60 minutes.

The thickness of the pixel of Xing Chenging is generally 0.5～5.0 μ m, is preferably 1.0～3.0 μ m like this.

In addition, as second method of making color filter, can adopt method disclosed in Japanese kokai publication hei 7-318723 communique, the TOHKEMY 2000-310706 communique etc., obtain each color pixel by ink-jetting style.In this method, at first, on the surface of substrate, form the next door that has shade function concurrently.Next, for example will be dispersed with by ink discharge device that the fluid composition of the coloured composition of the present invention of red stain is sprayed onto in the formed next door, then, carry out prebake, make solvent evaporation.Next, after the exposure of as required this being filmed, by after cure it solidified, form red pattern of pixels.

Then, use green or each blue coloured composition, with above-mentioned green pixel pattern and the blue pixel pattern of similarly on same substrate, forming successively.Thus, can obtain on substrate, disposing the color filter of redness, green and blue three primary colors pattern of pixels.But among the present invention, the order that forms each color pixel is not limited to said sequence.

In addition, above-mentioned next door not only has shade function, and performance is used to make the coloured composition of all kinds that is sprayed onto in the dividing regions that the function of colour mixture does not take place, so compare with employed black matrix in above-mentioned first method, thickness is thicker.Therefore, the next door uses the black radiation-ray sensitive composition to form usually.

The substrate that uses when forming color filter, the light source of radioactive ray and prebake with after the method and the condition of curing identical with the first above-mentioned method.So, the thickness of the pixel that forms by ink-jetting style and the height in next door are same degree.

On the pattern of pixels that obtains like this, form diaphragm as required after, form nesa coating by sputter.After forming nesa coating, and then form separator, also can make color filter.Separator uses radiation-ray sensitive composition to form usually, but also can make the separator (black separator) with light-proofness.In this case, use the colored radiation-sensitive composition that is dispersed with black colorant, but coloured composition of the present invention also can perform well in the formation of described black separator.

The color filter of the present invention that obtains like this is because brightness and excitation are high, so exceedingly useful to color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc.

Color liquid crystal display device

Color liquid crystal display device of the present invention possesses color filter of the present invention.

Color liquid crystal display device of the present invention can adopt suitable structure.For example can adopt such structure: with the driving of disposing thin film transistor (TFT) (TFT) substrate different with substrate on form color filter, drive with substrate and the substrate that is formed with color filter and dispose across the liquid crystal layer subtend; Can also adopt such structure: form color filter disposing on the surface of driving with substrate of thin film transistor (TFT) (TFT), this substrate disposes across the liquid crystal layer subtend with the substrate that is formed with ITO (being doped with the indium oxide of tin) electrode.Back one structure can significantly improve aperture opening ratio, has the advantage of the liquid crystal display cells that can obtain bright and high definition.

Color liquid crystal display device of the present invention is except that cold cathode fluorescent tube (CCFL:Cold Cathode Fluorescent Lamp), and can possess with the White LED is the backlight unit of light source.As White LED, for example can enumerate, use has the red LED of independent spectrum, green LED and blue led and obtain the White LED of white light, display predetermined colors in combination LED, green LED and blue led obtain the White LED of white light by colour mixture, combined blue LED, red LED and green-emitting phosphor obtain the White LED of white light by colour mixture, combined blue LED, red light-emitting phosphor and green emitting fluorophor obtain the White LED of white light by colour mixture, by blue led and YAG is the White LED that the colour mixture of fluorophor obtains white light, combined blue LED, orange luminescence fluorophor and green emitting fluorophor obtain the White LED of white light by colour mixture, make up ultraviolet LED, red light-emitting phosphor, green emitting fluorophor and blue-light-emitting fluorescent material obtain the White LED of white light etc. by colour mixture.

Color liquid crystal display device of the present invention can be used TN (Twisted Nematic, twisted-nematic) type, STN (Super Twisted Nematic, supertwist is to row) type, IPS (In-Planes Switching, switching in the face) type, VA (Vertical Alignment, vertical orientated) liquid crystal mode that type, OCB (Optically Compensated Birefringence, optical compensation curved arrangement) type etc. are suitable.

Embodiment

Below, enumerate embodiment, embodiments of the present invention more specifically are described.But the invention is not restricted to following embodiment.

＜(B) multipolymer is synthetic 〉

Synthesis example 1

In possessing the flask of stirrer, with methoxy poly (ethylene glycol) monomethacrylates (manufacturing of PME-200 Japan Oil Co) (hereinafter referred to as " PME-200 ") 0.6g, n-BMA (hereinafter referred to as " nBMA ") 12.9g, methyl methacrylate (hereinafter referred to as " MMA ") 10.5g, 2,2 '-azoisobutyronitrile (hereinafter referred to as " AIBN ") 323mg and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters (ピ ラ ゾ one Le-1-ジ チ オ カ Le ボ Application acid シ ア ノ (ジ メ チ Le) メ チ Le エ ス テ Le) 833mg is dissolved among the toluene 30mL, carries out 30 minutes nitrogen bubbles.Slowly stir, make the temperature of reaction solution rise to 57 ℃, kept this temperature 34 hours, carry out active free radical polymerization thereafter.

Next, AIBN 211mg and dimethylaminoethyl methacrylate (hereinafter referred to as " DAMA ") 4.1g are dissolved among the toluene 20mL, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 34 hours active free radical polymerizations at 57 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising A block with the repetitive that derives from DAMA and segmented copolymer with B block of the repetitive that derives from PME-200, nBMA and MMA.The multipolymer note that obtains is made " multipolymer (B-1) ".

Synthesis example 2

In possessing the flask of stirrer, the AIBN of MMA, the 295mg of methacrylic acid-2-Octyl Nitrite (hereinafter referred to as " EHMA ") of nBMA, the 2.8g of PME-200, the 10.6g of 1.4g, 7.0g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 726mg are dissolved in the 30mL toluene, carry out 30 minutes nitrogen bubbles.Slowly stir, make the temperature of reaction solution rise to 60 ℃, kept this temperature 24 hours, carry out active free radical polymerization thereafter.

Next, the AIBN of 352mg and the DAMA of 6.2g are dissolved in the 20mL toluene, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 24 hours active free radical polymerizations at 60 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising the A block and segmented copolymer of repetitive with source DAMA with B block of the repetitive that derives from PME-200, nBMA, EHMA and MMA.Resulting multipolymer note is made " multipolymer (B-2) ".

Synthesis example 3

In possessing the flask of stirrer, the AIBN of MMA, the 352mg of the benzyl methacrylate (hereinafter referred to as " BzMA ") of EHMA, the 1.7g of nBMA, the 6.7g of PME-200, the 5.0g of 1.4g, 7.0g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 649mg are dissolved in the 30mL toluene, carry out 30 minutes nitrogen bubbles.Slowly stir, make the temperature of reaction solution rise to 62 ℃, kept this temperature 20 hours, carry out active free radical polymerization thereafter.

Next, the AIBN of 448mg and the DAMA of 6.2g are dissolved in the 20mL toluene, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 20 hours active free radical polymerizations at 62 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising A block with the repetitive that derives from DAMA and segmented copolymer with B block of the repetitive that derives from PME-200, nBMA, EHMA, BzMA and MMA.Resulting multipolymer note is made " multipolymer (B-3) ".

Compare synthesis example 1

In possessing the flask of stirrer, the AIBN of MMA, the 256mg of BzMA, the 5.6g of EHMA, the 1.7g of nBMA, the 5.0g of PME-200, the 6.4g of 5.6g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 660mg are dissolved in the 30mL toluene, carry out 30 minutes nitrogen bubbles.Slowly stir, make the temperature of reaction solution rise to 60 ℃, kept this temperature 24 hours, carry out active free radical polymerization thereafter.

Next, the AIBN of 189mg and the DAMA of 3.6g are dissolved in the 20mL toluene, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 24 hours active free radical polymerizations at 60 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising A block with the repetitive that derives from DAMA and block copolymer solution with B block of the repetitive that derives from PME-200, nBMA, EHMA, BzMA and MMA.Resulting multipolymer note is made " multipolymer (b-1) ".

Compare synthesis example 2

In possessing the flask of stirrer, the AIBN of MMA, the 236mg of nBMA, the 7.0g of PME-200, the 6.6g of 7.8g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 610mg are dissolved in the 30mL toluene, carry out 30 minutes nitrogen bubbles., slowly stir, make the temperature of reaction solution rise to 60 ℃, kept this temperature 24 hours, carry out active free radical polymerization thereafter.

Next, the AIBN of 342mg and the DAMA of 6.6g are dissolved in the 20mL toluene, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 24 hours active free radical polymerizations at 60 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising A block with the repetitive that derives from DAMA and segmented copolymer with B block of the repetitive that derives from PME-200, nBMA and MMA.Resulting multipolymer note is made " multipolymer (b-2) ".

Compare synthesis example 3

In possessing the flask of stirrer, the AIBN of MMA, the 240mg of BzMA, the 7.0g of EHMA, the 1.7g of nBMA, the 6.7g of 7.0g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 690mg are dissolved in the 30mL toluene, carry out 30 minutes nitrogen bubbles.Slowly stir, make the temperature of reaction solution rise to 62 ℃, kept this temperature 20 hours, carry out active free radical polymerization thereafter.

Next, the AIBN of 290mg and the DAMA of 5.6g are dissolved in the 20mL toluene, carry out 30 minutes nitrogen replacements, will be added on through the solution of nitrogen replacement in the above-mentioned reaction solution, carry out 20 hours active free radical polymerizations at 62 ℃.By concentrating under reduced pressure with solvent exchange be propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %s thereafter.So, obtain comprising A block with the repetitive that derives from DAMA and segmented copolymer with B block of the repetitive that derives from nBMA, EHMA, BzMA and MMA.Resulting multipolymer note is made " multipolymer (b-3) ".

The mensuration of＜Mw and Mw/Mn 〉

Mw of (B) multipolymer that obtains in above-mentioned each synthesis example and Mn measure by the GPC of following specification.The copolymerization ratio (quality %) of each monomer of measurement result in (B) multipolymer is shown in Table 1.

Device: GPC-104 (Showa Denko K. K's manufacturing).

Post: KD-G, KF-603, KF-602, KF-601 are used in combination.

Moving phase: DMF.

The mensuration of＜amine value 〉

Measure the amine value of (B) multipolymer that obtains in above-mentioned each synthesis example with following main points.Measurement result is shown in table 1.

Precision weighing copolymer solution 0.5g to 1mg unit places glass container.Add acetic anhydride/acetic acid=9/1 (volume ratio) 20ml and dissolve, placed 3 hours in room temperature.Thereafter, further add acetate 30ml after, use potential difference (PD) determinator AT-510 (manufacturing of capital of a country electronics industry Co., Ltd.), carry out titration with 0.1mol/l perchloric acid-acetic acid solution.Similarly carry out blank test.0.1mol/l perchloric acid-acetic acid solution dripping quantity by (B) multipolymer and blank test calculates amine value (mgKOH/g of unit).

Table 1

	Synthesis example 1	Synthesis example 2	Synthesis example 3	Compare synthesis example 1	Compare synthesis example 2	Compare synthesis example 3
							The copolymerization name	B-1	B-2	B-3	b-1	b-2	b-3
PME-200	2	5	5	20	28	0
							nBMA	46	38	18	23	23.5	25
EHMA	0	10	24	18	0	24
							BzMA	0	0	6	6	0	6
MMA	37.5	25	25	20	25	25
							DAMA	14.5	22	22	13	23.5	20
Mw/Mn	1.53	1.46	1.89	1.73	1.71	1.75
							Mw	7900	7800	7500	8300	8500	8100
The amine value	52	79	79	46	84	71

The preparation of＜dispersible pigment dispersion and evaluation 〉

Embodiment 1

Use is as C.I. naphthol green 58 (manufacturing of DIC society) 7.2 mass parts of colorant and C.I. pigment yellow 1504.8 mass parts, multipolymer (B-1) solution 10 mass parts (nonvolatile component=40 quality %), as propylene glycol methyl ether acetate 70 mass parts and propylene glycol monomethyl ether 8 mass parts of solvent, utilize ball mill to handle, preparation dispersible pigment dispersion (A-1).

Measure the viscosity of resulting dispersible pigment dispersion with E type viscosity meter (manufacturing of Tokyo gauge).And, the dispersible pigment dispersion that obtains is filled in the front glass container, under air-tight state in 23 ℃ leave standstill 14 days after, use E type viscosity meter (manufacturing of Tokyo gauge) to measure viscosity once more.And, calculate the viscosity of preserving after 14 days increment rate with respect to the viscosity that has just prepared, be evaluated as during increment rate less than 10% " A ", increment rate is 10% to be evaluated as " B " when above.Evaluation result is shown in table 2.

Embodiment 2～4 and comparative example 1～5

In preparation example 1, the quantitative change of colorant, (B) multipolymer and solvent is more as shown in table 2, in addition, prepare colorant dispersion (A-2)～(A-9) similarly to Example 1 and estimate.Evaluation result is listed in table 2.

In the table 2, " G58 ", be meant C.I. naphthol green 58, " Y150 " is meant C.I. pigment yellow 150, " Y179 " is meant the C.I. solvent yellow 179 as organic dyestuff, and " PGMEA " is meant propylene glycol methyl ether acetate, " PGME " is meant propylene glycol monomethyl ether, and " BYK6919 " is meant commercially available dispersant B YK-LPN6919 (manufacturing of Bi Ke chemistry (BYK) society).Need to prove that BYK-LPN6919 is the dispersant solution that contains the segmented copolymer of have repetitive (1) and repetitive (2), amine value=120mgKOH/g (being converted into nonvolatile component), nonvolatile component=60 quality %.

Table 2

Synthesizing of＜resin glue 〉

Synthesis example 4

In the flask that possesses cooling tube and stirring machine, nBMA, 15.0g hydroxyethyl methylacrylate, 20.0g styrene and the 20.0g methacrylic acid of BzMA, the 20.0g of 25.0g are dissolved in the 200g propylene glycol methyl ether acetate, and then add 2 of the AIBN of 3.0g and 5.0g, 4-diphenyl-4-methyl-1-pentene, 15 minutes nitrogen of its post-purge.Behind the nitrogen purging, on one side reactant liquor is stirred and nitrogen bubble, being heated to 80 ℃ on one side, polymerization 5 hours obtains containing the solution of 33 quality % resin glues (E-1) thus.This resin glue (E-1) utilizes GPC (eluting solvent: weight-average molecular weight=10 of tetrahydrofuran) measuring, 500 by polystyrene conversion, utilize GPC (eluting solvent: ratio=2.5 of tetrahydrofuran) measuring by the weight-average molecular weight and the number-average molecular weight of polystyrene conversion.

The preparation of＜colored radiation-sensitive composition and evaluation 〉

The preparation of colored radiation-sensitive composition

Embodiment 5

With dispersible pigment dispersion (A-1) 100 mass parts, resin glue (E-1) solution 33.5 mass parts as resin glue, M-402 (dipentaerythritol acrylate is a major component) 9.7 mass parts of making as the Toagosei Co., Ltd of crosslinking chemical, (trade name Irgacure 369 for butane-1-ketone as the 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) of Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals society makes) 4.3 mass parts and mix as the 3-ethoxyl ethyl propionate of solvent, the preparation solid component concentration is the colored radiation-sensitive composition of 20 quality %.

The evaluation of time comes off

After using spin coater to be coated on the colored radiation-sensitive composition that obtains on the glass substrate, carry out 2 minutes prebake, form filming of thickness 2.5 μ m with 100 ℃ heating plates.Next, behind this substrate cool to room temperature,, use radioactive ray that high-pressure sodium lamp will comprise 365nm, 405nm and each wavelength of 436nm across photomask with 1,000J/m to filming on the substrate ²Exposure to the exposure of respectively filming.By 23 ℃ 0.04 weight % potassium hydroxide aqueous solution be sprayed onto filming substrate on, spray development thereafter.At this moment, measure time (coming off the time) till peeling off fully of filming until unexposed portion.So the time that comes off is evaluated as " A " during less than 60 seconds, come off the time more than 60 seconds and less than be evaluated as " B " in the time of 120 seconds, come off the time more than 120 seconds and less than be evaluated as " C " in the time of 180 seconds, the time that comes off is evaluated as " D " in time more than 180 seconds.This time is short more, and developing powder is fast more, has the advantage of the pitch time that can shorten the color filter manufacturing.Evaluation result is listed in table 3.

The evaluation of colorimetric properties

Use spin coater that the colored radiation-sensitive composition that obtains is coated on the glass substrate, then, carry out 2 minutes prebake with 100 ℃ heating plates, different 3 of formation thickness film.Next, behind these substrate cool to room temperature,, use radioactive ray that high-pressure sodium lamp will not comprise 365nm, 405nm and each wavelength of 436nm across photomask ground with 1,000J/m to filming on the substrate ²Exposure to the exposure of respectively filming., in 180 ℃ carry out 20 minute after cure, on substrate, form cured film thereafter.To resulting 3 cured film, the MCPD2000 that uses color analysis instrument (Otsuka Electronics Co., Ltd. to make) with illuminant-C, 2 degree visual angles measure chromaticity coordinate value in the CIE colour systems (x, y) and values (Y).Chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.590 and values (Y) by measurement result.Evaluation result is listed in table 3.

Embodiment 6～8 and comparative example 5～9

In embodiment 5, the kind of dispersible pigment dispersion is changed to as shown in table 3, in addition, carry out colored radiation preparation of compositions and evaluation similarly to Example 5.Evaluation result is listed in table 3.

Table 3

Claims (9)

1. a coloured composition is characterized in that, contains:

A: comprise the colorant of pigment,

B: comprise A block and B block, the amine value is the segmented copolymer of the above and not enough 80mgKOH/g of 50mgKOH/g, described A block has the above repetitive (1) with following formula (1) expression of 60 quality %, described B block have with the repetitive (2) of following formula (2) expression and

C: solvent,

In the formula (1), X represents divalent linking group, R ¹Expression hydrogen atom or methyl, R ²And R ³Represent that independently of each other hydrogen atom maybe can have the alkyl of substituent chain or ring-type, R ²And R ³Can mutually combine and form ring texture,

In the formula (2), R ⁴Represent that independently of each other carbon number is 2～4 alkylidene, R ⁵The expression carbon number is 1～6 alkyl, R ⁶Expression hydrogen atom or methyl, n represents 1～150 integer.

2. coloured composition as claimed in claim 1, wherein, in the described formula (1), X is-COO-R ⁸-(*) base, described R ⁸Expression methylene, carbon number are that 2～10 alkylidene or carbon number are 2～10 alkylidene oxyalkylene, (*) binding site that combines with N of expression.

3. coloured composition as claimed in claim 1 or 2, wherein, the weight-average molecular weight Mw of described B segmented copolymer and the ratio Mw/Mn of number-average molecular weight Mn are 1.0～1.8.

4. coloured composition as claimed in claim 1 or 2 wherein, contains phthualocyanine pigment as colorant.

5. coloured composition as claimed in claim 1 wherein, further contains D crosslinking chemical and E resin glue.

6. coloured composition as claimed in claim 5 wherein, further contains dyestuff as colorant.

7. coloured composition as claimed in claim 5 wherein, further contains the E Photoepolymerizationinitiater initiater.

8. color filter, it possesses the dyed layer that uses each described coloured composition in the claim 5～7 and form.

9. color liquid crystal display device, it possesses the described color filter of claim 8.