CN102213916B - Coloured composition, color filter and color liquid crystal display device - Google Patents

Abstract

The present invention relates to coloured composition, color filter and color liquid crystal display device.The invention provides the color composition for color filter of colorimetric properties, alkali-developable and excellent storage stability.The feature of described coloured composition is, contains: (A) comprises the colorant of pigment; (B) comprise A block and B block, amine value is more than 50mgKOH/g and less than the segmented copolymer of 80mgKOH/g, described A block has more than 60 quality % and derives from the repetitive with amino ethylenically unsaturated monomers, and described B block has the repetitive deriving from the ethylenically unsaturated monomers with alkylene glycol chain; (C) 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 manufacture color filter, known following method: on substrate coating pigment decentralized colored radiation-sensitive composition and after carrying out drying, pattern form irradiates radioactive ray (hereinafter referred to as " exposure ") to dry coating by the expected, and develop, obtain each color pixel (patent documentation 1 ~ 2) thus.In addition, the method (patent documentation 3) utilizing the optical polymerism composition being dispersed with carbon black to form black matrix is also known.And then also the colored resin composition of 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 for liquid crystal display cells or solid-state imager, the requirement of adjoint high brightness and high-contrast, 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 propose a kind of scheme in patent documentation 5, in order to effectively be disperseed by highly micronized pigment with a small amount of addition, the segmented copolymer that use amine value is 80mgKOH/g ~ 150mgKOH/g is as spreading agent.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2-144502 publication

Patent documentation 2: Japanese Unexamined Patent Publication 3-53201 publication

Patent documentation 3: Japanese Unexamined Patent Publication 6-35188 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2000-310706 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2009-25813 publication

Summary of the invention

But when the segmented copolymer that in use patent documentation 5, the amine value of proposition is high is as spreading agent, the alkali-developable of coloured composition is deteriorated, so bring obstacle to the batch production of color filter.When particularly combination pigment and dyestuff use as colorant, the deterioration of alkali-developable becomes remarkable.Therefore, strongly wish to develop: realize the requirement of high-contrast in recent years and high brightness and the also excellent color composition for color filter of alkali-developable.

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

In view of described truth, present inventor has performed further investigation, found that, by using specific segmented copolymer, above-mentioned problem can be solved, complete the present invention.

That is, the invention provides a kind of coloured composition, it is characterized in that, contain: (A) comprises the colorant of pigment; (B) comprise A block and B block, amine value is more than 50mgKOH/g and less than the segmented copolymer (hereinafter also referred to " (B) multipolymer ") of 80mgKOH/g, described A block has the repetitive (1) that more than 60 quality % represent by following formula (1), and described B block has the repetitive represented by following formula (2); (C) solvent.

(in formula (1), X represents divalent linking group, R ¹represent hydrogen atom or methyl, R ²and R ³represent that hydrogen atom maybe can have the alkyl of substituent chain or ring-type independently of each other, R ²and R ³can be combined with each other and form ring texture.)

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

In addition, the invention provides to possess and use this coloured composition and the color filter of dyed layer that formed and the color liquid crystal display device possessing this color filter.Herein, " dyed layer " means each color pixel used in color filter, black matrix, black separator etc.

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

Therefore, coloured composition of the present invention can extremely be suitable for making the various color filters headed by the color separation color filter of color liquid crystal display device color filter, solid-state imager, organic EL display element color filter, Electronic Paper 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, the present invention is described in detail.

coloured composition

Below, the constituent for coloured composition of the present invention is described.

-(A) colorant-

Coloured composition of the present invention contains pigment as (A) colorant.As pigment, being not particularly limited, can be any one in organic pigment, inorganic pigment.In the present invention, pigment can be used alone or mix two or more and use.Certainly, also can by organic pigment and inorganic pigment used in combination.

As above-mentioned organic pigment, such as 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 can be enumerated piperazine series pigments, Kui phthalein ketone series pigments, isoindoline series pigments, phthualocyanine pigment etc.

In addition, as above-mentioned inorganic pigment, such as titanium dioxide, barium sulphate, calcium carbonate, zinc paste, lead sulfate, chrome yellow, zinc yellow, colcother (red iron oxide (III)), cadmium red, ultramarine can be enumerated, Prussian blue, chrome oxide green, cobalt green, umber, titanium are black, synthesis is iron black, carbon black etc.

(B) the particularly phthualocyanine pigment in these pigment can be stablized and disperse well by multipolymer.In phthualocyanine pigment, as blue pigment, such as CuPc can be enumerated.More particularly, can enumerate at pigment index (C.I.; TheSociety0fDyersandColourists society issue) in classify as pigment compound, namely with the 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) multipolymer is particularly suitable for disperseing the C.I. pigment blue 15 in these phthalocyanine system blue pigments: 6.

In addition, in phthualocyanine pigment, as viridine green, the metal phthalocyanine of such as chlorination and/or bromination can be enumerated, more specifically can enumerate CuPc, Phthalocyanine Zinc, magnesium phthalocyanine, aluminum phthalocyanine, phthalocyanine titanium, phthalocyanine vanadium, manganese phthalocyanine, FePC, Cobalt Phthalocyanine, Nickel Phthalocyanine, Tin Phthalocyanine, phthalocyanine germanium etc.

(B) multipolymer is suitable for the chlorination CuPc, chlorination bromination CuPc, brominated phthalocyanine copper, chlorination bromination Phthalocyanine Zinc, the brominated phthalocyanine zinc that disperse in these phthalocyanine system viridine greens, particularly chlorination bromination Phthalocyanine Zinc.Chlorination bromination Phthalocyanine Zinc is preferably the structure that following formula (I) represents.

(in formula (I), Y represents hydrogen atom, chlorine atom or bromine atoms independently of each other, in whole Y 10 ~ 15 be bromine atoms, 1 ~ 6 for chlorine atom.)

It should be noted that, in pigment index (C.I.) name, chlorination CuPc is the pigment classifying as C.I. pigment Green 7, and chlorination bromination CuPc is the pigment classifying as C.I. pigment green 36, and chlorination bromination Phthalocyanine Zinc is the pigment classifying as C.I. naphthol green 58.

In the present invention, also can pass through recrystallization method, reprecipitation method, solvent cleaning method, sublimed method, vaccum heating method or their combination by refining for pigment rear use.In addition, pigment also can use after its particle surface modification with resin as required.As the resin of the particle surface modification by pigment, the vector resin such as described in Japanese Unexamined Patent Publication 2001-108817 publication or the commercially available various resins for pigment dispersion can be enumerated.As the resin-coated method of carbon blacksurface, the method that such as Japanese Unexamined Patent Publication 9-71733 publication, Japanese Unexamined Patent Publication 9-95625 publication, Japanese Unexamined Patent Publication 9-124969 publication etc. are described can be adopted.In addition, organic pigment uses after primary particle miniaturization preferably by the process of so-called salt mill.As the method for salt mill process, such as method disclosed in Japanese Unexamined Patent Publication 08-179111 publication can be adopted.

, in color composition for color filter, by using dyestuff as colorant, the high brightness that can not reach with pigment separately and high-contrast can be realized.But when using dyestuff as colorant, the alkali-developable of coloured composition is significantly deteriorated.In coloured composition of the present invention, by using (B) multipolymer as pigment dispersing agent, even if combination pigment and dyestuff use as colorant, also can obtain the good coloured composition of alkali-developable.As dyestuff, can enumerate such as with the compound of 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 Huang 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. black 7 based dyes such as azo such as grade of mordant dyeing,

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

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

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

Based dye such as methine such as disperse yellow 201 grade.

In the present invention, when using dyestuff as colorant, dyestuff can be used alone or mix two or more and use.

From the viewpoint of forming the high and black matrix of the pixel of excitation excellence or light-proofness excellence of brightness, (A) colorant containing proportional be 5 ~ 70 quality % in the solid constituent of coloured composition usually, preferably 5 ~ 60 quality %.At this, solid constituent refers to the composition beyond aftermentioned solvent.

-(B) multipolymer-

In the present invention, (B) multipolymer is the composition playing function as pigment dispersing agent, comprise A block and B block, amine value to be more than 50mgKOH/g and less than the segmented copolymer of 80mgKOH/g, wherein A block has the repetitive (1) that more than 60 quality % represent by above-mentioned formula (1), and B block has the repetitive (2) represented by above-mentioned formula (2).It should be noted that, " there is the above repetitive of 60 quality % (1) " refer to repetitive (1) in A block containing proportional be more than 60 quality %.

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

In addition ,-the NR of above-mentioned formula (1) ²r ³in, R ²and R ³representing that hydrogen atom maybe can have the alkyl of substituent chain or ring-type independently of each other, is the alkyl of 1 ~ 4 as the preferred carbon number of alkyl, particularly preferably methyl, ethyl, propyl group, butyl.In substituting group on alkyl, as the substituting group on chain alkyl, halogen atom, alkoxy, benzoyl etc. can be enumerated.In addition, as the substituting group in cyclic hydrocarbon group, the alkyl of chain, halogen atom, alkoxy etc. can be enumerated.It should be noted that, R ²and R ³represented chain alkyl comprises any one alkyl of straight-chain and branched.

In addition, R ²and R ³also can be combined with each other and form ring texture, as ring texture, the nitrogen heterocyclic ring monocycle of such as 5 ~ 7 rings or the condensed ring of 2 these monocycle condensations can be enumerated.Nitrogen heterocyclic ring does not preferably have aromaticity, more preferably saturated rings.Specifically can enumerate such as following example.

These ring texturees also can have substituting group further.

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

(B) the A block of multipolymer can have above-mentioned repetitive (1) and the repetitive except repetitive (1).As the example of such repetitive, the ethylenically unsaturated monomers deriving from and there is the nitrogen heterocycles such as pyridine radicals, imidazole radicals, pyrazolyl, triazolyl, tetrazole radical, imidazolinyl, tetrahydro-pyrimidine base can be enumerated; There is the repetitive etc. of the ethylenically unsaturated monomers of quaternary ammonium base.

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

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

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

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

(B) as long as the structure of multipolymer comprises the A block of the repetitive (1) with more than 60 quality % and has the segmented copolymer of B block of repetitive (2), just be not particularly limited, but be preferably A-B segmented copolymer or B-A-B segmented copolymer.

(B), in 1 A block of multipolymer, also two or more repetitive (1) can be contained.Now, repetitive of more than two kinds (1) can be contained in A block with the either type of random copolymerization, block copolymerization.In addition, the repetitive (1) in A block containing proportional be preferably more than 75 quality %, be particularly preferably more than 90 quality %.

(B), in 1 B block of multipolymer, also two or more repetitive (2) can be contained.Now, repetitive of more than two kinds (2) can be contained in B block with the either type of random copolymerization, block copolymerization.In addition, when having repetitive (3) and other repetitive in B block, these repetitives can contain two or more respectively in 1 B block.Now, each repetitive can be contained in B block with the either type of random copolymerization, block copolymerization.Repetitive (2), repetitive (3) and other repetitive also can be contained in B block with the either type of random copolymerization, block copolymerization.

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

(B) the amine value of multipolymer is more than 50mgKOH/g and less than 80mgKOH/g, but is preferably 52mgKOH/g ~ 79mgKOH/g.Herein, amine value represents with the alkali number in every 1g spreading agent solid constituent to be the mg number of the KOH of equivalent.

In addition, in (B) multipolymer, repetitive (2) containing proportional in whole repetitive be preferably 1 ~ 30 quality %, be more preferably 1 ~ 25 quality %.

By (B) multipolymer is set as such mode, coloured composition that is dispersed and alkali-developable excellence can be obtained.

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

(B) multipolymer can be manufactured by known method, such as, and can by will the monomer of above-mentioned each repetitive be provided to carry out living polymerization to manufacture.As living polymerization, Japanese Unexamined Patent Publication 9-62002 publication, Japanese Unexamined Patent Publication 2002-31713 publication, P.Lutz, P.Massonetal, Polym.Bull. can be adopted, 12,79 (1984); B.C.Anderson, G.D.Andrewsetal, Macromolecules, 14,1601 (1981); K.Hatada, K.Ute, etal, Polym.J., 17,977 (1985); K.Hatada, K.Ute, etal, Polym.J., 18,1037 (1986), the right hand great Yi ， field Tagayasu Dens 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.Hertleretal, Macromolecules, the known method recorded in 20,1473 (1987) etc.

As the monomer providing repetitive (1), (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) acrylate propyl ester, (methyl) acrylic acid lignocaine propyl ester etc. can be enumerated such as.

As the monomer providing repetitive (2), such as polyglycol (n=1 ~ 5) methyl ether (methyl) acrylate, polyglycol (n=1 ~ 5) ether (methyl) acrylate, polyglycol (n=1 ~ 5) propyl ether (methyl) acrylate, polypropylene glycol (n=1 ~ 5) methyl ether (methyl) acrylate, polypropylene glycol (n=1 ~ 5) ether (methyl) acrylate, polypropylene glycol (n=1 ~ 5) propyl ether (methyl) acrylate etc. can be enumerated.

As the monomer providing repetitive (3), such as (methyl) methyl acrylate can be enumerated, (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) phenylethyl acrylate etc.

In addition; as the monomer that copolymerization can occur in A block together with providing the monomer of repetitive (1), the monomer that (methyl) acrylamidopropyl trimethyl ammonium chloride, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) acrylyl oxy-ethyl triethyl ammonium chloride, (methyl) acrylyl oxy-ethyl (4-benzoylbenzyl) ditallowdimethyl ammonium bromide, (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, (methyl) acrylyl oxy-ethyl benzyl diethylammonium chloride and following formula represent can be enumerated such as.

(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 be used alone or mix two or more use.(B) content of multipolymer is generally 1 ~ 100 mass parts relative to 100 mass parts pigment, is preferably 5 ~ 70 mass parts, more preferably 10 ~ 50 mass parts.(B), when the content of multipolymer is too much, developability is likely impaired.

In the present invention, in order to improve dispersiveness, also known spreading agent can be contained further.As known spreading agent, such as carbamate system spreading agent, polyethyleneimine system spreading agent, polyoxyethylene alkyl ether system spreading agent, polyoxyethylene alkyl phenyl ether system spreading agent, polyethylene glycol di system spreading agent, sorbitan fatty acid ester system spreading agent, fatty acid modified Polyester spreading agent, dispersant containing acrylic, pigment derivative etc. can be enumerated.

As the concrete example of such spreading agent, commodity can be enumerated and be called EFKA (manufacture of EFKAChemicalsBV (EFKA) society), Disperbyk (manufacture of Bi Ke chemistry (BYK) society), Supreme Being Si Balong (nanmu originally changes into Co., Ltd. and manufactures), Solsperse (manufacture of Lubrizol society), KP (Shin-Etsu Chemial Co., Ltd's manufacture), Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacture), EFTOP (manufacture of TochemProducts society), MEGAFAC (Dainippon Ink. & Chemicals Inc's manufacture), FLUORAD (manufacture of Sumitomo 3M Co., Ltd.), ASAHIGUARD, SURFLON (above for Asahi Glass Co., Ltd manufactures) etc.In addition, as the concrete example of pigment derivative, the sulfonic acid etc. of CuPc, diketopyrrolopyrrolecocrystals, Kui phthalein ketone can be enumerated.

-(C) solvent-

Coloured composition of the present invention is prepared usually as follows: first, in (C) solvent, use such as ball mill, roller mill etc. to pulverize with (B) multipolymer together with other compositions to add as required the colorant comprising pigment and mix, disperse, making dispersible pigment dispersion.Then, when giving curability and alkali-developable to coloured composition of the present invention, in this dispersible pigment dispersion, add (D) described later ~ (F) composition and (C) solvent added further as required and adjuvant, mix.As (C) solvent, as long as composition (A) composition and (B) composition, other compositions described later that form coloured composition are dispersed or dissolved, and do not react with these compositions, there is volatile solvent of appropriateness, just can be suitable for choice for use.

As such solvent, can enumerate such as:

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, 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, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) the alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether,

(gathering) the alkylene glycol monoalkyl ethers acetate esters such as 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, acetic acid 3-methoxybutyl, acetic acid-3-methyl-3-methoxybutyl;

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

The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone;

The diacetate esters classes such as propylene-glycol diacetate, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters;

The alkoxyl carboxylate classes such as 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxybutyl propionic ester;

Other the 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, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester;

Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;

The 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;

The ketols such as diacetone alcohol;

Acid amides or the lactams etc. such as DMF, DMA, 1-METHYLPYRROLIDONE.

In the present invention, solvent can be used alone or mix two or more and use.

In these solvents, when modulating above-mentioned dispersible pigment dispersion, preferably use at least one be selected from (gathering) alkylene glycol monoalkyl ethers class, (gathering) alkylene glycol monoalkyl ethers acetate esters, diacetate esters class and alkoxyl carboxylate class.Its containing proportional in the whole solvents contained by dispersible pigment dispersion be preferably more than 80 quality %, be more preferably more than 90 quality %.

In addition, (gathering) alkylene glycol monoalkyl ethers class, (gathering) alkylene glycol monoalkyl ethers acetate esters, in diacetate esters class and alkoxyl carboxylate class, particularly preferably 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, acetic acid 3-methoxybutyl, dipropylene glycol monomethyl ether acetic acid esters, propylene-glycol diacetate, 1, 3-butylene glycol diacetate esters, 1, 6-hexanediol diacetate esters, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate.

Be not particularly limited the content of solvent, but preferably the total concentration except each composition after desolventizing of this coloured composition becomes the amount of 5 ~ 50 quality %, particularly preferably described total concentration becomes the amount of 10 ~ 40 quality %.By being set as such mode, dispersiveness, stability, coloured composition that coating is good can be obtained.

-(D) crosslinking chemical-

Coloured composition of the present invention can be made to contain (D) crosslinking chemical.Thereby, it is possible to give coloured composition Thermocurable or radiation-curable.Herein, (D) crosslinking chemical refers to the compound of the polymerizable groups with more than 2.As polymerizable groups, such as ethylenic unsaturated group, epoxy ethyl, oxetanylmethoxy, N-alkoxyl-methyl amino etc. can be enumerated.In the present invention, as (D) crosslinking chemical, preferably there is the compound of more than 2 (methyl) acryloyl groups or there is the compound of more than 2 N-alkoxyl-methyl amino.

As the above-mentioned concrete example with the compound of more than 2 (methyl) acryloyl groups, can enumerate and aliphatic polyhydroxy compound and (methyl) acrylic acid be reacted and multifunctional (methyl) acrylate of obtaining, through multifunctional (methyl) acrylate of caprolactone modification, through multifunctional (methyl) acrylate of alkylene oxide modification, make to have polyfunctional carbamate (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate react and obtain, make to have (methyl) acrylate of hydroxyl and anhydride reaction and multifunctional (methyl) acrylate etc. with carboxyl obtained.

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

In addition, as above-mentioned multifunctional (methyl) acrylate through caprolactone modification, the compound recorded in paragraph (0015) ~ (0018) of such as Japanese Unexamined Patent Publication 11-44955 publication can be enumerated.As above-mentioned multifunctional (methyl) acrylate through alkylene oxide modification, oxirane and/or epoxy pronane modification two (methyl) acrylate of bisphenol-A can be enumerated, 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 the above-mentioned compound with more than 2 N-alkoxyl-methyl amino, the compound etc. such as with melamine structure, benzoguanamine structure, urea structure can be enumerated.It should be noted that, melamine structure, benzoguanamine structure refer to have the triazine ring of more than 1 or phenyl replaces the chemical constitution of triazine ring as basic framework, are the concepts also comprising melamine compound, benzoguanamine compound or their condensation product.As the concrete example of compound with more than 2 N-alkoxyl-methyl amino, N can be enumerated, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-tetra-(alkoxy methyl) benzoguanamine, N, N, N, N-tetra-(alkoxy methyl) glycoluril etc.

In these multi-functional monomers, preferably make the aliphatic polyhydroxy compound of more than 3 yuan and (methyl) acrylic acid react and obtain multifunctional (methyl) acrylate, multifunctional (methyl) acrylate through caprolactone modification, polyfunctional carbamate (methyl) acrylate, there is multifunctional (methyl) acrylate, the N of carboxyl, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-tetra-(alkoxy methyl) benzoguanamine.In the high-intensity colored layer, excellent surface smoothness of the colored layer, and it is difficult to produce scum (to dirty me cry), the film remains in the light shielding layer on the substrate unexposed portions and so on, in making more than 3 yuan of aliphatic hydroxy compound (meth) acrylic acid obtained by reaction with a polyfunctional (meth) acrylates, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyfunctional (meth) acrylate having a carboxyl group, and particularly preferable to pentaerythritol triacrylate succinic anhydride is reacted with the compound obtained, so dipentaerythritol pentaacrylate succinic anhydride is reacted with the compound obtained.

In the present invention, (D) crosslinking chemical can be used alone or mix two or more and use.

Relative to 100 mass parts (A) colorant, the content of (D) crosslinking chemical in the present invention is preferably 10 ~ 1,000 mass parts, particularly preferably 20 ~ 500 mass parts.Now, if the content of crosslinking chemical is very few, then likely can not get sufficient curability.On the other hand, if the content of crosslinking chemical is too much, then when giving coloured composition alkali-developable of the present invention, tendencies such as there is alkali-developable reduction, easily produce scum on the substrate in unexposed portion or on light shield layer, film is residual.

-(E) resin glue-

Coloured composition of the present invention can be made to contain (E) resin glue.Thereby, it is possible to give coloured composition alkali-developable and the cohesiveness with substrate.As such resin glue, be not particularly limited, but preferably there is the resin of the acidic functionality such as carboxyl, phenolic hydroxyl group.Wherein, preferably have the polymkeric substance (hereinafter referred to as " carbonyl bearing polymer ") of carboxyl, can enumerate the ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (e1) ") such as with more than 1 carboxyl can the multipolymer of ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (e2) ") of copolymerization with other.

As above-mentioned unsaturated monomer (e1), can enumerate such as (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.

These unsaturated monomers (e1) can be used alone or mix two or more and use.

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

The N-position substituted maleimide amine that N-phenylmaleimide, N-N-cyclohexylmaleimide are such;

Styrene, α-methyl styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to the such aromatic ethenyl compound of vinylbenzyl glycidyl ether, 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 ether (methyl) acrylate, polypropylene glycol (n=2 ~ 10) methyl ether (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, ethylene-oxide-modified (methyl) acrylate of p-cumylphenol, (methyl) glycidyl acrylate, (methyl) acrylic acid 3, 4-epoxycyclohexanecarboxylate, 3-((methyl) acryloyloxymethyl) oxetanes, (methyl) acrylate that 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane is such,

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

The macromonomer etc. at the end of polymer molecular chain with list (methyl) acryloyl group that polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane are such.

These unsaturated monomers (e2) can be used alone or mix two or more and use.

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

As the concrete example of unsaturated monomer (e1) with the multipolymer of unsaturated monomer (e2), such as multipolymer disclosed in Japanese Unexamined Patent Publication 7-140654 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-31308 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 11-258415 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2004-101728 etc. can be enumerated.

In addition; in the present invention; such as Japanese Unexamined Patent Publication 5-19467 publication, Japanese Unexamined Patent Publication 6-230212 publication, Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 09-325494 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 2008-181095 publication etc. Suo Gongkai, also can be used in side chain and there is the carbonyl bearing polymer of the polymerism unsaturated links such as (methyl) acryloyl group as resin glue.

What the resin glue in the present invention utilized GPC (eluting solvent: tetrahydrofuran) to measure is generally 1 by the weight-average molecular weight of polystyrene conversion, 000 ~ 100, and 000, preferably 3,000 ~ 50,000.If this weight-average molecular weight is too small, the reductions such as the residual film ratio of then obtained overlay film, or pattern form, thermotolerance etc. are impaired, and electrical characteristics likely worsen, on the other hand, if weight-average molecular weight is excessive, then resolution reduces, or pattern form is impaired, and likely easily produce dry foreign matter when utilizing gap nozzle mode to be coated with.

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

Resin glue in the present invention can be manufactured by known method, can also control its structure, molecular weight, molecular weight distribution by such as method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, International Publication No. 07/029871 pamphlet etc.

In the present invention, resin glue can be used alone or mix two or more and use.

In the present invention, relative to (A) colorant of 100 mass parts, the content of resin glue is generally 10 ~ 1,000 mass parts, preferably 20 ~ 500 mass parts.If the content of resin glue is very few, then likely such as alkali-developable reduces, or the storage stability of the coloured composition obtained reduces, on the other hand, if the content of resin glue is too much, then colorant concentration reduces relatively, so be likely difficult to reach the aim colour concentration as film.

-(F) Photoepolymerizationinitiater initiater-

Coloured composition of the present invention can be made to contain (F) Photoepolymerizationinitiater initiater.Thereby, it is possible to give coloured composition radiation-sensitive.It is the compound being produced the spike that can cause the polymerization of above-mentioned (D) crosslinking chemical by the exposure of the radioactive ray such as luminous ray, ultraviolet, far ultraviolet, electron ray, X ray for (F) of the present invention Photoepolymerizationinitiater initiater.

As such Photoepolymerizationinitiater initiater, can enumerate such as 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, many rings quinone based compound, diazonium based compound, acid imide sulphonic acid ester based compound etc.

In the present invention, Photoepolymerizationinitiater initiater can be used alone or mix two or more and use.As Photoepolymerizationinitiater initiater, be preferably selected from least one in thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound.

In the present invention in preferred Photoepolymerizationinitiater initiater, as the concrete example of thioxanthones based compound, thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2 can be enumerated, 4-bis-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.

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

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

In addition, when using bisglyoxaline based compound as Photoepolymerizationinitiater initiater, can improve sensitivity in preferably share hydrogen donor.Said " hydrogen donor " means the compound that can provide hydrogen atom to the free radical produced by bisglyoxaline based compound by exposure herein.As hydrogen donor, such as 2-mercaptobenzothiazole, 2-sulfydryl benzo can be enumerated the amine system hydrogen donors such as the mercaptan system hydrogen donors such as azoles, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(lignocaine) benzophenone.In the present invention, hydrogen donor can be used alone or mix two or more use, can improve further sensitivity in, preferably more than a kind mercaptan system hydrogen donor and more than a kind amine system hydrogen donor are combinationally used.

In addition, as the concrete example of above-mentioned triazine based compound, can 2 be enumerated, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(5-methylfuran-2-base) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(furans-2-base) 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, 4-Dimethoxyphenyl) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-etc. have the triazine based compound of halogenated methyl.

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

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

In the present invention, relative to 100 mass parts (D) crosslinking chemical, the content of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 120 mass parts, particularly preferably 1 ~ 100 mass parts.Now, if the content of Photoepolymerizationinitiater initiater is very few, then may be insufficient by exposing being solidified with of carrying out, on the other hand, if this content is too much, then there is formed dyed layer when developing easily from the tendency that substrate comes off.

-adjuvant-

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

As adjuvant, the such as filling agent such as glass, aluminium oxide can be enumerated, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl) class, the surfactants such as fluorine system surfactant, silicon system surfactant, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxy-propyltrimethoxy silane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the closely sealed promoter such as 3-mercaptopropyi trimethoxy silane, the antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-DI-tert-butylphenol compounds, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl) ultraviolet light absorber such as-5-chlorobenzotriazole, alkoxy benzophenone class, the anti flocculants such as sodium polyacrylate, malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, the residue improver such as 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-PD, 2-amino-1,3-propanediol, amino-1, the 2-butylene glycol of 4-, the developability improvers etc. such as mono succinate (2-(methyl) acryloyl-oxyethyl) ester, phthalic acid list (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate.

color filter and manufacture method thereof

The dyed layer that color filter of the present invention possesses use coloured composition of the present invention and formed.

As the method manufacturing color filter, first can enumerate following method.First, light shield layer (black matrix) is formed in the mode divided the part forming pixel as required on a surface of a substrate.Next, after coating is dispersed with the fluid composition of radiation-ray sensitive composition of the present invention of such as red stain on the substrate, carries out prebake, solvent is evaporated, form film.Then, across photomask, this film is exposed, then, use alkaline developer development, removing is dissolved in the unexposed portion of film.Thereafter, by after cure, form the pel array that red pixel pattern is configured to by regulation sequence.

Next, use each colored radiation-sensitive composition of green or blueness, carry out as described above the coating of each colored radiation-sensitive composition, prebake, exposure, development and after cure, form green pixel array and blue pixel array successively on the same substrate.Thus, the color filter being configured with redness, green and blue three primary colors pel array on substrate can be obtained.But in the present invention, the order forming each color pixel is not limited to said sequence.

In addition, black matrix can be formed in the following way, namely, photoetching process is utilized to make desired pattern to be formed the metallic films such as the chromium formed by sputtering or evaporation, but also can use the colored radiation-sensitive composition being dispersed with black colorant, be formed in the same manner as in time forming above-mentioned pixel.

As the substrate used when forming color filter, such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. can be enumerated.

In addition, as required, the pre-treatment that is suitable for can also be implemented in advance, as the chemicals process, Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. that utilize silane coupling agent etc. to carry out to these substrates.

When colored radiation-sensitive composition is coated substrate, the rubbing method that spray-on process, rolling method, method of spin coating (spin-coating method), slot coating processes, scraper rubbing method etc. are suitable can be adopted, but particularly preferably adopt spin-coating method, slot coating processes.

Drying under reduced pressure and heat drying combination carry out by prebake usually.Drying under reduced pressure is usually until reach 50 ~ 200Pa to carry out.In addition, the condition of heat drying is normally 70 ~ 110 DEG C of dryings about 1 ~ 10 minute.

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

As the light source of the radioactive ray used when forming pixel and/or black matrix, can enumerate the LASER Light Source etc. such as lamp source or Argon ion laser, YAG laser, XeCl quasi-molecule laser, nitrogen laser such as 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, but optimal wavelength is at the radioactive ray of 190 ~ 450mm scope.

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

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

Also the such as water-miscible organic solvent such as methyl alcohol, ethanol, surfactant etc. can be added in right amount in above-mentioned alkaline developer.It should be noted that, usually wash after alkali development.

As development treatment method, spray development method, spray development method, immersion development method can be applied, soak and put (puddle) development method etc.Development conditions preferably carries out 5 ~ 300 seconds at normal temperature.

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

The thickness of the pixel of such formation is generally 0.5 ~ 5.0 μm, is preferably 1.0 ~ 3.0 μm.

In addition, as the second method manufacturing color filter, can adopt disclosed in Japanese Unexamined Patent Publication 7-318723 publication, Japanese Unexamined Patent Publication 2000-310706 publication etc., be obtained the method for each color pixel by ink-jetting style.In the method, first, the next door having shade function concurrently is formed on a surface of a substrate.Next, by ink discharge device, the fluid composition of the coloured composition of the present invention being dispersed with such as red stain is sprayed onto in formed next door, then, carries out prebake, solvent is evaporated.Next, after as required this film being exposed, by after cure and make it solidify, form red pattern of pixels.

Then, use each coloured composition of green or blueness, form green pixel pattern and blue pixel patterns successively on the same substrate as described above.Thus, the color filter being configured with redness, green and blue three primary colors pattern of pixels on substrate can be obtained.But in the present invention, the order forming each color pixel is not limited to said sequence.

In addition, above-mentioned next door not only has shade function, and plays the function for making the assorted coloured composition be sprayed onto in dividing regions that colour mixture not occur, so compared with the black matrix used in the first above-mentioned method, thickness is thicker.Therefore, next door uses black radiation-ray sensitive composition to be formed usually.

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

In the pattern of pixels obtained like this, after forming diaphragm as required, form nesa coating by sputtering.After forming nesa coating, and then form separator, also can make color filter.Separator uses radiation-ray sensitive composition to be formed usually, but also can make the separator (black separator) with light-proofness.In this case, use the colored radiation-sensitive composition being 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 obtained like this due to brightness and excitation 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.Such as can adopt such structure: on the substrate different from the driving substrate being configured with thin film transistor (TFT) (TFT), form color filter, driving substrate configures across liquid crystal layer subtend with the substrate being formed with color filter; Can also adopt such structure: on the surface of driving substrate being configured with thin film transistor (TFT) (TFT), form color filter, this substrate configures across liquid crystal layer subtend with the substrate being formed with ITO (indium oxide doped with tin) electrode.A rear structure can significantly improve aperture opening ratio, has and can obtain becoming clear and the advantage of the liquid crystal display cells of high definition.

Color liquid crystal display device of the present invention is except cold cathode fluorescent tube (CCFL:ColdCathodeFluorescentLamp), and can possess with White LED is the backlight unit of light source.As White LED, can enumerate such as, use the red LED with 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 phosphor body obtain the White LED of white light by colour mixture, the White LED of white light is obtained by the colour mixture of blue led and YAG system fluorophor, combined blue LED, orange luminescence fluorophor and green-emitting phosphor body obtain the White LED of white light by colour mixture, combination ultraviolet LED, red light-emitting phosphor, green-emitting phosphor body and blue-light-emitting fluorescent material obtain the White LED etc. of white light by colour mixture.

Color liquid crystal display device of the present invention can apply TN (TwistedNematic, twisted-nematic) type, STN (SuperTwistedNematic, supertwist to row) type, IPS (In-PlanesSwitching, in face switch) type, VA (VerticalAlignment, vertical orientated) liquid crystal mode that type, OCB (OpticallyCompensatedBirefringence, optical compensation curved arrangement) type etc. are suitable.

Embodiment

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

The synthesis > of < (B) multipolymer

Synthesis example 1

In the flask possessing stirrer, by methoxy poly (ethylene glycol) monomethacrylates (manufacture 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 mono-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 in toluene 30mL, carry out 30 minutes nitrogen bubbles.Thereafter slowly stir, make the temperature of reaction solution rise to 57 DEG C, keep this temperature 34 hours, carry out active free radical polymerization.

Next, AIBN211mg and dimethylaminoethyl methacrylate (hereinafter referred to as " DAMA ") 4.1g is dissolved in toluene 20mL, carry out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 34 hours active free radical polymerizations at 57 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, obtain comprising the A block with the repetitive deriving from DAMA and there is the segmented copolymer of B block of the repetitive deriving from PME-200, nBMA and MMA.The multipolymer obtained is denoted as " multipolymer (B-1) ".

Synthesis example 2

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

Next, the DAMA of AIBN and 6.2g of 352mg is dissolved in 20mL toluene, carries out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 24 hours active free radical polymerizations at 60 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, the segmented copolymer of the A block obtaining comprising the repetitive with source DAMA and the B block with the repetitive deriving from PME-200, nBMA, EHMA and MMA.Obtained multipolymer is denoted as " multipolymer (B-2) ".

Synthesis example 3

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

Next, the DAMA of AIBN and 6.2g of 448mg is dissolved in 20mL toluene, carries out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 20 hours active free radical polymerizations at 62 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, obtain comprising the A block with the repetitive deriving from DAMA and there is the segmented copolymer of B block of the repetitive deriving from PME-200, nBMA, EHMA, BzMA and MMA.Obtained multipolymer is denoted as " multipolymer (B-3) ".

Relatively synthesis example 1

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

Next, the DAMA of AIBN and 3.6g of 189mg is dissolved in 20mL toluene, carries out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 24 hours active free radical polymerizations at 60 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, obtain comprising the A block with the repetitive deriving from DAMA and there is the block copolymer solution of B block of the repetitive deriving from PME-200, nBMA, EHMA, BzMA and MMA.Obtained multipolymer is denoted as " multipolymer (b-1) ".

Relatively synthesis example 2

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

Next, the DAMA of AIBN and 6.6g of 342mg is dissolved in 20mL toluene, carries out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 24 hours active free radical polymerizations at 60 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, obtain comprising the A block with the repetitive deriving from DAMA and there is the segmented copolymer of B block of the repetitive deriving from PME-200, nBMA and MMA.Obtained multipolymer is denoted as " multipolymer (b-2) ".

Relatively synthesis example 3

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

Next, the DAMA of AIBN and 5.6g of 290mg is dissolved in 20mL toluene, carries out nitrogen displacement in 30 minutes, the solution of replacing through nitrogen is added in above-mentioned reaction solution, carries out 20 hours active free radical polymerizations at 62 DEG C.Thereafter, by reduced pressure concentration solvent be replaced into propylene glycol methyl ether acetate and make nonvolatile component be 40 quality %.So, obtain comprising the A block with the repetitive deriving from DAMA and there is the segmented copolymer of B block of the repetitive deriving from nBMA, EHMA, BzMA and MMA.Obtained multipolymer is denoted as " multipolymer (b-3) ".

The mensuration > of <Mw and Mw/Mn

Mw and Mn of (B) multipolymer obtained in above-mentioned each synthesis example is measured by the GPC of following specification.Measurement result is shown in Table 1 together with the copolymerization ratios (quality %) of each monomer in (B) multipolymer.

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

Post: KD-G, KF-603, KF-602, KF-601 are combined.

Mobile phase: DMF.

The mensuration > of < amine value

The amine value of (B) multipolymer obtained in above-mentioned each synthesis example is measured with following main points.Measurement result is shown in table 1.

Precision weighing copolymer solution 0.5g to 1mg unit, is placed in glass container.Add acetic anhydride/acetic acid=9/1 (volume ratio) 20ml to dissolve, place 3 hours in room temperature.Thereafter, after adding acetic acid 30ml further, use potential difference (PD) determinator AT-510 (manufacture 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.Amine value (unit mgKOH/g) is calculated by the 0.1mol/l perchloric acid-acetic acid solution dripping quantity of (B) multipolymer and blank test.

Table 1

	Synthesis example 1	Synthesis example 2	Synthesis example 3	Relatively synthesis example 1	Relatively synthesis example 2	Relatively synthesis example 3
							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
Amine value	52	79	79	46	84	71

The preparation of < dispersible pigment dispersion and evaluation >

Embodiment 1

Be used as C.I. naphthol green 58 (manufacture 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 of solvent and propylene glycol monomethyl ether 8 mass parts, utilize ball mill to process, prepare dispersible pigment dispersion (A-1).

The viscosity of the dispersible pigment dispersion obtained is measured with E type viscosity meter (manufacture of Tokyo gauge).Further, the dispersible pigment dispersion obtained is filled in front glass container, leave standstill 14 days in 23 DEG C under air-tight state after, uses E type viscosity meter (manufacture of Tokyo gauge) again to measure viscosity.And, calculate the increment rate of the viscosity of preservation after 14 days relative to the viscosity just prepared, be evaluated as " A " when increment rate is less than 10%, be evaluated as " B " when increment rate is more than 10%.Evaluation result is shown in table 2.

Embodiment 2 ~ 4 and comparative example 1 ~ 5

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

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

Table 2

The synthesis > of < resin glue

Synthesis example 4

In the flask possessing cooling tube and stirring machine, nBMA, 15.0g hydroxyethyl methylacrylate of BzMA, 20.0g of 25.0g, 20.0g styrene and 20.0g methacrylic acid are dissolved in 200g propylene glycol methyl ether acetate, and then add 3.0g AIBN and 5.0g 2,4-diphenyl-4-methyl-1-pentene, its post-purge 15 minutes nitrogen.Nitrogen stirs and nitrogen bubble reactant liquor, while be heated to 80 DEG C, is polymerized 5 hours after purging, and obtains the solution containing 33 quality % resin glues (E-1) thus.Weight-average molecular weight=10 by polystyrene conversion that this resin glue (E-1) utilizes GPC (eluting solvent: tetrahydrofuran) to measure, 500, ratio=2.5 of the weight-average molecular weight by polystyrene conversion that utilizes GPC (eluting solvent: tetrahydrofuran) to measure and number-average molecular weight.

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

the preparation of colored radiation-sensitive composition

Embodiment 5

By dispersible pigment dispersion (A-1) 100 mass parts, as resin glue (E-1) solution 33.5 mass parts of resin glue, as M-402 (dipentaerythritol acrylate is major component) 9.7 mass parts that the Toagosei Co., Ltd of crosslinking chemical manufactures, as 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone (the trade name Irgacure369 of Photoepolymerizationinitiater initiater, CibaSpecialtyChemicals society manufactures) 4.3 mass parts and mixing as the 3-ethoxyl ethyl propionate of solvent, prepare the colored radiation-sensitive composition that solid component concentration is 20 quality %.

come off the evaluation of time

Use spin coater to be coated with on the glass substrate by the colored radiation-sensitive composition obtained, carry out 2 minutes prebake with the heating plates of 100 DEG C, form the film of thickness 2.5 μm.Next, after this substrate cool to room temperature, to the film on substrate, use high-pressure sodium lamp will to comprise the radioactive ray of each wavelength of 365nm, 405nm and 436nm with 1,000J/m across photomask ²exposure each film is exposed.Thereafter, by being sprayed onto on the film on substrate by 0.04 % by weight potassium hydroxide aqueous solution of 23 DEG C, carry out spray development.Now, the time (coming off the time) till the film in unexposed portion is peeled off completely is measured.So, be evaluated as " A " when the time of coming off is less than 60 seconds, be evaluated as " B " when the time that comes off is more than 60 seconds and less than 120 seconds, be evaluated as " C " when the time that comes off is more than 120 seconds and less than 180 seconds, be evaluated as " D " when the time that comes off is more than 180 seconds.This time is shorter, and developing powder is faster, has the advantage that can shorten the pitch time that color filter manufactures.Evaluation result is listed in table 3.

the evaluation of colorimetric properties

Use spin coater to be coated with on the glass substrate by the colored radiation-sensitive composition obtained, then, carry out 2 minutes prebake with the heating plates of 100 DEG C, form 3 films that thickness is different.Next, after these substrate cool to room temperature, to the film on substrate, use high-pressure sodium lamp will not to comprise the radioactive ray of each wavelength of 365nm, 405nm and 436nm with 1,000J/m across photomask ²exposure each film is exposed.Thereafter, cure after carrying out 20 minutes in 180 DEG C, substrate forms cured film.To obtained 3 cured film, use color analysis instrument (MCPD2000 that Otsuka Electronics Co., Ltd. manufactures) with the chromaticity coordinate value (x, y) in illuminant-C, 2 degree of visual angle mensuration CIE colour systems and values (Y).Chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.590 by measurement result and values (Y).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 preparation and the evaluation of colored radiation composition similarly to Example 5.Evaluation result is listed in table 3.

Table 3

Claims (7)

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

A: the colorant comprising pigment,

B: comprise A block and B block, amine value is more than 50mgKOH/g and less than the segmented copolymer of 80mgKOH/g, described A block has the repetitive (1) that more than 60 quality % represent by following formula (1), described B block has the repetitive that the repetitive (2) that represents by following formula (2) and formula (3) represent, the copolymerization ratios of the repetitive that the repetitive that the described formula (2) in described B block represents/this formula (3) represents is 1/99 ~ 30/70 by quality ratio, and

C: solvent,

Further, the weight-average molecular weight Mw of described B block multipolymer and the ratio Mw/Mn of number-average molecular weight Mn is 1.0 ~ 1.8,

In formula (1), X is-COO-R ⁸-(*) base, described R ⁸represent that carbon number is the alkylidene of 2 ~ 10, (*) represents the binding site be combined with N, R ¹represent hydrogen atom or methyl, R ²and R ³represent that hydrogen atom maybe can have the alkyl of substituent chain or ring-type independently of each other, R ²and R ³can be combined with each other and form ring texture,

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

In formula (3), R ⁹represent alkyl, the aryl or aralkyl of chain or ring-type, R ¹⁰represent hydrogen atom or methyl.

2. coloured composition as claimed in claim 1, wherein, containing phthualocyanine pigment as colorant.

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

4. coloured composition as claimed in claim 3, wherein, contains dyestuff further as colorant.

5. coloured composition as claimed in claim 3, wherein, further containing F Photoepolymerizationinitiater initiater.

6. a color filter, it possesses and uses coloured composition according to any one of claim 2 ~ 5 and the dyed layer that formed.

7. a color liquid crystal display device, it possesses color filter according to claim 6.