CN1987649A - Photo setting composition and color filter - Google Patents

Photo setting composition and color filter Download PDF

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Publication number
CN1987649A
CN1987649A CN 200610172462 CN200610172462A CN1987649A CN 1987649 A CN1987649 A CN 1987649A CN 200610172462 CN200610172462 CN 200610172462 CN 200610172462 A CN200610172462 A CN 200610172462A CN 1987649 A CN1987649 A CN 1987649A
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acid
mentioned
compound
composition
pigment
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真崎庆央
牛丸晶
冲田务
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Fujifilm Electronic Materials Co Ltd
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Fujifilm Electronic Materials Co Ltd
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Abstract

The present invention provides a light-solidified composition, wherein includes colorant, alkali-dissolved resin, polymerized compound and photopolymerization initiator. The acid number of alkali-dissolved resin is 100 KOHmg/g to 300 KOHmg/g. The photopolymerization initiator at least includes the compounds containing SH group, the compounds of the following formula (I), and the compound of the following famula (II). In the formula (I), X represents halogen atom, n is the integer of 1 to 4. In the formula (II), R is C1-4 alkyl.

Description

Photocurable composition and color filter
Technical field
The present invention relates to be fit to be produced on the Photocurable composition and the color filter of the color filter that uses in liquid crystal display cells or the solid-state imager.Particularly relate to the high-accuracy color filter that uses in the little liquid crystal indicator (LCD) of the size that is fit to be produced on display frame and can guarantee light sensitivity and good Photocurable composition and the color filter of development tolerance with low exposure.
Background technology
Color filter is an indispensable member of formation in the liquid crystal indicator.
The color filter that is used for the small size LCD such as display part of mobile phone or digital camera, following described trend etc. is arranged, promptly, in order to improve picture element density and to improve colorrendering quality, show size generation microminiaturization, perhaps for example added that cyan constituted 4 look demonstrations etc. in the image demonstration with RGB three looks in the past with pixel unit.Even demonstration is become under the situation of the polychrome more than four looks from the past three looks with pixel, pixel also has the trend of microminiaturization.For example, with regard in the past monitor usefulness or the TV usefulness color filter of LCD, the size of pixel is more than the 80 μ m.But under the situation that is used for the smaller display part of mobile telephone terminal or digital camera equidimension, its pixel size is below the 50 μ m.
Forming with photoetching process under the situation of color filter, if pixel diminishes, then at the interface of pixel and substrate, the bottom surface of pixel is developed the liquid dissolving easily and corrodes, and peels off from substrate, has the problem that can't form pixel thus.
Here, above-mentioned " size of pixel " under the situation of the common pixel that is shaped as rectangle, is meant the minimum edge of this rectangular pixels.Promptly if rectangle just is meant its minor face.This is because the bottom surface of minimum edge is developed the liquid dissolving easily and corrodes.
At the problems referred to above, the spy open disclose in the flat 10-104412 communique by and can form the Photocurable composition and the color filter of pattern with ISO with Photoepolymerizationinitiater initiater and mercaptan based compound.
In addition, the spy opens and discloses in the 2000-221675 communique and with the color filter Photocurable composition of lophine dimer and mercaptan based compound.
And then the spy opens and discloses the outstanding Photocurable composition of photo-curable that contains benzophenone, imidazole compound and have the compound of mercapto in the 2000-284478 communique.
But the mercaptan based compound that is contained in wherein can make development decline, so the exploring degree of pixel might become abundant inadequately.
Summary of the invention
The objective of the invention is to, provide be fit to be manufactured on the high-accuracy color filter that uses in the little liquid crystal indicator of display frame size (LCD), can guarantee Photocurable composition that light sensitivity and development tolerance are good and the color filter that uses said composition to form with low exposure.
In view of above-mentioned truth, the inventor etc. concentrate on studies, found that, the Photocurable composition that contains the bigger alkali soluble resins of Photoepolymerizationinitiater initiater as described below and acid number by use, can address the above problem, thereby finished the present invention, described Photoepolymerizationinitiater initiater contains these three kinds of compounds of compound, lophine dimer and Michler's keton of SH base.
That is, the present invention realizes by following scheme.
＜1〉a kind of Photocurable composition wherein contains colorant, alkali soluble resins, polymerizable compound and Photoepolymerizationinitiater initiater,
The acid number of above-mentioned alkali soluble resins is more than the 100KOHmg/g, below the 300KOHmg/g,
Above-mentioned Photoepolymerizationinitiater initiater contains the compound of SH base at least, with the compound of following formula (I) expression and the compound of representing with following formula (II).
[changing 1]
Figure A20061017246200051
(in formula (I), X represents halogen atom, and n represents 1～4 integer.)
[changing 2]
Figure A20061017246200061
(in formula (II), R represents that carbon number is 1～4 alkyl.)
＜2〉above-mentioned＜1〉the middle Photocurable composition of putting down in writing, the compound of the wherein above-mentioned SH of containing base is at least a kind that selects from the compound with following formula (III)～(V) expression.
[changing 3]
Figure A20061017246200062
(HSR 1) mC(R 2SH) n (V)
(in formula (III), (IV), R is independent separately, and expression hydrogen atom, carbon number are 1～6 alkyl or nitro, and A represents N, S or O.In formula (V), R 1, R 2Independent separately, the expression carbon number is 1～6 alkyl, and m and n represent 1～3 integer, m+n=4 independently of one another.)
＜3〉above-mentioned＜1〉or＜2〉the middle Photocurable composition of putting down in writing, wherein above-mentioned polymerizable compound is the compound with alkylene oxide chain.
＜4〉a kind of color filter wherein has and uses above-mentioned＜1 〉～＜3 in the demonstration pixel of the polychrome that forms by photoetching process of the Photocurable composition of any record.
＜5〉above-mentioned＜4〉color filter of record, wherein above-mentioned demonstration is more than the 5 μ m, below the 50 μ m with the size of pixel.
＜6〉above-mentioned＜4〉or＜5〉record color filter, wherein have the above above-mentioned demonstration pixel of 4 looks.
By the present invention, can provide to be fit to be produced on the high-accuracy color filter that uses in the little liquid crystal indicator of display frame size (LCD), can to guarantee light sensitivity and the good Photocurable composition of development tolerance with low exposure.
In addition, by the present invention, can use above-mentioned Photocurable composition to provide to be suitable for the high-accuracy color filter of the little liquid crystal indicator of display frame size (LCD).
Embodiment
＜Photocurable composition 〉
Photocurable composition of the present invention (below, be also referred to as " composition of the present invention "), contain colorant, alkali soluble resins, polymerizable compound and Photoepolymerizationinitiater initiater, the acid number of above-mentioned alkali soluble resins be 100KOHmg/g above, below the 300KOHmg/g, above-mentioned Photoepolymerizationinitiater initiater contains the compound of SH base at least, with the compound of following formula (I) expression and the compound of representing with following formula (II).
Here, " acid number of alkali soluble resins is 100～300KOHmg/g " is meant that the acid number of above-mentioned alkali soluble resins integral body is 100～300KOHmg/g.
That is, using under the situation of a kind of alkali soluble resins, the acid number of employed alkali soluble resins is 100～300KOHmg/g, and situation with alkali soluble resins more than 2 kinds under, the total acid number that is meant alkali soluble resins is 100～300KOHmg/g.
In the composition of the present invention, can contain solvent or pigment derivative, surfactant as required, contain the spreading agents such as polymkeric substance of polar group.
By containing spreading agent, can improve the stability of Photocurable composition of the present invention, the stability when improving long preservation.
Below, each composition that contains in the composition of the present invention is elaborated.
＜alkali soluble resins 〉
At least contain a kind of alkali soluble resins in the Photocurable composition of the present invention.
With regard to the alkali soluble resins that uses in the composition of the present invention, as long as having the acidic functionality (for example carboxyl, phenol hydroxyl etc.) and the acid number of alkali soluble resins that show alkali-developable is in the scope of 100～300KOHmg/g, just be not particularly limited, wherein, from improving the viewpoint of alkali-developable, acid number is preferably 120～300KOHmg/g, is preferably 140～300KOHmg/g especially.
Acid number by making above-mentioned alkali soluble resins for example is not vulnerable to the influence of the compound that contains SH etc. beyond the alkali soluble resins in above-mentioned scope, can improve alkali-developable, thereby be preferred.
Above-mentioned alkali soluble resins is, (polymerizable compound is as required when containing the alkylene oxide chain) do not contain the adhesive ingredients of alkylene oxide chain when polymerizable compound described later does not contain the alkylene oxide chain, can improve when developing non-exposure portion for the dissolubility of developer solution, effectively prevent the residue that develops, form sharp-pointed pattern.
As concrete example, the wire organic high molecular polymer that preferably dissolves in organic solvent and can develop with weak alkaline aqueous solution.
As such wire organic high molecular polymer, can enumerate the polymkeric substance that has carboxylic acid at side chain, for example, the spy open clear 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy open clear 59-53836 number, spy open put down in writing in clear 59-71048 number each communique, methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc., in addition, the acid cellulose derivant that equally has a carboxylic acid at side chain also can use.In addition, materials that form to the polymkeric substance addition acid anhydrides with hydroxyl etc. and polycarboxylated styrene are resin, polysiloxane series resin, poly-((methyl) acrylic acid 2-hydroxyl ethyl ester), polyvinyl pyrrolidone or polyoxyethylene, polyvinyl alcohol (PVA) etc., also can use.
Wherein, the preferred acrylic acid series copolymer that carries out the combination of multiple monomer easily and carry out MOLECULE DESIGN easily more preferably will contain the monomer of phosphate and contain the acrylic acid series copolymer of the monomer of alkylene oxide chain as the comonomer composition.
This acrylic acid series copolymer can synthesize by making above-mentioned monomer component by free radical polymerization, coordination polymerization, cationic polymerization, anionic polymerisation etc. copolymerization take place usually.
As alkali soluble resins, monomer 1) and contain the monomer (monomer 2) of alkylene oxide chain preferably use monomer (the sour composition monomer: that contains phosphate to the major general as acrylic acid series copolymer of comonomer composition (below, be also referred to as " alkali soluble resins among the present invention ") etc.
In addition, the alkali soluble resins among the present invention can synthesize by making above-mentioned monomer component by free radical polymerization, coordination polymerization, cationic polymerization, anionic polymerisation etc. copolymerization take place usually.
The polystyrene conversion weight-average molecular weight (Mw) of utilizing GPC to measure of the alkali soluble resins among the present invention, preferred 3,000～100,000, more preferably 5,000～30,000.
(monomer that contains phosphate)
With regard to regard to the monomer that contains phosphate of the copolymer composition of the alkali soluble resins among the present invention,, just can use so long as have the monomer of ethene unsaturated group and phosphate with being not particularly limited.
From easy polymerization, the viewpoint of starting with easily, wherein, preferably at least a kind of phosphate ester monomer selecting from phosphoric acid methacryloxy ethyl ester, two (methacryloxyethyl) esters of phosphoric acid, methacryloxy ethylene glycol phosphate particularly, can be enumerated [H 2C=CR 1-CO-O-(CH 2) n-O-] mPO (OH) 3-m, [H 2C=CR 2-CO-O-(C 2H 5O) n-O-] mPO (OH) 3-mDeng.Here, m is 1 or 2 integer, and n is 1～20, preferred 1～10, most preferably 1～5 integer, R 1, R 2Independent separately, be H or CH 3
Among the present invention, as the monomer component of the above-mentioned monomer that contains phosphate content (mol ratio), preferred 5～35 moles of %, more preferably 10～25 moles of % with respect to alkali soluble resins.If the content of the above-mentioned monomer that contains phosphate is not in above-mentioned scope, alkali solubility can reduce, and in addition, if surpass above-mentioned scope, can reduce for the dissolubility of solvent.
(monomer that contains the alkylene oxide chain)
With regard to regard to the monomer that contains the alkylene oxide chain of the copolymer composition of the alkali soluble resins among the present invention, so long as have the monomer that can carry out polymerization of alkylene oxide chain, just be not particularly limited, preferably use (methyl) acrylate monomer that contains polyalkyleneimine chain of following general formula (1) expression.
[changing 4]
General formula (1)
In general formula (1), R 3Expression hydrogen atom or methyl.In addition, in general formula (1), (EO) nThe expression polyoxyethylene chain, (PO) mThe expression polyoxypropylene chains, (BO) lExpression polyoxy butylene chain.
In general formula (1), (EO) n(PO) m(BO) lBinding sequence can arbitrary decision.Above-mentioned polyoxyethylene chain (EO) nBe the addition product of oxirane, the adduct number of oxirane is represented with n.
In addition, above-mentioned polyoxypropylene chains (PO) mBe the addition product of epoxypropane, the adduct number of epoxypropane is represented with m.And then, above-mentioned polyoxy butylene chain (BO) lBe meant the addition product of epoxy butane, the adduct number of epoxy butane is represented with l.
In general formula (1), n represents 2～20 integer, and m and l represent 0～10 integer respectively.As said n, preferred 4～15 integer, as above-mentioned m, preferred 0～10 integer, as above-mentioned l, preferred 0～10 integer.Wherein, 2≤(m+n+l)≤30, preferred 4≤(m+n+l)≤20.
R in the general formula (1) 4Expression hydrogen atom, carbon number are 1～12 straight or branched alkyl or with the group of following general formula (2) expression, preferably straight or branched alkyl.As this straight or branched alkyl, can enumerate carbon number and be 1～4 alkyl, particularly, can enumerate methyl, ethyl, propyl group, butyl, isopropyl, isobutyl.
[changing 5]
General formula (2)
In general formula (2), R 5Expression hydrogen atom or carbon number are 1～13 straight or branched alkyl, and preferred hydrogen atom or carbon number are 1～3 alkyl.As abovementioned alkyl, preferred carbon number is 1～3 alkyl, particularly, and preferable methyl, ethyl, isopropyl.In addition, p represents 0～5 integer, preferred 0～2 integer.
Among the present invention, as with the monomer component of (methyl) acrylate monomer that contains polyoxyethylene chain of above-mentioned general formula (1) expression content (mol ratio), preferred 2～20 moles of %, more preferably 3～10 moles of % with respect to alkali soluble resins.In addition, if with (methyl) acrylate monomer that contains polyoxyethylene chain of above-mentioned general formula (1) expression contain the above-mentioned scope of quantity not sufficient, the screening characteristics of coating liquid on substrate that then contains Photocurable composition is insufficient, can't effectively reach effect of the present invention.In addition, if surpass above-mentioned scope, then the dispersiveness of colorant or dissolubility reduce sometimes.
As (methyl) acrylate monomer that contains polyoxyethylene chain with above-mentioned general formula (1) expression, for example can enumerate oxirane modification cresols acrylate (m=4, trade name: ア ロ ニ Star Network ス TO-901), oxirane modified acroleic acid dodecyl ester (m=10, trade name: ア ロ ニ Star Network ス TO-950), oxirane modified acroleic acid tridecyl ester (m=10, trade name: ア ロ ニ Star Network ス TO-951), 2-ethylhexyl polyethylene glycol acrylate (m=4, trade name: ア ロ ニ Star Network ス TO-946), 2-ethylhexyl polyethylene glycol acrylate (m=8, trade name: ア ロ ニ Star Network ス TO-947), 2-ethylhexyl polyethylene glycol acrylate (m=12, trade name: ア ロ ニ Star Network ス TO-948), 2-ethylhexyl polyethylene glycol acrylate (m=20, trade name: ア ロ ニ Star Network ス TO-949), more than be East Asia synthetic (strain) system product;
Ethoxy-diglycol acrylate (m=2, trade name: ラ イ ト ア Network リ レ one ト EC-A), methoxyl-triethylene glycol acrylate (m=3, trade name: ラ イ ト ア Network リ レ one ト MTG-A), methoxyl-polyethylene glycol acrylate (m=9, trade name: ラ イ ト ア Network リ レ one ト 130A), phenoxy group-polyethylene glycol acrylate (m=2, trade name: ラ イ ト ア Network リ レ one ト P-200A), nonyl phenyl-polyoxyethylene chain addition product acrylate (m=4, trade name: ラ イ ト ア Network リ レ one ト NP-4EA), nonyl phenyl-polyoxyethylene chain addition product acrylate (m=8, trade name: ラ イ ト ア Network リ レ one ト NP-8EA), more than be common prosperity society chemistry (strain) system product;
Polyethylene glycol acrylate (m ≈ 6～8, trade name: Block レ Application マ one AE-350), polyethylene glycol methacrylate-styrene polymer (m ≈ 2, trade name: Block レ Application マ one PE-90), polyethylene glycol methacrylate-styrene polymer (m ≈ 4～5, trade name: Block レ Application マ one PE-200), polyethylene glycol methacrylate-styrene polymer (m ≈ 7～9, trade name: Block レ Application マ one PE-350), methoxy poly (ethylene glycol) one acrylate (m ≈ 2, trade name: Block レ Application マ one AME-400), methoxy polyethylene glycol methacrylate-styrene polymer (m ≈ 2, trade name: Block レ Application マ one PME-100), methoxy polyethylene glycol methacrylate-styrene polymer (m ≈ 4, trade name: Block レ Application マ one PME-200), methoxy polyethylene glycol methacrylate-styrene polymer (m ≈ 9, trade name: Block レ Application マ one PME-400), polypropylene glycol methacrylate (n ≈ 9, trade name: Block レ Application マ one PP-500), polypropylene glycol methacrylate (n ≈ 12, trade name: Block レ Application マ one PP-800), polyglycol polypropylene glycol methacrylate (m=7, n=3, trade name: Block レ Application マ one 70PEP-370B), polyglycol polytetramethylene glycol methacrylate (m=10, n=5, trade name: Block レ Application マ one 50PET-800), octyloxy polyglycol polypropylene glycol monomethyl acrylate (m ≈ 8, n ≈ 6, trade name: Block レ Application マ one 50POEP-800B), octyloxy polyglycol polyoxy propylene glycol monomethyl acrylate (m ≈ 8, n ≈ 6, trade name: Block レ Application マ one 50AOEP-800B), more than be Japanese grease (strain) system product;
NK ester M-20G), methoxyl diglycol methacrylate (m=4, trade name: NK ester M-40G), methoxyl diglycol methacrylate (m=9, trade name: NK ester M-90G), phenoxy group diglycol acrylate (m=2, trade name: NK ester AMP-20G), more than be Xin Zhong village chemical industry (strain) system product etc. methoxyl diglycol methacrylate (m=2, trade name:.
(other monomer components)
-monomer 3-
In the alkali soluble resins among the present invention, preferably when containing above-mentioned monomer 1～2, also contain methacrylic acid benzyl ester (BzMA), styrene (St), methyl styrene, acrylic acid benzyl ester etc. (below, be sometimes referred to as " monomer 3 ") as one of monomer component.Wherein, preferable methyl acrylic acid benzyl ester.By the monomer component of further use methacrylic acid benzyl ester, can improve the intensity of filming that obtains by composition of the present invention as the alkali soluble resins among the present invention.As above-mentioned methacrylic acid benzyl ester, be fit to use material with following general formula (3) expression.
[changing 6]
General formula (3)
In general formula (3), R 6Expression hydrogen atom or methyl.R 7Expression hydrogen atom, carbon number are 1～6 alkyl, preferred hydrogen atom, methyl, ethyl.In addition, in general formula (3), q represents 0～5 integer, preferred 0～2.
Among the present invention, as the above-mentioned methacrylic acid benzyl ester of monomer component content (mol ratio) with respect to alkali soluble resins, preferred 50 moles below the %, particularly, further preferred 0～40 mole of %.If the content of methacrylic acid benzyl ester surpasses 50 moles of %, the thixotropism of solution (thixotropy) increases, and the film thickness uniformity of coated film easily descends sometimes.
-monomer 4-
And then, in the alkali soluble resins among the present invention, can when containing above-mentioned monomer 1～2, contain and be selected from (methyl) hydroxy-ethyl acrylate (HEMA, HEA), in (methyl) hydroxypropyl acrylate and 2-hydroxyl-3-phenoxy propyl (methyl) acrylate at least a kind (below, be called " monomer 4 " sometimes) is as one of monomer component.Also use monomer 4 by monomer component, can improve the thermotolerance of filming that obtains by composition of the present invention as the alkali soluble resins among the present invention, and then, can form high the filming of connecting airtight property with substrate etc., can prevent films is stripped from.
As above-mentioned monomer 4, preferred especially (methyl) hydroxy-ethyl acrylate.As above-mentioned monomer 4, for example, can enumerate hydroxy propyl methacrylate (trade name: Block レ Application マ one P, Japanese grease (strain) system), 2-hydroxyl-3-phenoxy propyl (methyl) acrylate (trade name: ア ロ ニ Star Network ス M-5700, East Asia chemistry (strain) system), acrylic acid 2-hydroxypropyl acrylate (trade name: ラ イ ト エ ス テ Le HOP-A, common prosperity society chemistry (strain) system).
Among the present invention,, be preferably 30 moles below the % as the monomer component of above-mentioned monomer 4 content (mol ratio) with respect to alkali soluble resins, more preferably 20 moles below the %, particularly, further preferred 3～10 moles of %.If the content of above-mentioned monomer 4 surpasses 30 moles of %, then the thixotropism as coating liquid will increase, and the film uniformity that is coated with of coated film descends sometimes easily.
(other alkali soluble resinss)
In composition of the present invention, as above-mentioned alkali soluble resins, the alkali soluble resins in the present invention, can and with the alkali soluble resins of other structure.For example, multipolymer that preferably constitutes by (methyl) acrylic acid and methacrylic acid benzyl ester or the multipolymer that constitutes by (methyl) acrylic acid, methacrylic acid benzyl ester and (methyl) hydroxy-ethyl acrylate etc.
Under the situation of alkali soluble resins as above-mentioned alkali soluble resins of using separately among the present invention, the containing ratio of the alkali soluble resins in the composition of the present invention is 10～50 quality % with respect to whole solid constituent, more preferably 10～40 quality %.
In addition, and situation with the alkali soluble resins of other structure under, total containing ratio of other alkali soluble resins in the composition of the present invention is preferably 10～50 quality %.In composition of the present invention,, can't carry out alkali smoothly and develop if the content of alkali soluble resins is very few.On the other hand, if too much, as the viscosity increased of coating liquid, the applied thickness homogeneity will deterioration, and it is uneven to be easy to generate coating, and the tolerance of perhaps developing sometimes also can reduce.
＜colorant 〉
In the composition of the present invention, painted in order to make composition, contain colorant.
As being used for colorant of the present invention, can use a kind or mix to use two or more known in the past various pigment, dyestuff separately.
As the pigment that can be used for composition of the present invention, can use known in the past various inorganic pigments or organic pigment.In addition, no matter be inorganic pigment or organic pigment, consider the high permeability of color filter pixel, the tiny as far as possible material of all preferred use, if also consider the operability of solidification compound as coating fluid, the mean grain size of above-mentioned pigment is preferably 0.01 μ m～0.1 μ m, more preferably 0.01 μ m～0.05 μ m.
In addition, as above-mentioned inorganic pigment, can enumerate metallic compounds such as metal oxide, metal complex salt, particularly, can enumerate the oxide of metals such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the composite oxides of above-mentioned metal.
As above-mentioned organic pigment, for example, can enumerate following material.
C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I. pigment orange 36,38,43,71;
C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C.I. pigment violet 19,23,32,39;
C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I. pigment Green 7,36,37;
C.I. pigment brown 25,28;
C.I. pigment black 1
Deng.
In the present invention, can especially preferably use the pigment that has the N atom of alkalescence in the structural formula of pigment.These pigment with N atom of alkalescence can show good dispersiveness in composition of the present invention.Still not fully aware of about its mechanism, but can be speculated as because of the good cause of the affinity of optical polymerism compound and pigment.
As the pigment that preferably uses in the present invention, can enumerate following pigment.But, the present invention is not limited to these.
C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,
C.I. pigment orange 36,71,
C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264,
C.I. pigment violet 19,23,32,
C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66,
C.I. pigment black 1
These organic pigments can use separately, can also use various combination in order to improve excitation.The concrete example of combinations thereof is as follows.
For example, use pigment as green (G), the preferred halogenated phthalocyanines series pigments that uses separately, perhaps, preferably using halogenated phthalocyanines series pigments and two diazonium is that yellow uitramarine, Kui phthalein ketone are that yellow uitramarine, azomethine are that yellow uitramarine or isoindoline are the potpourri of yellow uitramarine.
For example, as such example, preferred
C.I. pigment Green 7,36,37 and
C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185
Potpourri.
The mass ratio of viridine green and yellow uitramarine is preferably 100: 5～and 100: 150.Be difficult to suppress the transmitance of 400nm～450nm light if above-mentioned mass ratio less than 100: 5, becomes sometimes, can't improve excitation.In addition, if surpass 100: 150, predominant wavelength can be near long wavelength side, and the deviation alternate with the NTSC aim colour can increase.As above-mentioned mass ratio, preferred especially 100: 30～100: 120 scope.
Green in the composition of the present invention (G), preferably accounts in the nonvolatile component of composition more than the 38 quality % from the viewpoint of look characteristic with the containing ratio of pigment, more preferably 38～70 quality %, preferred especially 40～60 quality %.
If colorant is very few, then can't obtain the colourity that is fit to as color filter sometimes.On the other hand, if too much, photocuring can't fully carry out, reduce as film strength, the development tolerance when perhaps alkali develops will become narrow.
As using pigment as the redness (R) of colorant in the Photocurable composition of the present invention, can use anthraquione pigmentss, perylene series pigments, diketopyrrolopyrroles series pigments separately, the mixed stocker pigment or their central at least a and two diazonium that have perhaps made up these reds are that yellow uitramarine, isoindoline are that yellow uitramarine or Kui phthalein ketone are the mixed stocker pigment of yellow uitramarine etc.
For example, as anthraquione pigmentss, can enumerate C.I. paratonere 177; As the perylene series pigments, can enumerate C.I. paratonere 155, C.I. paratonere 224; As the diketopyrrolopyrroles series pigments, can enumerate C.I. paratonere 254.
Considering from the angle of color reproduction, also can be the potpourri with C.I. pigment yellow 13 9.In addition, the mass ratio of red pigment and yellow uitramarine be preferably 100: 5～100: 50.If less than 100: 5, then be difficult to the transmitance of inhibition from 400nm to 500nm light, can't improve excitation.In addition, surpassing under 100: 50 the situation, predominant wavelength will be near short wavelength side, can increase with the deviation of NTSC target form and aspect.Particularly as above-mentioned mass ratio, 100: 10～100: 30 scope is only.In addition, being used in combination under the situation of red pigment, can regulate according to colourity.
In Photocurable composition of the present invention, can be used as the containing ratio of the red pigment (R pigment) of colorant, viewpoint from the look characteristic, preferably in the nonvolatile component of composition, account for more than the 35 quality %, 35～75 quality % more preferably, more preferably 37～70 quality % are preferably 39～65 quality % especially.
If colorant is very few, there is the trend can not get the colourity that is fit to as color filter.On the other hand, if too much, photocuring can not fully carry out, reduce as film strength, in addition, the development tolerance when alkali develops has the narrow trend of stenosis.
As in Photocurable composition of the present invention, using pigment as the blueness (B) of colorant, can use phthualocyanine pigment separately, perhaps use phthualocyanine pigment with dioxazine is the potpourri of violet pigment.For example preferred C.I. pigment blue 15: 6 and the potpourri of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100: 0～and 100: 30, more preferably below 100: 10.
The containing ratio of the blue pigment in the composition of the present invention (B pigment), from the viewpoint of look characteristic, preferably in the nonvolatile component of composition, account for more than the 17 quality %, more preferably 17～70 quality %, more preferably 19～65 quality % are preferably 21～60 quality % especially.
If colorant is very few, there is the trend can not get the colourity that is fit to as color filter.On the other hand, if too much, photocuring can not fully carry out, reduce as film strength, in addition, the development tolerance when alkali develops has the trend that becomes narrow.
In Photocurable composition of the present invention, can be used as the containing ratio of the green pigment (C pigment) of colorant, viewpoint from the look characteristic, preferably in the nonvolatile component of composition, account for more than the 20 quality %, 25～70 quality % more preferably, more preferably 27～60 quality % are preferably 30～55 quality % especially.
If colorant is very few, there is the trend can not get the colourity that is fit to as color filter.If too much on the other hand, photocuring can not fully carry out, and reduces as film strength, and in addition, the development tolerance when alkali develops has the trend that becomes narrow.As the above-mentioned cyan pigment in the composition of the present invention, for example can enumerate an amount of pigment that has mixed blue 15:3 of blue pigment C.I. and yellow uitramarine C.I. pigment yellow 13 8,139,150,185 etc.
In addition, the mass ratio of blue pigment and yellow uitramarine be preferably 100: 45～100: 100.
In Photocurable composition of the present invention, can be used as the containing ratio of the magenta pigment (M pigment) of colorant, viewpoint from the look characteristic, preferably in the nonvolatile component of composition, account for more than the 20 quality %, 25～70 quality % more preferably, more preferably 27～60 quality % are preferably 30～55 quality % especially.
If colorant is very few, there is the trend can not get the colourity that is fit to as color filter.If a side is too much, photocuring can not fully carry out, and reduces as film strength, and in addition, the development tolerance when alkali develops has the trend that becomes narrow.
As the above-mentioned magenta pigment in the composition of the present invention, for example can enumerate red pigment C.I. red 81,122,209 etc.
In Photocurable composition of the present invention, can be used as the containing ratio of the yellow uitramarine (Y pigment) of colorant, viewpoint from the look characteristic, preferably in the nonvolatile component of composition, account for more than the 20 quality %, 25～70 quality % more preferably, more preferably 27～60 quality % are preferably 30～55 quality % especially.
If colorant is very few, there is the trend can not get the colourity that is fit to as color filter.On the other hand, if too much, photocuring can not fully carry out, reduce as film strength, in addition, the development tolerance when alkali develops has the trend that becomes narrow.
As the above-mentioned yellow pigment in the composition of the present invention, for example can enumerate yellow uitramarine C.I. Huang 138,139,150,185 etc.
In composition of the present invention, in the scope that does not influence effect of the present invention, can use dyestuff as colorant.
Dyestuff as adding in the present composition is not particularly limited, and can use the known dyestuff that is used for color filter in the past.For example, can use the spy and open clear 64-90403 communique, the spy opens clear 64-91102 communique, Te Kaiping 1-94301 communique, Te Kaiping 6-11614 communique, the spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 instructionss, United States Patent (USP) the 5th, 667, No. 920 instructionss, United States Patent (USP) the 5th, 059, No. 500 instructions, Te Kaiping 5-333207 communique, Te Kaiping 6-35183 communique, Te Kaiping 6-51115 communique, Te Kaiping 6-194828 communique, Te Kaiping 8-211599 communique, Te Kaiping 4-249549 communique, Te Kaiping 10-123316 communique, Te Kaiping 11-302283 communique, Te Kaiping 7-286107 communique, the spy opens the 2001-4823 communique, Te Kaiping 8-15522 communique, Te Kaiping 8-29771 communique, Te Kaiping 8-146215 communique, Te Kaiping 11-343437 communique, Te Kaiping 8-62416 communique, the spy opens the 2002-14220 communique, the spy opens the 2002-14221 communique, the spy opens the 2002-14222 communique, the spy opens the 2002-14223 communique, Te Kaiping 8-302224 communique, Te Kaiping 8-73758 communique, Te Kaiping 8-179120 communique, disclosed pigment in the Te Kaiping 8-151531 communique etc.
As chemical constitution, can use that pyrazoles azo system, anilino-azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzal base system, oxonols (オ キ ソ ノ one Le) are, the dyestuff of Pyrazolotriazole azo system, pyridone azo system, anthocyanin system, phenothiazine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system etc.
In addition, carry out in employing under the situation of the resist system that water or alkali develops, from removing the deluster bonding agent of not irradiation portion and/or the viewpoint of dyestuff fully, in the scope of not damaging effect of the present invention, can use acid dyes and/or its derivant by developing.
In addition, can also use direct dyes, basic-dyeable fibre, mordant dye, acid mordant dyes, azo dyes, disperse dyes, oil-soluble dyes, food dye and/or their derivant etc.
As above-mentioned acid dyes, as long as have acidic-groups such as sulfonic acid or carboxylic acid, just be not particularly limited, but to consider with respect to organic solvent or developer solution dissolubility, with the salt of alkali compounds form property, absorbance, with composition in all necessary performance such as interaction, photostability, thermotolerance of other compositions select.
Enumerate the object lesson of above-mentioned acid dyes below, but be not limited.For example, can enumerate:
The purple N of acid alizarine, acid black 1,2,24,48, Blue VRS, 7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324:1, acid chrome violet K, acid fuchsin, acid green 1,3,5,9,16,25,27,50, acid orange 6,7,8,10,12,50,51,52,56,63,74,95, azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274, acid violet 6B, 7,9,17,19, Indian yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243, edible Huang 3, and the derivant of these dyestuff.
Wherein, as above-mentioned acid dyes, preferred acidic black 24, acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324:1, acid orange 8,51,56,63,74, azogeramine, 4,8,34,37,42,52,57,80,97,114,143,145,151,183,217, acid violet 7, Indian yellow 17,25,29,34,42,72,76,99,111,112,114,116,184,243, the derivant of dyestuff such as ACID GREEN 25 and these dyestuffs.
In addition, go back preferably above-mentioned acid dyes in addition, that azo is, xanthene is, phthalocyanine is, go back preferably use C.I. soluble blue 44,38; C.I. solvable orange 45; The derivant of acid dyess such as rhodamine B, rhodamine 110 and these dyestuffs.
Containing ratio to colorant in the total solid composition of composition of the present invention is not particularly limited, and from the viewpoint of look characteristic, is preferably 10～60 quality %.If colorant is very few, exist can not get as color filter the trend of suitable colourity.On the other hand, if too much, photocuring can not fully carry out, reduce as film strength, in addition, the development tolerance (development boundary) when alkali develops has the trend that becomes narrow.
In the present invention, in order to improve dispersing of pigments, can add known in the past pigment dispersing agent or surfactant.As these spreading agents, use multiple compound, for example, can enumerate Disperbyk161 (30 quality % solution of the propylidene methyl ethyl glycol acetate of segmented copolymer and the mixed solvent of butyl acetate (PVC Star Network ケ ミ one (strain) corporate system), phthalocyanine derivates (commercially available product EFKA-745 (エ Off カ society system)), ソ Le ス パ one ス 5000 (ゼ ネ カ (strain) system); Organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ one No.75, No.90, No.95 (common prosperity society oil chemistry industry (strain) system), W001 kations such as (abundant merchant's systems) are surfactant; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan aliphatic ester are surfactant; W004, W005, W017 negative ion such as (abundant merchant's systems) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (the above gloomy system of industry (strain) down), デ イ ス パ one ス エ イ De 6, デ イ ス パ one ス エ イ De 8, デ イ ス パ one ス エ イ De 15, デ イ ス パ one ス エ イ De 9100 macromolecule dispersing agents such as (サ Application ノ プ コ systems); Various ソ Le ス パ one ス spreading agents (ゼ ネ カ (strain) system) such as ソ Le ス パ one ス 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; ア デ カ プ Le ロ ニ Star Network L 31, F 38, and L 42, and L 44, L 61, and L 64, and F 68, and L 72, P 95, and F 77, and P 84, F 87, P 94, L 101, and P 103, F 108, L 121, P-123 (rising sun electrification (strain) system) and イ ソ ネ Star ト S-20 (Sanyo changes into (strain) system), Disperbyk 101,103,106,108,109,111,112,116,130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (PVC Star Network ケ ミ one (strain) society systems) etc.
＜polymerizable compound 〉
Then, the polymerizable compound that uses in the composition of the present invention is described.
As above-mentioned polymerizable compound, as long as have at least 1 can addition polymerization vinyl and can polymerization, just be not particularly limited, but boiling point is the compound with ethene unsaturated group more than 100 ℃ under the preferred normal pressure, wherein, more preferably above acrylate compounds of 4 functional groups.
As above-mentioned have at least 1 can addition polymerization ethene unsaturated group and boiling point under the normal pressure be compound more than 100 ℃, can enumerate polyglycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate, the acrylate or the methacrylate of simple function groups such as (methyl) acrylic acid phenoxy group ethyl ester, polyglycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, hexanediol (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, carrying out the compound that (methyl) acroleic acid esterification forms behind the alkylene oxides such as addition of ethylene oxide or epoxypropane on the polyfunctional alcohols such as glycerine or trimethylolethane, poly-(methyl) acroleic acid esterification thing of pentaerythrite or dipentaerythritol, at the public clear 48-41708 of spy number, special public clear 50-6034 number, the spy opens the urethane acrylate class of putting down in writing in clear 51-37193 number each communique, open clear 48-64183 number the spy, special public clear 49-43191 number, the polyester acrylate class of putting down in writing in special public clear 52-30490 number each communique is as the polyfunctional acrylate or the methacrylates such as epoxy acrylate class of epoxy resin and (methyl) acrylic acid reaction product.And then, can also use the will Vol.20 of the bonding association of Japan, No.7, in 300～308 pages as photo-curable monomer and oligomer and the material of introducing.
Carry out the material of (methyl) acroleic acid esterification behind above-mentioned addition of ethylene oxide in the polyfunctional alcohol or the epoxypropane, open in the flat 10-62986 communique all on the booksly together with its object lesson as general formula (1) and (2) the spy, these also can be used as polymerizable compound.
Wherein, get involved the structure that alkylene oxide chains such as ethylene glycol, propylene glycol residue are arranged in preferred dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate and their acryloyl group.By using these to have with the compound of oxirane as the alkylene oxide chain of representative, can promote the affinity in the Photocurable coating film, improve development, thereby be preferred.
Also can use their oligomeric.These optical polymerism compounds can use a kind separately, can also be used in combination more than 2 kinds.
The use amount of these polymerizable compounds, the total solid composition 100 quality % with respect to Photocurable composition are preferably 20～200 quality %, more preferably 50～120 quality %.If it is very few or too much that the use amount of polymerizable compound is compared with above-mentioned scope, can cause solidifying insufficient, so not preferred.
＜Photoepolymerizationinitiater initiater 〉
Photoepolymerizationinitiater initiater among the present invention contains the compound of SH base, at least with the compound of following formula (I) expression and the compound of representing with following formula (II).
The compound of-usefulness formula (I) expression-
Composition of the present invention contains the compound of useful following formula (I) expression.
[changing 7]
Figure A20061017246200221
In above-mentioned formula (I), X represents halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom), and n represents 1～4 integer.
As above-mentioned X, preferred fluorine atom, chlorine atom, bromine atoms, more preferably fluorine atom, chlorine atom, especially preferably fluorine atom, chlorine atom.Under n described later is situation more than 2, can be different atoms.
As said n, preferred especially 1～2.The position of substitution as above-mentioned Xn just is not particularly limited, when n=1, and preferred ortho position.As the substituting group of formula (I) and the combination of n, the more preferably combination of preferred example separately.
As the preferred example of above-mentioned formula (I), can enumerate 2-(o-chlorphenyl)-4,5-diphenyl-imidazole base dimer etc.
Content as the compound of representing with above-mentioned formula (I) in the composition of the present invention is not particularly limited, wherein, with respect to the 100 quality % of the total solid composition in the composition, be preferably 0.1～15 quality %, more preferably 0.5～10 quality %, preferred especially 1～10 quality %.
Very few during when the content of above-claimed cpd less than 0.1 quality %, can't obtain enough light sensitivity, in addition, when content surpasses 15 quality % and too much the time, can't form pattern well sometimes.
The compound of-usefulness formula (II) expression-
Composition of the present invention contains the compound of useful following formula (II) expression.
[changing 8]
In above-mentioned formula (II), R represents that carbon number is 1～4 alkyl.
As the alkyl of above-mentioned R, separate, particularly preferred carbon number is 1～3.
Abovementioned alkyl can have nothing in common with each other, also can be identical.
As the preferred example of above-mentioned formula (II), can enumerate dimethylamino benzophenone, dipropyl aminobenzophenone, Methylethyl aminobenzophenone, methyl-propyl benzophenone, ethyl propyl benzophenone.
Content as the compound of representing with above-mentioned formula (II) in the composition of the present invention is not particularly limited, wherein, with respect to the 100 quality % of the total solid composition in the composition, preferred 0.1～10 quality %, preferred especially 1～10 quality %.
-contain the compound of SH base-
In composition of the present invention,, contain the compound of SH base in order to improve the light sensitivity in when exposure.
As the above-mentioned compound that contains the SH base, be not particularly limited, wherein, and the viewpoint of the light sensitivity when exposing from further improving, that preferably selects from the compound with following formula (III)～(V) expression is at least a.
[changing 9]
(HSR 1) mC(R 2SH) n (V)
In formula (III), (IV), R is independent separately, and expression hydrogen atom, carbon number are 1～6 alkyl or nitro, and A represents N, S or O.In formula (V), R 1, R 2Independent separately, the expression carbon number is 1～6 alkyl, and m and n are independent separately, the integer of expression 1～3, m+n=4.
Below, formula (III), (IV) are elaborated.
In above-mentioned formula (III), (IV), R is independent separately, and expression hydrogen atom, carbon number are 1～6 alkyl or nitro, and A represents N, S or O.
As the R among above-mentioned formula (III), (IV), independent separately, preferred especially 1～3 alkyl, nitro.Abovementioned alkyl can have nothing in common with each other, also can be identical.
As the A among above-mentioned formula (III), (IV), preferred N, S, O, more preferably N, S, especially preferably N.
As the preferred example of above-mentioned formula (III), can enumerate A is that N, R are the compound of H.
(V) is elaborated to above-mentioned formula.
In above-mentioned formula (V), as using R 1, R 2The alkyl of expression, independent separately, preferred carbon number is 1～6 alkyl, preferred especially carbon number is 2～4 alkyl.Abovementioned alkyl can have nothing in common with each other, also can be identical.
As the preferred example of above-mentioned formula (V), can enumerate pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four mercaptoacetates.
In the present invention, in the scope of not damaging effect of the present invention, can use above-mentioned Photoepolymerizationinitiater initiater in addition.
As this Photoepolymerizationinitiater initiater, for example, can use the spy and open the Lu of flat 57-6096 communique record for the Jia oxadiazole; Special public clear 59-1281 communique, spy open the halogenated methyl-s-triazine isoreactivity halogen compounds of records such as clear 53-133428 communique; The aromatic carbonyl of ketal, acetal or the benzoin alkylether class etc. of record such as U.S. Pat P-4318791, Europe patent disclosure EP-88050A; The aromatic ketone compound of the benzophenone of U.S. Pat P-4199420 record etc.; (sulfo-) the xanthene ketone or the acridine compound of Fr-2456741 record; The compound of the Coumarins of Te Kaiping 10-62986 communique record or lophine dimer class etc.; Above-mentioned formula (I)～(V) Photoepolymerizationinitiater initiaters in addition such as the organic boron coordination compound of sulfonium of Te Kaiping 8-015521 communique etc.
In the present invention, as above-mentioned formula (I)～(V) Photoepolymerizationinitiater initiater in addition, can and with acetophenone system, ketal system, benzophenone series, benzoin system, benzoyl system, xanthone system, triazine system, Lu for Photoepolymerizationinitiater initiaters such as Jia oxadiazole system, acridine system, Coumarins system, lophine dimer class system, di-imidazoles systems.
As above-mentioned acetophenone is Photoepolymerizationinitiater initiater, for example, can enumerate 2,2-diethoxy acetophenone, p-dimethylamino benzoylformaldoxime, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, p-dimethylamino benzoylformaldoxime, 4 '-isopropyl-2-hydroxy-2-methyl-propiophenone etc.
As above-mentioned ketal is Photoepolymerizationinitiater initiater, for example, can enumerate benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetal etc.
As above-mentioned benzophenone series Photoepolymerizationinitiater initiater, for example, can enumerate benzophenone, 4,4 '-dichloro benzophenone, 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino acetone-1 etc.
As above-mentioned benzoin system or benzoyl is Photoepolymerizationinitiater initiater, for example, can enumerate benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoic acid ester etc.
As above-mentioned xanthone is Photoepolymerizationinitiater initiater, for example, can enumerate diethyl thio-xanthene-one, diisopropyl thio-xanthene-one, an isopropyl-thio-xanthone, chlorine thio-xanthene-one etc.
As above-mentioned triazine is Photoepolymerizationinitiater initiater, for example, can enumerate 2, two (the trichloromethyl)-6-p-methoxyphenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-p-methoxyl-styrenes of 4--s-triazine, 2, two (the trichloromethyl)-6-(1-p-dimethylaminophenyl)-1 of 4-, 3-butadienyl-s-triazine, 2, two (the trichloromethyl)-6-xenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-(p-methyl biphenyl) of 4--s-triazine, p-hydroxyl-oxethyl styryl-2,6-two (trichloromethyl)-s-triazine, methoxyl-styrene-2,6-two (trichloromethyl)-s-triazine, 3,4-dimethoxy-styryl-2,6-two (trichloromethyl)-s-triazine, 4-benzo tetrahydrofuran (ベ Application ズ オ キ ソ ラ Application)-2,6-two (trichloromethyl)-s-triazine, 4-(o-bromo-p-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 4-(p-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine etc.
Is Photoepolymerizationinitiater initiater as above-mentioned Lu for the Jia oxadiazole, for example, can enumerate 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.
As above-mentioned acridine is Photoepolymerizationinitiater initiater, for example, can enumerate 9-phenylacridine, 1, two (9-acridinyl) heptane of 7-etc.
As above-mentioned Coumarins is Photoepolymerizationinitiater initiater, for example, can enumerate 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.
As above-mentioned lophine dimer class is Photoepolymerizationinitiater initiater, for example, can enumerate 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole base dimer, 2-(2, the 4-Dimethoxyphenyl)-4,5-diphenyl-imidazole base dimer etc.
In addition; as above-mentioned Photoepolymerizationinitiater initiater; can enumerate 1-phenyl-1; 2-propanedione-2-(o-ethoxy carbonyl) oxime, O-benzoyl-4 '-(benzo sulfydryl) benzoyl-hexyl-ketoxime, 2; 4; 6-trimethylphenyl carbonyl-diphenylphosphine acyl group oxide, hexafluoro idol phosphorus-trialkyl benzene base phosphonium salt, 2,2 '-benzothiazole based bisulfide etc.
In the present invention, be not limited to above Photoepolymerizationinitiater initiater, can also use other known initiating agents.For example, can use at United States Patent (USP) the 2nd, 367, disclosed vicinal polyketone alcohol aldehyde glycosyl in No. 660 instructionss (PVC シ Na one Le Port リ ケ ト Le ア Le De ニ Le) compound, at United States Patent (USP) the 2nd, 367, No. 661 and the 2nd, 367, disclosed alpha-carbonyl compound in No. 670 instructionss, at United States Patent (USP) the 2nd, 448, disclosed accidental cause ether in No. 828 instructionss, at United States Patent (USP) the 2nd, 722, aromatic series accidental cause (acyloin) compound that disclosed α in No. 512 instructionss-hydrocarbon replaces, at United States Patent (USP) the 3rd, 046, No. 127 and the 2nd, 951, disclosed polynucleation quinone compound in No. 758 instructionss, at United States Patent (USP) the 3rd, 549, the combination of disclosed triallyl imidazoles dimer/p-aminophenyl ketone in No. 367 instructionss, disclosed benzothiazole based compound/trihalomethyl group-above-mentioned formula (I)～(V) materials in addition such as s-triazine based compound in the public clear 51-48516 communique of spy.
In addition, these Photoepolymerizationinitiater initiaters can also and be used.
In the present invention, the use amount of above-mentioned Photoepolymerizationinitiater initiater is 0.1～10.0 quality % of the total solid composition of Photocurable composition, preferred 0.5～5.0 quality %.When the use amount of Photoepolymerizationinitiater initiater than 0.1 quality % after a little while, can be difficult to carry out polymerization, in addition, when surpassing 10.0 quality %, film strength can weaken.
＜solvent 〉
When modulation composition of the present invention, can use solvent.As above-mentioned solvent, can enumerate 3-hydracrylic acid alkyl esters such as ester class, for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, glycolic acid butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxy butyrate methyl esters, 2-oxy butyrate ethyl etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diglycol monomethyl ether, diglycol monoethyl ether, diethylene glycol-butyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.; Ketone, for example methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc.; Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.
In the middle of these solvents, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol acetate etc. are preferably used as the solvent among the present invention.
These solvent can use separately, can also make up more than 2 kinds and use.
＜fluorine series organic compound 〉
In composition of the present invention, can contain fluorine-containing rate is the fluorine series organic compound of 3～40 quality %.Can further improve the characteristic of composition thus as coating liquid.
The fluorine-containing rate of above-mentioned fluorine series organic compound is 3～40 quality %, preferred 5～30 quality %, more preferably 7～25 quality %.
If the fluorine-containing rate of fluorine series organic compound is lower, can't obtain effect of sufficient aspect applied thickness homogeneity or the province's fluidity, in addition, if containing ratio is excessive, the dissolubility in composition can be insufficient.
By making composition of the present invention contain the fluorine series organic compound, can improve characteristics of liquids as coating liquid, can improve the homogeneity of applied thickness or economize fluidity.Particularly the screening characteristics to substrate is improved, even if having filming of homogeneous film thickness with what a spot of liquid measure also can obtain not having uneven thickness.
As above-mentioned fluorine series organic compound, for example, can enumerate Megafac F 171, Megafac F 172, Megafac F 173, Megafac F 177, Megafac F141, Megafac F 142, Megafac F 143, Megafac F 144, MegafacR 30, Megafac F 437 (above is big Japanese ink (strain) system product), Off ロ ラ one De F C 430, Off ロ ラ one De FC 431, Off ロ ラ one De FC 171 (above is Sumitomo 3M (strain) system product), サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC 1068, サ one Off ロ Application SC-381, サ one Off ロ Application SC-383, サ one Off ロ Application S 393, サ one Off ロ Application KH-40 (above is Asahi Glass (strain) system product) etc.
In addition, by containing above-mentioned fluorine series organic compound, can improve flowability as coating liquid, reduce the interfacial tension of substrate and coating liquid, improvement is to the wetting state of substrate, even and if the film of number μ m degree also can obtain the less coated film of uneven thickness degree.Particularly when coated film is thin, for the slit coating of the disconnected liquid on easy appearance coating inequality or uneven thickness even the applicator surface, can bring good result.
As the addition of above-mentioned fluorine series organic compound, be preferably 0.001～2.0 quality % with respect to coating solution total amount, more preferably 0.005～1.0 quality %.
＜other composition 〉
In composition of the present invention, can cooperate various additives as required, for example the macromolecular compound beyond the filling agent, above-mentioned alkali soluble resins, the surfactant beyond above-mentioned, connect airtight promoter, antioxidant, ultraviolet light absorber, anti flocculant etc.
As the object lesson of these additives, can enumerate: filling agents such as glass, aluminium oxide; Itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid, acid cellulose derivant, at the alkaline bleach liquor soluble resins such as phenoxy resin that have the addition acid anhydrides forms on the polymkeric substance of hydroxyl material, alcohol soluble nylon, form by bisphenol-A and chloropropylene oxide; The surfactant of nonionic system, kation system, negative ion system etc. specifically can be enumerated phthalocyanine derivates (commercially available product EFKA-745 (gloomy industry system down)); Organic siloxane polymer KP 341 (SHIN-ETSU HANTOTAI's chemical industry system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ one No.75, No.90, No.95 (common prosperity society oil chemistry industry system), W001 kations such as (abundant merchant's systems) is a surfactant; (nonionics such as the system プ of BASF AG Le ロ ニ Star Network L 10, L 31, L 61, L 62,10 R5,17 R2,25 R2, テ ト ロ ニ Star Network 304,701,704,901,904,150R1 are surfactant for polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan aliphatic ester; W004, W005, W017 negative ion such as (abundant merchant's systems) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (above is gloomy industry system down), デ イ ス パ one ス エ イ De 6, デ イ ス パ one ス エ イ De 8, デ イ ス パ one ス エ イ De 15, デ イ ス パ one ス エ イ De 9100 macromolecule dispersing agents such as (サ Application ノ プ コ systems); Various ソ Le ス パ one ス spreading agents (ゼ ネ カ (strain)) such as ソ Le ス パ one ス 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 system); ア デ カ プ Le ロ ニ Star Network L 31, F 38, and L 42, and L 44, and L 61, and L 64, and F 68, and L 72, and P 95, and F 77, and P 84, F 87, P 94, L 101, and P 103, F 108, L 121, P-123 (rising sun electrification system) and イ ソ ネ Star ト S-20 (Sanyo's system of changing into);
Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone;
With anti flocculants such as sodium polyacrylates.
In addition,, can in composition of the present invention, add organic carboxyl acid, preferably add molecular weight and be the low-molecular-weight organic carboxyl acid below 1000 if will promote the not alkali dissolution of the irradiation portion development that further improves composition of the present invention of light.Particularly, for example can add formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, aliphatics monocarboxylic acid such as sad; The aliphatic dicarboxylic acid of oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, Brazilian diacid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid etc.; The aliphatic tricarboxylic acids of tricarballylic acid, aconitic acid, camphoronic acid etc.; Benzoic acid, toluic acid, cumidic acid, 2,3-mesitylenic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid; Aromatic series polybasic carboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetate, coumalic acid, umbellic acid.
In composition of the present invention, except above-mentioned, also preferably add thermal polymerization and prevent agent, for example can use quinhydrones, p-metoxyphenol, di-t-butyl-p-cresols, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc.
The manufacture method of＜Photocurable composition of the present invention 〉
Composition of the present invention can be modulated by the following method.Promptly, colorant, alkali soluble resins, polymerizable compound, Photoepolymerizationinitiater initiater and other adjuvants of using as required, with solvent, and, be modulated into composition through using the mixing dispersion step of various mixers, dispersion machine mixing dispersion.
In addition, mix dispersion step and preferably constitute, but also can omit mixing dispersion by the processing of loosing of mixing dispersion and the differential that carries out thereafter.
The preferable production process of composition of the present invention is as follows: with the alkali soluble resins that contains the alkali soluble resins among the present invention, colorant is carried out mixing dispersion treatment, and to make the viscosity after the mixing dispersion treatment be 10,000mPas is above, preferred 100, the higher viscosity of ratio that 000mPas is above, then, add above-mentioned alkali soluble resins, carry out differential and loose to handle, and the viscosity that differential is loose after handling is 1, the following lower viscosity of following, the preferred 100mPas of 000mPas.
The machinery that uses in mixing dispersion treatment is difference with its manufacturing scale, can use the extruder of two rollers, three rollers, bowl mill, drum-type mixing roll, dispersion machine, kneading machine, kneading extruder, homogenizer, mixer, single shaft and twin shaft etc., can when applying strong shearing force, disperse.Then, add solvent and originally contain the alkali soluble resins of the alkali soluble resins in the invention, the main sand mill that uses longitudinal type or horizontal type, needle mill (ピ Application ミ Le), slit muller, ultrasonic dispersing machine etc., utilizing particle diameter is that the pearl that is formed by glass, zirconia etc. of 0.1～1mm carries out the differential processing of loosing.In addition, can also omit mixing dispersion treatment.At this moment, alkali soluble resins among usefulness the present invention and solvent are to pigment and spreading agent or the dispersion of surface conditioning agent enforcement pearl.
In addition, relevant mixing, the detailed content of disperseing is also on the books in " the Paint Flow and Pigment Dispersion " of T.C.Patton work (John Wiley and Sons society periodical in 1964) etc.
＜color filter 〉
Color filter of the present invention is characterised in that, has the composition that uses the invention described above and the demonstration pixel of the multiple color that forms by photoetching process.
Make color filter by the composition that uses the invention described above through photoetching process, can obtain being suitable for the outstanding high-accuracy color filter of the little liquid crystal indicator of display frame size (LCD).
By coating methods such as rotation (spin coating) coating, slit coating, curtain coating coating, roller coat, above-mentioned composition of the present invention directly or across other layer is coated on the substrate, form the coated film of composition, mask pattern across regulation exposes afterwards, only make by light-struck coated film partly to be cured, develop, form the pattern-like tunicle that constitutes by each color pixel with developer solution, by such photoetching process, can make each color filter.
Radioactive ray as use this moment especially preferably use ultraviolet rays such as g line, h line, i line.
As manufacturing method of color filter of the present invention, be preferably as follows described method, promptly utilize slit coating that composition of the present invention directly or across other layer is coated on the substrate and after forming coated film, successively above-mentioned coated film is carried out the method that drying, pattern exposure and alkali develop.Thus, can be produced on the color filter that uses in liquid crystal display cells or the solid-state imager, and low in technologic difficulty, quality height and cost are low.
Be not eluted in the aqueous alkali by carrying out above-mentioned alkali development treatment, making in the above-mentioned exposure, only the part of residual light curing by light-struck part.As developer solution, if can dissolve light not the composition of irradiation portion coated film and do not dissolve the developer solution of illumination part, just can use any developer solution.
Then, the developer solution that flush away is unnecessary is implemented to carry out heat treated (afterwards curing) after the drying under 50 ℃～240 ℃ temperature.By every kind of color is repeated above-mentioned operation successively, can make the curing tunicle.Can obtain color filter thus.
As substrate, for example can enumerate the alkali-free glass that in liquid crystal display cells etc., uses, soda-lime glass, hard (registered trademark) glass, quartz glass and be attached with the material of nesa coating above the glass at these, or the components of photo-electric conversion substrate of use in solid-state imager etc., for example silicon substrate etc.Can also use plastic base.On these substrates, be formed with the secret note that each pixel is isolated usually.
In addition, preferably on the surface of plastic base, have gas barrier layer and/or solvent resistance layer.
When dry (prebake) is applied to the coated film of the composition of the present invention on the substrate, utilize heating plate, heating furnace etc. under 50 ℃～140 ℃ temperature, to carry out 10～300 seconds.
The applied thickness of the coated film of composition of the present invention (dry back) is generally 0.3～5.0 μ m, is preferably 0.5～3.5 μ m, most preferably is 1.0～2.5 μ m.
As developer solution,, just can use any developer solution so long as can dissolve composition dissolves of the present invention and not dissolve the composition of illumination part.Particularly, can use the combination of various organic solvents or the aqueous solution of alkalescence.
As organic solvent, can enumerate the above-mentioned solvent that when preparation composition of the present invention, uses.
Development temperature is generally 20 ℃～30 ℃, and development time is generally 10～120 seconds, preferred 20～90 seconds.
Aqueous solution as above-mentioned alkalescence, for example, use is dissolved with NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium orthosilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1 with the concentration of 0.001～10 quality %, preferred 0.01～1 quality %, 8-diazabicylo-[5,4,0]-alkaline aqueous solution of alkali compounds such as 7-undecylene.Wherein, when using the developer solution of forming by such alkaline aqueous solution, after development, wash (flushing) usually with water.
After to cure be the heating that is used to make after the development that completion of cure carries out, heat (cure bake) at about 200 ℃～220 ℃ usually.
Carry out curing after this when handling, can as above-mentioned condition, use heating plate or heater meanses such as convective oven (heated air circulation type dryer), high frequency heating machine, in a continuous manner or intermittent mode the coated film after developing is handled.
In the color filter of the present invention, the demonstration pixel that on aforesaid substrate, has multiple color, this demonstration is more than the 5 μ m, below the 50 μ m with the size of pixel, this is suitable for the little LCD of display part equidimension of mobile phone, digital camera etc., its size more preferably 10 μ m above, below the 40 μ m, more preferably 15 μ m above, below the 30 μ m, be preferably especially 20 μ m above, below the 30 μ m.
Here, when above-mentioned demonstration pixel is under the situation of rectangle, size is meant the length of minimum edge.
When using Photocurable composition of the present invention, its advantage is, compares with composition in the past, can obtain the littler pixel of size under the pattern contour good state.
Above-mentioned demonstration pixel in the color filter of the present invention, can be the above multiple color pixel of 2 kinds of colors, wherein, from the viewpoint of color reproduction, contrast, preferably in 3 kinds of colors in the past such as RGB, add color and become 4 kinds of demonstration pixels more than the color more than a kind such as cyan.By being 4 kinds more than the color, compare with 3 kinds of colors such as RGB in the past, can enlarge the color reproduction territory that can show, have bigger tolerance aspect the performance of color reproduction, contrast, so preferred.
In addition, as the thickness of the demonstration in the color filter of the present invention with pixel, be not particularly limited, from effective utilization of substrates such as silicon wafer, use the angle of shading (シ エ one デ イ Application グ) of the device of solid-state imager, trend towards attenuation, be preferably 0.2 μ m above, below the 2 μ m, more preferably 0.3 μ m above, below the 1.5 μ m, be preferably especially 0.4 μ m above, below the 1.0 μ m.
And then, for the colorant containing ratio of the demonstration in the color filter of the present invention, being not particularly limited with pixel, the viewpoint from look separates is preferably more than the 25 quality %, more preferably more than the 30 quality %, is preferably especially more than the 40 quality %.
As previously mentioned, color filter of the present invention is preferably used as the color filter that LCD uses, and can also be used for image sensor such as CCD, particularly surpass the high-resolution CCD element of 1,000,000 pixels or cmos element etc.
In addition,, mainly described the purposes that is used for color filter, but can also be used to be arranged on the black matrix between the pixel of color filter as the purposes of the composition of the invention described above.
Black matrix can form as follows, promptly, use black colorants such as carbon black, titanium be black as the colorant in the composition of the present invention, on substrate, form filming of Photocurable composition, afterwards this is filmed and carry out light exposure, alkali development, cure the curing that promotes film after carrying out again subsequently, can form black matrix thus.
[embodiment]
Be described more specifically the present invention with following embodiment, the present invention is not limited by the following examples.
＜LCD the modulation of Photocurable composition 〉
(embodiment 1～6)
Use pressure-even pulp crusher to stir also each composition of mixture table 1 record, modulation LCD Photocurable composition.
(comparative example 1～4)
Use pressure-even pulp crusher to mix each composition of table 2 record, modulate the LCD Photocurable composition.
[table 1]
The raw material name Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Acrylic acid series alkali soluble resins (1) ※1 6.25 6.25 - 6.25
Acrylic acid series alkali soluble resins (2) ※2 - - 6.25 -
C.I. paratonere 254 6.75 6.75 6.75 6.75
C.I. pigment yellow 13 9 1.69 1.69 1.69 1.69
PGMEA 34.2 34.2 34.2 34.2
EEP 45.0 45.0 45.0 45.0
DPHA ※3 4.12 - 4.12 4.12
DPCA-60 ※4 - 4.12 - -
Photoepolymerizationinitiater initiater (1) (2-benzimidazole mercaptan) 0.33 0.33 0.33 -
Photoepolymerizationinitiater initiater (2) (two (2-chlorphenyls)-4,5-diphenyl di-imidazoles) 0.99 0.99 0.99 0.99
Photoepolymerizationinitiater initiater (3) (diethylamino benzophenone) 0.66 0.66 0.66 0.66
Photoepolymerizationinitiater initiater (4) (pentaerythrite four (3-mercaptopropionic acid ester)) - - - 0.33
Fluorine is surfactant (F-144) 0.01 0.01 0.01 0.01
[table 2]
The raw material name Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Acrylic acid series alkali soluble resins (1) - 6.31 6.40 6.36
Acrylic acid series alkali soluble resins (3) ※5 6.25 - - -
C.I. paratonere 254 6.75 6.81 6.90 6.86
C.I. pigment yellow 13 9 1.69 1.74 1.94 1.80
PGMEA 34.2 34.2 34.2 34.2
EEP 45.0 45.0 45.0 45.0
DPHA 4.12 4.18 4.27 4.23
DPCA-60 - - - -
Photoepolymerizationinitiater initiater (1) (2-benzimidazole mercaptan) 0.33 - 0.48 0.44
Photoepolymerizationinitiater initiater (2) (two (2-chlorphenyls)-4,5-diphenyl di-imidazoles) 0.99 1.04 - 1.10
Photoepolymerizationinitiater initiater (3) (2-ethylamino benzophenone) 0.66 0.71 0.80 -
Photoepolymerizationinitiater initiater (4) (pentaerythrite four (3-mercaptopropionic acid ester)) - - - -
Fluorine is surfactant (F-144) 0.01 0.01 0.01 0.01
※ 1 acrylic acid series alkali soluble resins (1): BzMA (benzyl methacrylate)/MAA (methacrylic acid)=60/40 (mol ratio) multipolymer, weight-average molecular weight 10000, solid constituent acid number 167 (KOHmg/g)
※ 2 acrylic acid series alkali soluble resins (2): BzMA (benzyl methacrylate)/MAA (methacrylic acid)=70/30 (mol ratio) multipolymer, weight-average molecular weight 15000, solid constituent acid number 105 (KOHmg/g)
※ 3DPHA: dipentaerythritol six/five acrylate (Japanese chemical drug system)
※ 4DPCA-60: the alkylene oxide addition product (Japanese chemical drug system) of dipentaerythritol acrylate
※ 5 acrylic acid series alkali soluble resins (3): BzMA/MAA=85/15 (mol ratio) multipolymer, weight-average molecular weight 15000, solid constituent acid number 51 (KOHmg/g)
PGMEA (Glycol Monomethyl ether acetic acid esters)
EEP (3-ethoxyl ethyl propionate)
Fluorine is surfactant (F-144): (Megafac F 144, big Japanese ink (strain) system)
＜LCD the evaluation of Photocurable composition 〉
According to following steps the LCD that obtains has been carried out the development evaluation with Photocurable composition (colored resist) in embodiment 1～4, comparative example 1～4.
It is the results are shown in table 3.
[the minimum exploring pattern evaluation of development boundary]
(1) the colored resist that will prepare as described above is spun on the glass substrate Corning#1737 of Corning corporate system, and makes dried thickness reach 1.0 μ m, uses heating plate with 100 ℃ of heating 120 seconds, obtains dry coating.
(2) above-mentioned film is carried out convergence (プ ロ キ シ) exposure (ウ シ オ motor system).Exposure is 100mJ/cm 2, illumination is 20mW.In addition, used mask size is 50 μ m～wide wire shaped of 5 μ m.
(3) develop under 26 ℃ at 10% dilution with alkaline developer CD (Fujiphoto electronic material (strain) system) on this film.Observe the pattern after developing, measure minimum exploring pattern dimension (width).
In addition, between 10～100 seconds, change second number that develops simultaneously, the affirmation of the boundary of developing (being formed up to the second number that peels off from pattern).
[evaluation of lowest exposure amount]
(4) for the dry coating that in above-mentioned (1), obtains, at 10～300mJ/cm 2Between with 10mJ/cm 2For unit changes exposure, and under the condition identical, develop, measure and form the required lowest exposure amount of pattern with above-mentioned (3).Development time is 60sec.
[table 3]
Minimum exploring pattern (μ m) The development boundary Lowest exposure amount (mJ/cm 2)
Embodiment 1 7 20～90sec. 10
Embodiment 2 6 10～90sec. 10
Embodiment 3 8 30～90sec. 10
Embodiment 4 7 20～90sec. 10
Comparative example 1 15 60～1000sec. 20
Comparative example 2 - 10sec peels off 250
Comparative example 3 - 10sec peels off 270
Comparative example 4 - 10sec peels off 220
As from the foregoing, adopt under the situation of Photocurable composition of the present invention, can guarantee light sensitivity, realize wide development boundary with low exposure.In addition, can carry out the exploring of fine pattern, obtain being suitable for the result of high-accuracy color filter purposes.
Use the Photocurable composition that obtains in the above-described embodiments, can obtain high-accuracy color filter.
The making of the color filter that＜4 kinds of colors are above 〉
According to following step, use colored resist (Photocurable composition) by embodiment 1 and the preparation of following step, make color filter.
(1) colorant of embodiment 1 is replaced by respectively
(A) the C.I. pigment green 36 (=PG36)/C.I. pigment yellow 150 (=PY150)=100/50,
(B) C.I. pigment blue 15: 6 (=PB15:6)/the C.I. pigment Violet 23 (=PV23)=100/20,
(C) C.I. pigment blue 15: 3/C.I. pigment yellow 150 (=PY150)=100/100,
In addition, with embodiment 1 all identical prescriptions and condition under, the colored resist of preparation green light solidification compound, blue light solidification compound, cyan light solidification compound.
(2) the colored resist with embodiment 1 is spun on the glass substrate Corning#1737 of Corning corporate system, and makes dried thickness reach 2.0 μ m, uses heating plate in 100 ℃ of heating 120 seconds, obtains dry coating.
(3) above-mentioned film is carried out convergence exposure (ウ シ オ motor system).Exposure is 100mJ/cm 2, illumination is 20mW.In addition, the mask of use is the wide nemaline masks of 15 μ m.
(4) on this film, develop down at 26 ℃ with the 10 quality % dilutions of alkaline developer CD (Fujiphoto electronic material (strain) system), then with heating furnace in 230 ℃ carry out 60 minutes after cure, heating is burnt till.
(5), on identical glass substrate, make green pattern image (green pixel), blue pattern image (blue pixel), the pattern image (cyan pixel) of cyan successively, but will avoid each colour superimposition by identical operations.
Although the pixel wide of the color filter of Zhi Zuoing is less as described above, but can be made into the good color filter that does not have defective, peels off.

Claims (6)

1, a kind of Photocurable composition, wherein,
Contain colorant, alkali soluble resins, polymerizable compound and Photoepolymerizationinitiater initiater,
The acid number of described alkali soluble resins is more than the 100KOHmg/g, below the 300KOHmg/g,
Described Photoepolymerizationinitiater initiater contains the compound of SH base at least, with the compound of following formula (I) expression and the compound of representing with following formula (II),
In formula (I), X represents halogen atom, and n represents 1～4 integer,
Figure A2006101724620002C2
In formula (II), R represents that carbon number is 1～4 alkyl.
2, Photocurable composition as claimed in claim 1, wherein,
The compound of the described SH of containing base is at least a kind that is selected from in the compound of following formula (III)～(V) expression,
Figure A2006101724620003C1
(HSR 1) mC(R 2SH) n (V)
In formula (III), (IV), R represents that independently of one another hydrogen atom, carbon number are 1～6 alkyl or nitro, and A represents N, S or O; In formula (V), R 1, R 2Represent that independently of one another carbon number is 1～6 alkyl, m and n represent 1～3 integer, m+n=4 independently of one another.
3, Photocurable composition as claimed in claim 1, wherein,
Described polymerizable compound is the compound with alkylene oxide chain.
4, a kind of color filter, wherein,
Have and use the demonstration pixel of the described Photocurable composition of claim 1 by the multiple color of photoetching process formation.
5, color filter as claimed in claim 4, wherein,
Described demonstration is more than the 5 μ m, below the 50 μ m with the size of pixel.
6, as claim 4 or 5 described color filters, wherein,
Described demonstration pixel with color more than 4 kinds.
CN 200610172462 2005-12-22 2006-12-18 Photo setting composition and color filter Pending CN1987649A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101750887B (en) * 2008-12-19 2012-07-18 京东方科技集团股份有限公司 Photosensitive resin composition
CN103339568A (en) * 2011-01-25 2013-10-02 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for manufacturing printed wiring board
CN103412464A (en) * 2011-09-21 2013-11-27 Jsr株式会社 Colored composition, color filter and display element

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101750887B (en) * 2008-12-19 2012-07-18 京东方科技集团股份有限公司 Photosensitive resin composition
CN103339568A (en) * 2011-01-25 2013-10-02 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for manufacturing printed wiring board
CN103412464A (en) * 2011-09-21 2013-11-27 Jsr株式会社 Colored composition, color filter and display element

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