CN101067668B - Method of manufacturing color filter, color filter and displaying device - Google Patents

Method of manufacturing color filter, color filter and displaying device Download PDF

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Publication number
CN101067668B
CN101067668B CN 200710100977 CN200710100977A CN101067668B CN 101067668 B CN101067668 B CN 101067668B CN 200710100977 CN200710100977 CN 200710100977 CN 200710100977 A CN200710100977 A CN 200710100977A CN 101067668 B CN101067668 B CN 101067668B
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color filter
ink
monomer
pixel
substrate
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CN101067668A (en
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安藤豪
和地直孝
新居欣三
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Fujifilm Corp
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Fujifilm Corp
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Abstract

The invention provides a manufacturing method of color filter; the said color filter comprises plurality of pixels and bulkheads among the pixels. The method of the color filter at least comprises steps a), b) and c). a), forming the bulkheads consisted of the resin combination on the substrate; b), carrying out the plasma treatment on the substrate having the bulkheads; c), ink jetting with printing ink to form the pixels in the clearance of the bulkheads on the substrate, the said printing ink at least contains the C.I paratonere 254, a solvent, a surfactant and at least more than two polymerizability base monomers. The invention can provide a manufacturing method of a high-quality color filter which doesn't produce color mixing and white point, forms smooth pixel, has high contrast when displaying the device, and well restrains the color spot.

Description

Manufacturing method of color filter, color filter and display device
Technical field
The present invention relates to a kind of manufacturing method of color filter, utilize color filter that this manufacture method obtains and LCD, display device such as lcd tv, described color filter forms pixel with ink-jet method between ink-repellant next door.
Background technology
In recent years, notebook computer increased gradually with the needs of color monitors such as LCD and lcd tv, and was more and more higher to the requirement that characteristic improves and cost reduces of indispensable color filter in this display.
At present, as manufacturing method of color filter, implement decoration method, pigment dispersing method, electrolytic deposition method, print process etc.
For example, the method of operating of decoration method is as follows: form the water miscible polymer material layer as the material of dyeing usefulness on transparency carrier, after it is utilized photo-mask process to make pattern to be desirable shape, the pattern that obtains be impregnated in dye vat, obtain the pattern of painted mistake.By this operation is carried out 3 times repeatedly, form dyed layer by painted formation of 3 looks of R (red), G (green), B (indigo plant).
In addition, the pigment dispersing method was in vogue day by day in recent years, its method of operating is as follows: form the photo-sensitive resin that is dispersed with pigment on transparency carrier, by being made into pattern, can obtain monochromatic pattern, by this operation is carried out 3 times repeatedly, form painted dyed layer that constitutes by 3 looks of R, G, B.
The method of operating of electrolytic deposition method is as follows: on transparency carrier transparency electrode is formed pattern, impregnated in the electrophoretic coating liquid that adding has pigment, resin, electrolytic solution etc., first look is carried out electrolytic deposition.This operation is carried out 3 times repeatedly, form painted dyed layer that constitutes, carry out roasting at last by 3 looks of R, G, B.
The method of operating of print process is as follows: in thermosetting resin with pigment dispersing, by carrying out 3 printings repeatedly, apply R, G, B respectively after, carry out heat curing by making resin, form dyed layer.
When use has any one manufacture method in these methods, generally all on the dyed layer that obtains, form protective seam.
The common ground of these methods is, in order to form 3 color pixels of redness, green, blueness, need carry out 3 times identical operation repeatedly, and cost raises.And, also have following problem, because process number is many, so stock utilization reduces easily.
In order to overcome these problems, studying manufacturing method of color filter in recent years, described color filter forms black matrix with the pigment dispersing method, makes rgb pixel with ink-jet method.This ink-jetting style is given R, G, B printing ink of all kinds successively in the gap (recess) of black matrix, forms pixel.Utilize the method for ink-jetting style to have the advantage that manufacturing process is simple, cost is low.
As mentioned above, can seek the simplification and the cost reduction of manufacturing process owing to give the method for drop with ink-jetting style, so be applied to the manufacturing of color filter, but utilize the peculiar problem in the manufacturing of color filter of this ink-jetting style to be have " colour mixture " to reach the problem of " white point " and so on.
Colour mixture is meant following phenomenon: forming black matrix and giving printing ink in the gap of this black matrix (peristome) and when forming pixel portions, exceed the black matrix that becomes the next door, printing ink overflows, and mixes between pixel adjacent portion.
In addition, white point is meant following phenomenon: the wetting state of the glass in gap and side, next door and printing ink is poor, can not expand fully at gap area printing ink sometimes, forms the gap between next door and the printing ink given sometimes.
These colour mixtures and white point cause the demonstration of color spot and contrast reduction and so on bad.
As the technology that is used to prevent colour mixture and white point, attempt utilizing fluorine plasma treatment counter septum to carry out anti-printing ink and handle (for example) with reference to patent documentation 1, can utilize the high-quality color filter that the fluorine plasma treatment forms does not have colour mixture and white point.
But, in the above-mentioned patent documentation 1, be discussion, and the pigment system that uses in vogue is in recent years inquired in detail to dyestuff system.
Relative with it, pigment has distinct color, high colouring power, photostability etc., is widely used in a lot of fields, particularly is being used for the color filter of lcd tv, very preferably uses aspect photostability.
But in this pigment was, the cohesiveness of pigment, the existence of dispersion resin etc. caused its viscosity to rise easily, had the problem of ejection property deterioration in ink device.In addition, when viscosity was high, the printing ink of giving the gap in next door sometimes can't form good shape, formed the pixel of convex, became the reason that color spot produces.
Therefore, consider, be fit to use the monomer class as the polymerizable compound that contains in the printing ink from the viewpoint that viscosity is difficult to rise, ejection property is good.Wherein, especially consider the aspect that viscosity is not easy to improve, use the monofunctional monomer class more.
But when using the monofunctional monomer class as polymerizable compound, it is insufficient to give the curing of printing ink in gap in next door with ink-jetting style sometimes, and it is poor to solidify the ITO sputter suitable property of inadequate pixel when forming display device, and the result becomes the reason that color spot produces.
In addition, well-known, in above-mentioned pigment, in order to improve excitation, the red pixel during color filter is made is fit to use C.I paratonere (C.I.P.R) 254 very much.
But the problem that exists when using C.I.P.R254 is that when color filter was carried out display device, the contrast of red pixel reduced greatly.
[patent documentation 1] spy opens the 2003-344640 communique
Summary of the invention
The objective of the invention is to, solve the above-mentioned shortcoming that exists at present.
That is, the objective of the invention is to, a kind of high-quality manufacturing method of color filter and the color filter that utilizes this manufacture method to make are provided, described color filter does not have colour mixture and white point, and can form smooth pixel.In addition, provide a kind of high-quality display device, described display device contrast height can suppress the generation of color spot.
In view of above-mentioned actual conditions, the present inventor learns after painstakingly studying: when using C.I.P.R254, by using at least a kind of monomer as the polymerizable compound that is used for ink for inking with 2 above polymerism bases, the contrast that can prevent described red pixel reduces, simultaneously, the suitable property of good ITO can be obtained, the generation of color spot can be suppressed.But, using pigment as colorant, when use has the monomer of 2 the above polymerism bases simultaneously, its viscosity raises, and forms the pixel of convex, becomes the reason that color spot produces.
Relative with it, the present inventor further painstakingly studies the back and finds, by adding surfactant, can form the pixel of smooth, good shape, until having finished the present invention.
That is, the present invention relates to:
＜1〉a kind of manufacturing method of color filter, described color filter is characterized in that in the next door that has on the substrate between a plurality of pixels and pixel adjacent, its have at least successively following a), b) and c) operation.
A) on substrate, form the operation in the next door that constitutes by resin combination
B) implement the operation of plasma treatment to forming septate substrate
C) in the gap that is formed at the described next door on the substrate, give the operation that ink for inking forms pixel with ink-jet method, described ink for inking contains C.I paratonere 254, solvent, surfactant at least and has the monomer of 2 above polymerism bases.
＜2〉as described＜1〉described manufacturing method of color filter is characterized in that, described plasma treatment is an atmospheric plasma processes.
＜3〉as described＜1〉or＜2〉described manufacturing method of color filter, it is characterized in that described monomer is the monomer with 3 above polymerism bases.
＜4〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜3 〉, and described polymerism base is the base with the two keys of ethene.
＜5〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜4 〉, and described polymerism base is an epoxy radicals.
＜6〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜5 〉, and described polymerism base is selected from least a kind in acryloyl group and the methacryl.
＜7〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜6 〉, and described ink for inking contains at least a kind that is selected from Photoepolymerizationinitiater initiater and the thermal polymerization.
＜8〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜6 〉, and described surfactant contains fluorine.
＜9〉each described manufacturing method of color filter as described＜1 〉～＜8 〉, it is characterized in that, described surfactant has at least 1 structural unit a and at least 1 structural unit b that comes the monomer of free following general formula (b) expression of coming the monomer of free following general formula (a) expression, and the mass ratio (a/b) that contains at least a structural unit a and structural unit b is 20/80～80/20 multipolymer (below, be sometimes referred to as " specific fluorine is a surfactant ").
General formula (a)
Figure G200710100977020070514D000041
General formula (b)
In general formula (a), R 1Expression hydrogen atom or methyl, in addition, in the general formula (a)-C mF 2m + 1Be straight or branched, m represents 2～14 integer, and n represents 1～18 integer,
In general formula (b), R 2And R 3Represent hydrogen atom or methyl independently of one another, R 4The alkyl of expression hydrogen atom or carbon number 1～5, p and q represent 0～18 integer independently of one another, p and q do not represent 0 (zero) simultaneously,
Described R 4The alkyl of expression carbon number 1～5.
＜10〉each described manufacturing method of color filter is characterized in that as described＜1 〉～＜7 〉, at described c) after the operation, further through being selected from following d) and at least one operation e), make the ink composite polymerization form pixel.
D) operation of irradiation active energy ray behind the solvent in removing removal ink
E) operation that heats
＜11〉a kind of color filter is characterized in that, it utilizes described＜1 〉～＜10 in each described manufacture method be made.
＜12〉a kind of display device is characterized in that, it possesses described＜11〉described color filter.
According to the present invention, a kind of high-quality manufacturing method of color filter and the color filter that utilizes this manufacture method to make are provided, described color filter does not have colour mixture and white point, and can form smooth pixel.In addition, provide a kind of high-quality display device, described display device contrast height can suppress the generation of color spot.
Embodiment
Manufacturing method of color filter of the present invention can be manufactured on the color filter that has the next door between a plurality of pixels and pixel adjacent on the substrate, it is characterized in that, its have at least successively following a), b) and c) operation.
A) on substrate, form the operation (next door forms operation) in the next door that constitutes by resin combination
B) implement the operation (plasma treatment operation) of plasma treatment to forming septate substrate
C) in the gap that is formed at the described next door on the substrate, give the operation (pixel formation operation) that ink for inking forms pixel with ink-jet method, described ink for inking contains C.I.P.R paratonere 254, solvent, surfactant at least and has the monomer of 2 above polymerism bases.
Below, when explaining when of the present invention, at first above-mentioned ink for inking is described in detail, then, further manufacturing method of color filter, display device and manufacture method thereof are narrated.＜ink for inking 〉
Ink for inking of the present invention contains C.I.P.R paratonere 254 (colorant), solvent, surfactant at least and has the necessary composition of monomer conduct of 2 above polymerism bases.Colorant, spreading agent, bonding agent, Photoepolymerizationinitiater initiater, thermal polymerization or other adjuvant that can suitably contain other in addition.
Wherein, from guaranteeing that the viscosity of ink for inking is preferably below the above 50mPas of 3mPas, more preferably below the above 30mPas of 5mPas from the viewpoint consideration of the ejection of ink gun.Therefore, the viscosity of preferred ink for inking is not too high.
In addition, the preferred 10～50dyne/cm of surface tension, more preferably 20～40dyne/cm.
(polymerizable monomer)
As be used for ink for inking of the present invention (below, sometimes abbreviate " printing ink " as) polymerizable monomer, the cationically polymerizable compound that the polyreaction that free-radical polymerised compound that the polyreaction that can use utilization to be caused by the free radical activity kind is cured and utilization are caused by cationic species is cured, to contain at least a kind of monomer with 2 above polymerism bases (below, be sometimes referred to as " 2 officials can above monomer ") and be set at necessary condition.
Ink composite of the present invention can constitute free-radical polymerised composition when use has described free-radical polymerised compound, can constitute cationically polymerizable composition when use has the cationically polymerizable compound, and any formation all is fit to.
As mentioned above, when use C.I.P.R.254 formation color filter, when carrying out display device, the contrast of red pixel reduces, and by using the above monomer of above-mentioned 2 officials energy, can prevent the reduction of this contrast effectively.In addition, consider that the preferred especially monomer with 3 above polymerism bases that uses more preferably uses the monomer with 5 above polymerism bases from the viewpoint that obtains more significant effect.
In addition,, obtain the suitable property of good ITO, can be suppressed at the color spot that produces when carrying out display device effectively by using the above monomer of 2 officials energy.Consider that from obtaining the viewpoint that the suitable property of this ITO pays the preferred especially monomer with 3 above polymerism bases that uses more preferably uses the monomer with 5 above polymerism bases.
Account for more than the preferred 10 quality % of ratio of the above monomer of the overall 2 officials energy of polymerizable monomer, more preferably more than the 30 quality %.As the above monomer of 2 officials energy, preferably the viscosity under 25 ℃ is the monomer below the 7000mPas, more preferably the following monomer of 1000mPas, the especially preferably following monomer of 500Pas.
In addition, for the viscosity that makes ink for inking does not too raise, the functional group in the preferred monomers (polymerism base) number is below 15, more preferably below 6.The kind of polymerism base is not particularly limited, and selects in the scope that can too not raise in the viscosity of printing ink.
In addition,, give the adaptation with substrate in order to strengthen film strength, can be on a small quantity and to be used in viscosity under 25 ℃ be the above full-bodied polyfunctional monomer of 700mPas and the contour polar monomer of urethane acrylate, oligomer etc.And with aspect preferred polyfunctional monomer and high polar monomer and oligomer be not particularly limited, can use general material, for example have: cyamelide EO (oxirane) modification diacrylate, cyamelide EO modification triacrylate, 6-caprolactone modification three (acryloxy ethyl) isocyanuric acid ester, (for example East Ami synthesizes (strain) System ア ロ ニ Network ス M-1000 to urethane acrylate, M-1200, M-1210, M-1600), (for example ， East Ami synthesizes (strain) System ア ロ ニ Network ス M-6100 to polyester acrylate, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050) etc.
-free-radical polymerised compound-
As free-radical polymerised compound, specifically can exemplify compound shown below, but be not limited to these.Contain monomer, oligomer that 2 officials can be above in free-radical polymerised compound, wherein, the base that especially preferably contains base (more preferably acryloxy, methacryloxy) with ethene pair keys or epoxy radicals is as the polymerism base.
The above monomer of described 2 officials energy, oligomer for example has: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1, the 6-hexanediyl ester, neopentyl glycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropyleneglycol diacrylate, 1,4-butylene glycol two (methyl) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-normal-butyl-2-ethyl-1, the ammediol diacrylate, dihydroxymethyl-tristane diacrylate, hydroxyl trimethylace tonitric neopentylglycol diacrylate, 1,3-butylene glycol two (methyl) acrylate, ethoxylation bisphenol-A two (methyl) acrylate, propoxylated bisphenol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl two cyclopentane diacrylates, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, ethoxylated trimethylolpropane triacrylate, the propoxylation trimethylolpropane triacrylate, pentaerythritol triacrylate, the tetra methylol propane triacrylate, the tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, the caprolactone modification trimethylolpropane triacrylate, ethoxylation cyamelide triacrylate, three (2-hydroxyethyl isocyanuric acid ester) triacrylate, the propoxylated glycerol triacrylate, the tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate, the double trimethylolpropane tetraacrylate, the ethoxylation tetramethylol methane tetraacrylate, dipentaerythritol acrylate, the neopentyl glycol low-polyacrylate, 1,4-butylene glycol low-polyacrylate, 1,6-hexanediol low-polyacrylate, the trimethylolpropane low-polyacrylate, the pentaerythrite low-polyacrylate, urethane acrylate, epoxy acrylate, polyester acrylate etc.
In addition, 3 officials can be above the concrete example of polymerizable monomer, can exemplify the spy open the 2001-350012 communique described 3 officials in paragraph sequence number [0061]～[0063] can " market expectation of reactive monomer " described 3 officials that contain acrylate monomer that epoxy radicals monomer and special described 3 officials of paragraph sequence number [0016] that open the 2002-371216 communique can be above, methacrylate monomers and publish according to CMC can be above monomer etc.
In above-mentioned concrete example, preferred especially: trimethylolpropane triacrylate, trimethylolpropane PO (epoxypropane) modification triacrylate, trimethylolpropane EO (oxirane) modification triacrylate, tetramethylol methane tetraacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate etc.
These compounds can use a kind of or use two or more as required.
-cationically polymerizable compound-
The cationically polymerizable compound is to utilize the cationic species polymerization reaction take place that is produced by polymerization initiator, the compound that is cured.
Cationic polymerization rerum natura compound can exemplify the monomer as the known various known cationically polymerizables of cationically photopolymerizable monomer, for example can exemplify the spy and open flat 6-9714 number, spy and open 2001-31892 number, spy and open 2001-40068 number, spy and open 2001-55507 number, spy and open 2001-310938 number, spy and open 2001-310937 number, spy and the described vinethene compound of each communique, oxetane compound, oxirane compound etc. such as open 2001-220526 number.
The cationically polymerizable compound that has vinethene in functional group for example has: urethane is that vinethene (vinethene urethane), ester are vinethene etc.These oligomer can use or mix use separately.
In addition, the concrete example of aromatic epoxy resin, can exemplify the polyhydric phenol that has 1 aromatic ring at least or the polyglycidyl ether of its epoxide addition product, for example: bisphenol-A, Bisphenol F and in these materials further addition the glycidol ether, epoxy-Novolak resin, bisphenol-A phenolic varnish diglycidyl ether, bisphenol F phenolic varnish diglycidyl ether etc. of the compound of epoxide are arranged.
In addition, the concrete example of aromatic epoxy resin can exemplify the polyglycidyl ether of the polyvalent alcohol that has 1 ester ring type ring at least or cyclohexene, contain the cyclohexene oxide structures compound, contains the cyclopentene oxide structural compounds or contain the vinyl cyclohexane structural compounds by what the compound that will have the vinyl cyclohexane structure with oxygenant carried out that epoxidation obtains by what will contain with oxygenant that the cyclopentene cyclic compound carries out that epoxidation obtains.
For example have: the hydrogenation bisphenol A diglycidyl ether, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylic acid ester, 6-methyl-3,4-epoxycyclohexyl methyl-6-methyl-3, the 4-epoxycyclohexane carboxylate, 3,4-epoxy-3-methyl cyclohexane ylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylic acid ester, 3,4-epoxy-5-methyl cyclohexane ylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylic acid ester, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) cyclohexane-methyldioxane, two (3,4-epoxycyclohexyl methyl) adipate, the vinyl cyclohexene dioxide, 4 vinyl epoxy cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, methylene two (3, the 4-7-oxa-bicyclo[4.1.0), the dicyclopentadiene diepoxide, ethylene glycol bisthioglycolate (3,4-epoxycyclohexyl methyl) ether, methylene two (3, the 4-7-oxa-bicyclo[4.1.0), the bicyclopentadiene diepoxide, ethylene glycol bisthioglycolate (3,4-epoxycyclohexyl methyl) ether, ethylene two (3, the 4-epoxycyclohexane carboxylate), epoxy hexahydro-phthalic acid dioctyl ester, the own ester of epoxy hexahydro-phthalic acid two-2-methyl etc.
The concrete example of aliphatic epoxy resin can exemplify the poly glycidyl ester of polyglycidyl ether, the aliphatic long-chain polyprotonic acid of aliphatic polyol or its epoxide addition product, the multipolymer by the aliphatic long-chain unsaturated hydrocarbon being carried out the homopolymer that contains epoxy compounds, glycidyl acrylate or glycidyl methacrylate, glycidyl acrylate or glycidyl methacrylate that oxidation obtains with oxygenant etc.
The compound of representative for example has: 1, the 4-butanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, the triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, four glycidol ethers of pentaerythrite, four glycidol ethers of D-sorbite, six glycidol ethers of dipentaerythritol, the diglycidyl ether of polyglycol, the glycidol ether of polyvalent alcohols such as the diglycidyl ether of polypropylene glycol, in addition, by at propylene glycol, the polyglycidyl ether of the polyether glycol that the epoxide of addition more than a kind or 2 kinds obtains on the aliphatic polyols such as glycerine, the 2-glycidyl ester of aliphatic long-chain dibasic acid etc.And, a glycidol ether, the ethylene oxidic ester of higher fatty acid, epoxidised soybean oil, octyl epoxy stearate, butyl epoxy stearate, the epoxidation linseed wet goods of a glycidol ether of aliphatics higher alcohol and phenol, cresols, butylphenol and the Aethoxy Sklerol that obtains by addition epoxide on these materials.
In addition, can use epoxy compound as polymerizable monomer.Can use various epoxy compounds such as aromatic epoxy resin, aromatic epoxy resin as epoxy compound.
In addition, can also use the various epoxy compounds that can also use more than the 2 officials energy.For example, just setting volumes " epoxy resin handbook " Nikkan Kogyo Shimbun new guarantor prints in (clear and 62 years) etc. and extensively discloses these compounds.Specifically, bisphenol A type epoxy resin, bisphenol f type epoxy resin, the ozonidation bisphenol A type epoxy resin, bisphenol-s epoxy resin, diphenyl ether type epoxy resin, the p-dihydroxy-benzene type, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, phenol novolac type epoxy resin, o-cresol phenolic epoxy varnish, trihydroxy phenol methane type epoxy resin, trifunctional type epoxy resin, four phenylol ethane type epoxy resin, two pentadiene phenol type epoxy resin, the hydrogenation bisphenol A type epoxy resin, bisphenol-A contains nuclear polyhydroxy type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, glyoxal type epoxy resin, alicyclic type epoxy resin, heterocyclic-type epoxy resin etc.
Under the situation that is epoxy compound, consider to prevent color spot, preferably also with the compound that contains carboxylic acid.Contain the compound of carboxylic acid as this, can enumerate trihemellitic acid and pyromellitic acid.
For this carboxylic acid that contains the compound of carboxylic acid, consider and preferably carry out consolidated block for the viscosity of printing ink is adjusted to described preferable range.As the compound that carboxylic acid is carried out consolidated block, preferred alkyl vinyl ether, especially preferred primary alkyl vinyl ether.
As polyvalent carboxylic acid's acid anhydride concrete example, can enumerate: the aliphatics or the alicyclic carboxylic acid acid anhydride, 1 of butyric anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, six hydrogen butyric anhydrides, dimethyl tetrahydro butyric anhydride, Hai Mike acid (acid of Ha イ ミ Star Network) acid anhydride, Luo Jin acid (acid of ラ ジ Application) acid anhydride etc., 2,3, aliphatics polyvalent carboxylic acid's dianhydrides such as 4-butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic dianhydride; Aromatic series polyvalent carboxylic acid acid anhydrides such as PMA, trihemellitic acid acid anhydride, benzophenonetetracarboxylic acid acid anhydride; Ethylene glycol bisthioglycolate trimellitate, glycerine three trimellitates etc. contain the acid anhydrides of ester group, wherein optimization aromatic polyvalent carboxylic acid acid anhydride especially.In addition, the commercially available epoxy curing agent that is made of carboxylic acid anhydrides also can use well.
In addition, the polyvalent carboxylic acid's who uses as the present invention concrete example can be enumerated aliphatics polyvalent carboxylic acids such as succinic acid, glutaric acid, hexane diacid, BTCA, maleic acid, itaconic acid; Six hydrogen butyric acid, 1,2-cyclohexane-carboxylic acid, 1,2, aliphatics polyvalent carboxylic acid such as 4-cyclohexane tricarboxylic acids, cyclopentane thinking calculation and butyric acid, isophathalic acid, terephthalic acids, pyromellitic acid, trihemellitic acid, 1,4,5, aromatic series polyvalent carboxylic acids such as 8-naphthalene tetracarboxylic acid, benzophenonetetracarboxylic acid, wherein optimization aromatic polyvalent carboxylic acid.
Wherein, preferably use consolidated block aromatic series polyvalent carboxylic acid, especially preferred consolidated block trihemellitic acid and consolidated block pyromellitic acid.
These hardening agent can be used alone, and also can two or more mixing use.The use level of the hardening agent that the present invention uses is with respect to the composition that contains the machine of feeding (adhesive epoxy compound and multi-functional epoxy compound) 100 weight portions, to be generally 1～100 weight portion scope, preferred 5～50 weight portions.In addition, these polymer class can be used a kind of or use two or more as required.
In addition, in above-mentioned polymerizable monomer composition,, can suitably and use monofunctional monomer in order to reduce the viscosity of printing ink.These monofunctional monomers for example have: the spy open the acrylate monomer that contains epoxy radicals monomer and special paragraph sequence number [0015]～[0016] described simple function of opening the 2002-371216 communique of the described simple function of paragraph sequence number [0065] of 2001-350012 communique and methacrylate monomers, and " market expectation of reactive monomer " described 1 official of publishing according to CMC can monomer etc.
In the present invention, the use amount that the polymerizable monomer in the ink for inking is overall is more than the 10 quality % in the preferred printing ink solid constituent, more preferably more than the 30 quality %, further more than the preferred 50 quality %.
By making the overall use amount of polymerizable monomer be in above-mentioned scope, the contrast of the red pixel of the color filter after can preventing to use C.I.P.R.254 carry out display deviceization reduces, and in addition, can obtain the suitable property of good ITO.
(surfactant)
As mentioned above, the contrast of the red pixel of the color filter when preventing to use C.I.P.R.254 to carry out display device reduces and the viewpoint of the good suitable property of ITO is considered, in the present invention, use the monomer more than the 2 officials energy in printing ink, the above monomer of 2 officials energy also has the characteristic of the viscosity that improves printing ink but then.Therefore, during the printing ink of the monomer more than use contains 2 officials energy, the pixel unevenness of formation becomes convex.In addition, so-called convex is meant that center portion of pixels compares the shape of protuberance with the edge (approaching the part in next door) of pixel, when becoming this shape, produces the density unevenness in the pixel, becomes the color filter that color spot is arranged.What the present inventor painstakingly studied found that, can prevent this color spot by adding surfactant.Its mechanism of action is presumed as follows.
When being added with surfactant, usually supposition can obtain the pixel of the good shape (smooth) that the screening characteristics of the pixel faces (real estate) to printing ink improves, and distinguishes that above-mentioned effect does not obtain by improving wetting state.Specifically, when in printing ink, not adding surfactant and when adding surfactant, all do not change irrelevantly, can see that pixel is shaped as convex when not adding surfactant in the printing ink, the smooth phenomenon of primitive shape when adding surfactant with the contact angle of substrate.
This phenomenon can followingly be understood.
Because printing ink contains solvent and other adjuvant, thus begin the screening characteristics of substrate not poor.Even add surfactant under this state, it is also not too enough that the screening characteristics on the macroeconomic significance of considering from surface tension improves effect.Therefore, as mentioned above, it has been generally acknowledged that contact angle not too changes.On the other hand, when examining the printing ink that splashes into pixel, when not adding surfactant, next door recess protuberance, the protruding shape of the printing ink that fixedly splashes into is so that its film expansion in the drying way.Relative with it, when having added surfactant, do not fix protruding shape, carry out drying lentamente, form the pixel of smooth shape at last.
In general, the quantity of ink that splashes into ink discharge device is pL (micromicro liter) level, because considerably less (contact angle determination is a μ L level) and the surface area of unit volume are big, so drying may be very fast.Therefore, it has been generally acknowledged that, when not adding surfactant, drying, the film expansion of printing ink take place sharply.On the other hand, when having added surfactant, by the effect of surfactant, it is sharply dry to suppress printing ink, and China ink does not carry out film expansion ground and carries out drying, obtains the pixel of smooth, good shape.The effect of surfactant thinks, the surfactant part is present on the air interface of printing ink to cover ink pellet surface, the perhaps result of surfactant and solvent interaction of molecules.Therefore, in general, the planarization effect of surfactant with position that interaction between the solvent molecule of the very large fluorochemical surfactant of surface orientation, polyethylene oxide or polypropyleneoxide etc. may be big is big.Wherein, the effect of fluorochemical surfactant that effectively covers ink pellet surface is bigger, and the effect of fluorochemical surfactant that especially contains polyethylene oxide or polypropyleneoxide is good especially.
In addition, the shape of pixel can use contact surfagauge P-10 (Tenoor society system) to measure.Specifically, in the time accessing color filter,, then carefully from display device in the time can not obtaining color filter take out color filter and its pixel is measured the pixel of this color filter.As required, by color filter being implemented the processing of hydrochloric acid or sulfuric acid, can take out ITO.
The surfactant that is used for ink for inking of the present invention is not particularly limited, and can exemplify the spy and open the paragraph sequence number [0021] of flat 7-216276 communique and spy and open 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed surfactant as preferred surfactants.
Wherein, can prevent that in interpolation aspect the color spot, preferred surfactant contains fluorine with less amount, and contain polyethylene oxide or polypropyleneoxide also preferred because of identical reason, in addition, be polymkeric substance with same viewpoint preferred surfactant.The surfactant of special preferred fluoropolymer, contain the polymkeric substance of polyethylene oxide or polypropyleneoxide surfactant, comprise the fluoropolymer surface activating agent of polyethylene oxide or polypropyleneoxide.The weight-average molecular weight of polymeric surfactant preferably 1000～100000, more preferably 5000～40000.
As fluorine, preferably carbon number is 1～14 perfluoroalkyl, more preferably carbon number is 4～8 perfluoroalkyl.
Weight-average molecular weight among the present invention can be measured by GPC and try to achieve with polystyrene conversion.
Wherein, preferred especially following fluorine is a surfactant.
-fluorine be surfactant-
Ink composition for ink jet among the present invention preferably has the structural unit b of the structural unit a of at least 1 monomer that comes free following general formula (a) expression and at least 1 monomer that comes free following general formula (b) expression as surfactant, and the mass ratio (a/b) that contains at least a structural unit a and structural unit b is 20/80～80/20 multipolymer (below, be sometimes referred to as " specific fluorine is a surfactant ").The viewpoint of the pixel of, excellent in shape smooth from forming considers that preferred especially this fluorine is that surfactant is fluorine-containing macromolecule.
[changing 1]
General formula (a)
Figure G200710100977020070514D000131
General formula (b)
Figure G200710100977020070514D000132
The monomer of mutual-through type (a) expression (below, be also referred to as monomer and a) describe.
In general formula (a), R 1Expression hydrogen atom or methyl.In addition, in the general formula (a)-C mF 2m + 1Can be straight chain, also can be side chain.M represents 2～14 integer, is preferably 4～8 integer.N represents 1～18 integer, is preferably 2～10.
Described-C mF 2m+1For example have :-C 4F 9, C 6F 13, C 12F 25Deng.
With respect to the total amount of monomer a, described-C mF 2m+1Preferred 20～80 quality % of ratio, preferred especially 40～60 quality %.
In described monomer a, preferred especially R 1For hydrogen atom ,-C mF 2m+1Be C 6F 13, n is 2 compound.
The monomer of mutual-through type (b) expression (below, be also referred to as monomer b) describe.
In general formula (b), R 1And R 2Represent hydrogen atom or methyl independently of one another, R 4The alkyl of expression hydrogen atom or carbon number 1～5.P and q represent 0～18 integer independently of one another, and p and q do not represent 0 (zero) simultaneously.P and q preferred 2～8.
Described R 4Alkyl preferable methyl, the ethyl of the carbon number 1～5 of expression.
In described monomer b, preferred especially R 2Be hydrogen atom, R 3Be methyl, R 4For hydrogen atom, p are 7, q is 0 compound and R 2Be hydrogen atom, R 3Be hydrogen atom, R 4For hydrogen atom, p are 0, q is 7 compound.
The specific fluorine of 1 molecule is the monomer a that contains in the surfactant, can only be mutually identical a kind of of structure, also can be different mutually multiple of structure.To monomer b too.
Specific fluorine is that the quality average molecular weight Mw of surfactant is preferred 1000～100000, more preferably 5000～40000.
As mentioned above, specific fluorine is that surfactant is to carry out the multipolymer that copolymerization forms to described monomer a of major general and described monomer b, and the monomer a/ monomer b in the multipolymer is set at 20/80～80/20 than (mass ratio).In the time of in copolymerization ratio is described scope, giving ink-jet, so that it is when the recess of dividing imperceptibly with the next door, being surrounded by the next door makes its drying than the high lifting of wall in next door, can be with above the printing ink, promptly become the flattening surface of the painted areas of colored pixels.
Specific fluorine is the multipolymer that surfactant also preferably makes above-mentioned monomer a and b form with other any monomer copolymerization together.At this moment, beyond monomer a, the b can copolymerization other any monomer for example have: ethene base system monomers such as dienes, vinyl cyanide, ethene ethers, methacrylic acid, acrylic acid, itaconic acid, butenoic acid, maleic acid, partial esterification maleic acid, styrene sulfonic acid maleic anhydride, cinnamic acid, vinyl chloride, vinyl acetate such as styrene such as styrene, vinyltoluene, α-Jia Jibenyixi, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, vinylbenzenesulfonic acid sodium, aminobenzene ethene and derivant thereof, substituent, butadiene, isoprene etc.
For example, at specific fluorine is surfactant when being 100 mass parts, preferably the multipolymer more than 2 yuan or 3 yuan that is made of monomer a 20～80 mass parts and monomer b 80～20 mass parts, the multipolymer more than 3 yuan that is made of monomer a 20～80 mass parts and monomer b 80～20 mass parts and other any monomer (remaining mass parts).
And, the preferably multipolymer more than 2 yuan or 3 yuan that constitutes by monomer a 25～60 mass parts and monomer b 60～40 mass parts, the multipolymer more than 3 yuan that constitutes by monomer a 25～60 mass parts and monomer b 60～40 mass parts and other any monomer (remaining mass parts).
Specific fluorine is that surfactant is the multipolymer that forms to major general's monomer a, monomer b copolymerization, monomer whose arranged be not particularly limited, and can be random copolymerization, also can be any of regular, for example block copolymerization, graft copolymerization.
Specific fluorine is that surfactant can be formed molecular structure and/or monomer more than 2 kinds different material mixing uses.
Below, represent that specific fluorine is the concrete example of surfactant.But, be not limited to these concrete examples in the present invention.
[table 1]
Figure G200710100977020070514D000161
Be used for all surfaces activating agent of ink for inking of the present invention, preferred 1～100 quality % of the content that above-mentioned specific fluorine is a surfactant, more preferably 50～100 quality %, preferred especially 90～100 quality %.
In addition, the content of all surfaces activating agent in the ink for inking of the present invention, below the preferred 10 quality % of ink composite total amount, more preferably 0.01～8 quality %, preferred especially 0.05～5 quality %.Admittedly form branch with respect to printing ink, below the preferred 30 quality %, more preferably 0.01～15 quality %, preferred especially 0.1～10 quality %.When the content of all surfaces activating agent in the printing ink is in the described scope time, can form the pixel of excellent in shape more significantly, and then the generation of the demonstration inequality in the image can prevent effectively that image from showing the time.
(colorant)
In the present invention, the colorant that is used to form the ink composite of red pixel is a necessary condition to contain C.I paratonere (C.I.P.R.) 254, and can and wait with other known pigment in this ink composite and constitute.By using C.I.P.R.254, can be implemented in the high excitation that requires in the color monitor of notebook computer with LCD and lcd tv etc.
Wherein, the whole pigment that preferably contain C.I.P.R.254 disperse in the pigmented fluids composition equably, and therefore, preferred number average bead diameter is 0.01～0.12 μ m, is preferably 0.02～0.08 μ m especially.
Here, so-called particle diameter is meant, when a degree month year is carried out the electron microscope shooting, with this pigment image diameter of a circle of the same area.Number average bead diameter is the particle diameter that 100 particles is carried out the arithmetic mean of particle diameter.
The confirmation method that exists as C.I.P.R254 can adopt known analytical approachs such as infrared measure, Raman's optical spectroscopy, chromatography, mass spectrum method, various ultimate analyses.For easy viewpoint, preferred infrared measure, Raman's optical spectroscopy.Consider highly sensitive, preferred TOF-SIMS.A kind of analytic approach can be adopted, also the multiple analytic approach of employing can be made up.In order to improve the degree of accuracy of analysis, preferably use a plurality of analytic approachs to confirm, especially preferably adopt Raman's optical spectroscopy and TOF-SIMS to confirm.
The known dyestuff of described and usefulness or pigment for example can preferably use the spy to open that 2005-17716 communique [0038]～[0054] described pigment and dyestuff, spy open 2004-361447 communique [0068]～[0072] described pigment, the spy opens 2005-17521 communique [0080]～[0088] described colorant.Wherein, consider special preferred pigments from the storage stability of pixel.
In addition, be used for the ink composite of other color of manufacturing method of color filter of the present invention, in the ink composite of G (green), can exemplify the C.I. pigment green 36, in the ink composite of B (indigo plant), can exemplify the C.I. pigment blue 15: 6.
At this, to and the combination of the preferred pigments of usefulness describe, essential described C.I. paratonere 254 among the present invention is preferably with the combination of C.I. paratonere 177, C.I. paratonere 224, C.I. pigment yellow 13 9 or C.I. pigment Violet 23.
In addition, described C.I. pigment green 36 preferably with the combination of C.I. pigment yellow 150, C.I. pigment yellow 13 9, C.I. pigment yellow 185, C.I. pigment yellow 13 8 or C.I. pigment yellow 180, described C.I. pigment blue 15: the combination of 6 preferred and C.I. pigment Violet 23 or C.I. pigment blue 60s.
And the content of the C.I. paratonere 254 in the pigment of time spent, more than the preferred 80 quality %, more than the preferred especially 90 quality %.
In addition, C.I. pigment green 36 or C.I. pigment blue 15: each content of 6, more than the preferred 50 quality % of described C.I. pigment green 36, more than the preferred especially 60 quality %, described C.I. pigment blue 15: more than the 6 preferred 80 quality %, more than the preferred especially 90 quality %.
Pigment optimization uses as dispersion liquid.This dispersion liquid can add in the polymerizable compound described later (or vehicles and solvent) by the composition that the described pigment of premixed and pigment dispersing agent are obtained makes it disperse to prepare.The dispersion machine that uses when making described pigment dispersing is not particularly limited, and can exemplify " encyclopaedia of pigment " (Chao Warehouse nation and make work, first published, Chao Warehouse Books shop, 2000,438) described kneader, roller pulverizer, Aunar come known dispersion machines such as moral machine (ア ト ラ イ ダ one), super mixer, dissolving machine, homo-mixer, puddle mixer.And it is broken that the friction force that can utilize 310 described mechanical crushing by " encyclopaedia of pigment " to produce is carried out micro mist.
The particle diameter of colorant (pigment) is preferably 0.001～0.1 μ m in number average bead diameter, further preferred 0.01～0.08 μ m.Under this scope, can realize high contrast.
Need to prove that so-called " particle diameter " is meant the particle of electron micrograph image is used diameter when representing with its circle with area that so-called " number average bead diameter " is meant the particle diameter of obtaining particle and gets 100 average mean values.
The contrast of colored pixels can be by dwindling dispersion the particle diameter of pigment improve.Dwindling particle diameter can realize by the jitter time of regulating the pigment dispersing thing.In dispersion, can use described known dispersion machine.
Preferred 10～30 hours of jitter time, further preferred 18～30 hours, most preferably 24～30 hours.When jitter time was lower than 10 hours, pigment particle size was big sometimes, produced the releasing of the polarized light that is caused by pigment, and contrast reduces, and when it surpassed 30 hours, the viscosity of dispersion liquid rose sometimes, is difficult to spray from ink gun.
In addition, in the difference preferred 600 of the contrast of the painted areas that 2 kinds of colors are above,, preferably regulate pigment particle size in order to be adjusted in 600.
The contrast of each colored pixels of formation color filter is preferred more than 2000, and is more preferably more than 2800, further preferred more than 3000, most preferably more than 3400.When its contrast is lower than 2000, when observation has the image of liquid crystal indicator of this color filter, wholely sometimes become the impression of turning white, become the image that is difficult to see.In the difference of the contrast of each colored pixels preferred 600, more preferably in 410, further in preferred 350, most preferably in 200.When the difference of its contrast is in 600 the time, because the light leak amount of each the colored pixels portion during from black the demonstration does not have big difference, so the color balance of black demonstration is good.
Described what is called " contrast of colored pixels " is meant the contrast that every kind of color of the R, the G that constitute color filter, B is estimated separately.Set very for a short time by measuring the angle, can measure contrast at each pixel.The mensuration of contrast is following carries out: at the overlapping polaroid in the both sides of determinand, the polarization direction of polaroid is parallel to each other, under this state, side-irradiation backlight from a polaroid, measure brightness Y1, further making under the orthogonal state of polaroid, from the side-irradiation backlight of a polaroid by the light of another polaroid, measure brightness Y2, use the measured value that obtains to calculate Y1/Y2 by the light of another polaroid.Need to prove that it is identical with the polaroid of the liquid crystal indicator that is used to use color filter to be used for polaroid that contrast measures.As the polaroid that in mensuration, uses, preferably determine the polaroid of regulation.If the polaroid that can not obtain stipulating then can use to be applied to the polaroid on the display device and to measure contrast.
In order to obtain desirable color, concentration, the amount of the pigment in the ink composite can suitably be selected, and preferably with respect to the total amount of ink composite, is preferably more than the 3.0 quality %, more preferably more than the 5.0 quality %.
For the contrast of the color filter after carry out display deviceization, ready-made display device is very carefully decomposed, take out color filter part, measure as previously mentioned.
(polymerization initiator)
Be used for polymerization initiator of the present invention and can use any of Photoepolymerizationinitiater initiater and thermal polymerization, in addition, in polymerizable compound, can be used irradiation by active energy ray produce the free radical activity kind, cause free-radical polymerised compound polymerization radical polymerization initiator and produce cationic species, cause any of cationic polymerization initiators of the polymerization of cationically polymerizable compound.
-radical polymerization initiator-
Radical polymerization initiator can exemplify following material.Benzophenone series for example has: benzophenone, benzoyl benzoic acid, 4-phenyl benzophenone, 4,4-lignocaine benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide etc.; Thioxanthones system for example has: thioxanthones, 2-clopenthixal ketone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxyl group thioxanthones, isopropyl thioxanthone etc.; Acetophenone system for example has: 2-methyl isophthalic acid-(4-methyl mercapto) phenyl-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1,2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,2-dimethyl-2-hydroxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 4-phenoxy group dichloroacetophenone, diethoxy acetophenone, 1-hydroxycyclohexylphenylketone etc.; Benzoin system for example has: benzoin methyl ether, benzoin isobutyl ether, benzyl methyl ketal etc.; Acyl group phosphine oxygen system for example has: 2,4, and 6-trimethylbenzene acyl group diphenyl phosphine oxygen, two (2,4,6-trimethylbenzene acyl group) acyl group phosphine oxygen etc.
-cationic polymerization initiators-
Cationic polymerization initiators preference such as diazo salt, salt compounded of iodine, sulfonium salt, iron arene complex compound and organic polyhalide.Diazo salt, salt compounded of iodine and sulfonium salt for example have: special public clear 54-14277 communique, special public clear 54-14278 communique, spy open clear 51-56885 communique, United States Patent (USP) the 3rd, 708, No. 296 instructionss, the 3rd, 853, No. 002 described compound such as instructions of United States Patent (USP).
In addition, the light cationic polymerization initiators for example has: aromatic series diazo salt, aromatic series sulfonium salt, aromatic series salt compounded of iodine, aromatic ring alkene metallic compound, silicon compound/aluminium complex etc.
With respect to described polymerizable compound (quality), the amount of the polymerization initiator in the ink composite is preferably 5～60 quality %, more preferably 10～50 quality %.In the time of in polymerization initiator is described scope, can satisfy curable, not need to prolong irradiation time etc. with the intensity of general active energy ray.
(solvent)
Except that mentioned component, ink composite of the present invention will use solvent as necessary condition.When containing solvent, when splashing into, can give suitable flowability with ink-jet method, simultaneously, utilize the surfactant of having stated of the present invention to form flatness effectively.In the scope that does not influence effect of the present invention, the suitable amount of selective solvent.
The dissolving or the dispersion of functional materials such as the colorant that contains in the auxiliary ink composite of the present invention of the solvent among the present invention, polymerizable monomer, adjuvant, polymkeric substance, play the effect of the flowability that improves ink composite of the present invention, splash into etc. easily, simultaneously, after splashing into ink composite and drying of stipulating or thermal treatment, its major part (more than general 9 one-tenth) waits by evaporation and is removed.For example, polymerizable monomer also is liquid, and when adding this solvent therein, flowability is higher, easier splashing into.Usually the use boiling point is the solvent more than 100 ℃.In addition, stop up in order to prevent ink setting and shower nozzle, can use boiling point below 200 ℃, according to circumstances use boiling point is high boiling solvent more than this value.
Described solvent refer to " new edition solvent handbook " (organic synthesis Ke Association can Knitting, オ one ム She development capable) and " solvent handbook " (?Original Photo three ほ か Knitting, Talk Talk societies, 1976) described solvent, as concrete example, can use: ethylene glycol monoalkyl ether acetates such as ion exchange water, glycol monoethyl ether acetate; Diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether monoalkyl ethers; Diethylene glycol monoalky lether acetates such as diethylene glycol mono-n-butyl ether acetate; Propylene-glycol monoalky lether acetates such as propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate; 1,3 butylene glycol two acetate types such as 1,3 butylene glycol two acetic acid; Other ethers such as diethylene glycol dimethyl ether; Ketones such as cyclohexanone, 2-heptanone, 3-heptanone, butanone, methylisobutylketone, acetone; Lactic acid alkyl ester classes such as 2 hydroxy propanoic acid ethyl ester; Other ester classes such as 3-methyl-3-methoxyl butyl propionic ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, butyric acid ethyl ester, butyric acid isopropyl ester, the positive butyl ester of butyric acid, ethyl pyruvate; High boiling solvent classes such as gamma-butyrolacton.
The solid constituent amount of ink composition for ink jet of the present invention is preferably more than the 15 quality %, more preferably more than the 50 quality %.At this, so-called solid constituent is meant solvent composition in addition, about solvent as mentioned above.
Printing ink ink composite of the present invention considers that flatness pays, admittedly form component preferably 5～99 quality %, preferred 10～50 quality %, more preferably 10～30 quality %.Wherein, be meant solvent composition in addition Gu form to divide, and solvent is the solvent of having narrated.
＜color filter and manufacture method thereof 〉
Color filter among the present invention is that the next door that has the above pixel group of 2 kinds of different colors of color on the substrate and will constitute the light-proofness that each pixel of pixel group isolates mutually forms.Utilize ink-jet method that painted areas (dyed layer) is set in the gap (recess) that surrounds with the next door, form pattern of pixels and form.
Manufacturing method of color filter of the present invention is characterised in that it has 3 operations at least:
A) on substrate, form the operation (next door forms operation) in the next door that constitutes by resin combination
B) implement the operation (plasma treatment operation) of plasma treatment to forming septate substrate
C) in the gap that is formed at the described next door on the substrate, give the operation (pixel formation operation) that ink for inking forms pixel with ink-jet method, described ink for inking contains C.I.P.R.254, solvent, surfactant at least and has the monomer of 2 above polymerism bases.In addition, preferably at above-mentioned c) be provided with after the operation
D) operation of irradiation active energy ray behind the solvent in removing removal ink
E) operation that heats
Deng curing process.
-next door formation operation-
In manufacturing method of color filter of the present invention, the next door that forms the next door at first is set forms operation, this next door forms operation and uses dark composition to form the next door.
So-called dark composition, the preferred high composition of optical concentration, preferred optical concentration is for becoming 2.0～10.0 optical concentration when being formed with the photosensitive polymer combination layer that is equivalent to next door thickness.Preferred optical concentration is 2.5～6.0, preferred especially 3.0～5.0.In addition, when photo-sensitive resin and dark composition preferably make it solidify as described later in light-initiated system, also be important with respect to the optical concentration of exposure wavelength (being generally ultraviolet region), its value is preferably 2.0～10.0, more preferably 2.5～6.0, most preferably 3.0～5.0.In the time of in it is described scope, polymerizing curable is good, can form the next door of desired shape.Dark character can be used by various colorants such as dyestuff described later, pigment or the carbon of various forms or their material that constitutes and give, most preferably black.The optical concentration in next door is the absorbance of the light of the 555nm in next door.
Dark composition can use colorant and polymerization initiating system and polymerizable compound to constitute at least, described polymerization initiating system generally can exemplify the hot initiating system that uses thermal initiator, the light-initiated system that uses light trigger, preferably is made of light-initiated system.
When utilizing light-initiated system, constitute the formation in the next door of the color filter among the present invention, can suitably carry out by the following method, for example, before carrying out pixel formation operation described later and curing process, on at least one substrate, use dark composition to form photo-sensitive resin, the photo-sensitive resin (preferably under anoxia condition) that forms is exposed into pattern form, develops.As mentioned above, the next door is the partition pattern of isolating painted areas (pixel), and this painted areas splashes into the drop that utilizes curable printing ink of the present invention (ink composition for ink jet) with ink-jet method and forms.In addition, next door forms in the operation, after forming photo-sensitive resin and exposing, implements the plasma treatment as anti-printing ink processing at least, in addition, other operations such as calcination process can be set as required.
Below, so that be that the center describes as the situation that the polymerization initiating system constitutes with the light initiating system.
(formation of photo-sensitive resin)
The dark composition that photo-sensitive resin can use colorant, polymerizable compound and contain light-initiated system constitutes, as required, can further use bonding agent, known adjuvant, for example other one-tenth such as plastifier, filling agent, stabilization agent, polymerization inhibitor, surfactant, solvent, driving fit promoter assign to constitute.
Specifically, photo-sensitive resin can utilize following method to form, and gives dark composition and (contain for example polymerizable monomer, Photoepolymerizationinitiater initiater, bonding agent and colorant on substrate.) the method coating process of composition (preferred coated dark) and, use method (transfer printing) with the photosensitive transfer printing material transfer printing photo-sensitive resin on substrate that uses the photo-sensitive resin that dark composition is arranged etc.The details aftermentioned of dark composition and photosensitive transfer printing material.
When utilizing coating to form the method (coating process) of photo-sensitive resin, preferably use the slit-shaped nozzle or the slit coating machine in hole to apply with slit-shaped in the part of ejection liquid.
Specifically, can suitably use the spy to open 2004-89851 communique, spy opens 2004-17043 communique, spy and opens 2003-170098 communique, spy and open 2003-164787 communique, spy and open that 2003-10767 communique, spy are opened the 2002-79163 communique, the spy drives described slit-shaped nozzle and slit coating machines such as 2001-310147 communique.As other example, can use whirler, rotary emulsion film applicator, roll coater, curtain coater, scraper coating machine, metal thread bar to be coated with coating machines such as machine, extruder and to carry out.
When utilizing coating process, on substrate, be provided with and use dark composition coating to form the operation of photo-sensitive resin, as described later, coating is formed good photo-sensitive resin [(for example be preferably set to anoxia condition, further coating forms oxygen blocking layer on photo-sensitive resin, by this oxygen blocking layer or inert gas environment or reduced pressure)] expose, develop, make figure, form the next door thus.The formation of oxygen blocking layer can be same with the oxygen blocking layer of photosensitive transfer printing material described later.
Exposure, the details aftermentioned of developing.
When utilizing transfer printing, use photosensitive transfer printing material described later, the photo-sensitive resin of membranaceous formation on the false support is carried out in the real estate crimping or adds thermo-compressed pasting (stacked) with the roller or the flat board that have carried out heating and/or pressurization, the residual photo-sensitive resin that the described photo-sensitive resin of false support (under the anoxia condition) is arranged or further peel off false support of transfer printing, the described photo-sensitive resin that transfer printing is formed [(for example is preferably set to anoxia condition, by the oxygen blocking layer that on photo-sensitive resin, is provided with)] expose, develop, make pattern, form the next door thus.Exposure, the details aftermentioned of developing.
Specifically, utilize the spy to open flat 7-110575 communique, spy and open that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy drives the described stacked machine of 2002-148794 communique and laminating method carries out stacked.Need to prove, utilize the details aftermentioned of the transfer printing of photosensitive transfer printing material and transfer printing.
The bed thickness of photo-sensitive resin depends on the height in the next door of the solid constituent of dark composition and formation, is not particularly limited, in general, preferred 1.5～10 μ m, more preferably 1.8～7.0 μ m, further preferred 2.2～5.0 μ m.
～dark composition, photo-sensitive resin～
Below, to the dark composition that is used to form the next door and use the constituent of its photo-sensitive resin that forms to describe in detail.
-polymerizable compound-
Photo-sensitive resin or dark composition that the next door forms usefulness preferably contain at least a polymerizable compound.Be subjected to being cured, can form pattern from the effect of the spike of light-initiated system described later.
Polymerizable compound can exemplify simple function or polyfunctional monomer, preferred multi-functional monomer.Multi-functional monomer is the polymerizable monomer with 2 above polymerism bases, can be used alone, or can use with other combination of monomers together.
The concrete example of simple function or polyfunctional monomer; can exemplify: (methyl) tert-butyl acrylate; ethylene glycol bisthioglycolate (methyl) acrylate; (methyl) acrylic acid 2-hydroxypropyl acrylate; triethylene glycol two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; 2-ethyl-2-butyl propylene glycol two (methyl) acrylate; pentaerythrite three (methyl) acrylate; pentaerythrite four (methyl) acrylate; dipentaerythritol six (methyl) acrylate; dipentaerythritol five (methyl) acrylate; poly-hydroxyethyl trimethylolpropane tris (methyl) acrylate; three (2-(methyl) acryloyl group hydroxyethyl) isocyanuric acid ester; 1; the 4-di isopropenylbenzene; 1,4-dihydroxy benzenes two (methyl) acrylate; decanediol two (methyl) acrylate; styrene; the diallyl fumarate; triphen pregnancy acid triallyl; (methyl) lauryl acrylate; (methyl) acrylamide; xylylene two (methyl) acrylamide etc.
In addition, can also exemplify the reactant that (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, polyglycol one (methyl) acrylate etc. have diisocyanate such as the compound of hydroxyl and HDI, toluene diisocyanate, Xylene Diisocyanate.
In above-mentioned substance, preferred especially tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, three (2-acryloyl group hydroxyethyl) isocyanuric acid ester.
The content of the polymerizable compound in photo-sensitive resin or the dark composition, with respect to the total solid composition (quality) of layer or composition, preferred 5～80 quality %, preferred especially 10～70 quality %.In the time of in this content is above-mentioned scope, be effective for the patience of guaranteeing the relative alkaline developer behind the photocuring.
-light-initiated system-
Photo-sensitive resin or dark composition that the next door forms usefulness preferably contain at least a of light-initiated system.Light-initiated system utilizes the irradiation of luminous ray, ultraviolet ray, far ultraviolet, electron beam, X-ray isoradial (being also referred to as exposure) to produce the compound of the spike of the polymerization that causes described polymerizable compound, can suitably select from known compound.
For example can enumerate and contain trihalomethyl compound, acridine compound, acetophenone compounds, diimidazole compounds, compound in triazine class, benzoin compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, diazonium compounds etc.
In the above-mentioned substance, be preferably selected from and contain at least a of trihalomethyl compound, acridine compound, acetophenone compounds, diimidazole compounds, compound in triazine class, be preferably selected from especially and contain at least a of trihalomethyl compound and acridine compound.Contain trihalomethyl compound, acridine compound, versatility and cheap aspect all be useful.
The preferred especially described trihalomethyl compound that contains is 2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole, 2-(to the butyl phenyl ether vinyl)-5-trichloromethyl-1,3, the 4-oxadiazole, described acridine compound is the 9-phenylacridine, described compound in triazine class is that 6-[is to (N, N-two (ethoxycarbonylmethyl group) amino) phenyl]-2,4-two (trichloromethyl)-s-triazine, described benzophenone compound are michler's ketone, and described diimidazole compounds is 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Polymerization initiating system (particularly light-initiated system) can use more than 2 kinds except that using a kind separately simultaneously.
The total amount of the polymerization initiating system in photo-sensitive resin or the dark composition (particularly light-initiated system), with respect to the total solid composition (quality) of layer or composition, preferred 0.1～20 quality %, preferred especially 0.5～10 quality %.In the time of in this total amount is described scope, the curing efficiency height can solidify at short notice, and the picture pattern that forms during development can not be short of or the crackle of patterned surfaces.
Described light-initiated system can use hydrogen to supply with the body formation simultaneously.Can make sensitivity better aspect, hydrogen is supplied with body preferably with undefined sulfur alcohol compound, aminated compounds etc.At this, so-called " hydrogen supply body " is meant with respect to by the free radical of exposure by described Photoepolymerizationinitiater initiater generation, can supplies with the compound of hydrogen atom.
-colorant-
Photo-sensitive resin or dark composition that the next door forms usefulness preferably contain at least a colorant.By containing colorant, can form the visual picture that constitutes by desirable color.
Colorant can suitably use the spy to open paragraph sequence number [0038]～[0054] described pigment of 2005-17716 communique and dyestuff, the spy opens paragraph sequence number [0068]～[0072] described pigment of 2004-361447 communique, paragraph sequence number [0080]～[0088] described colorant that the spy opens the 2005-17521 communique.
Wherein, preferred organic pigment, inorganic pigment, dyestuff etc., when requiring photo-sensitive resin or dark composition to have light-proofness, can use potpourri of pigment such as opacifiers such as metal oxide powder, metallic sulfide powder, metal powders such as carbon black, titanium carbon, titanium dioxide, tri-iron tetroxide and red, blue, green etc.Can use known colorant (dyestuff, pigment).The example of the colorant of black can suitably be enumerated: carbon black, titanium carbon, iron oxide, titanium dioxide, graphite etc., preferred especially carbon black.
In addition, when selecting pigment as colorant, preferably it is dispersed in photo-sensitive resin or the dark composition.
The content of the colorant in photo-sensitive resin or the dark composition, with respect to the total solid composition (quality) of layer or composition, aspect the shortening development time, preferred 30～70 quality %, more preferably 40～60 quality %, further preferred 50～55 quality %.
Described pigment optimization uses as dispersion liquid.Add in the organic solvent described later (or vehicles) to make its dispersion by the composition that the described pigment of premixed and pigment dispersing agent are obtained to, can make this dispersion liquid.Described color spreading agent is meant the part that makes the medium of pigment dispersing at coating during for liquid condition, contains to combine the fixing part of coating (bonding agent) with the described pigment of liquid condition and with the composition (organic solvent) of its dissolved dilution.The dispersion machine that uses when making described pigment dispersing is not particularly limited, and can exemplify: " encyclopaedia of pigment " [Chao Warehouse nation makes work, first published, 438, Chao Warehouse Books shops (2000)] described kneader, roller pulverizer, Aunar come known dispersion machines such as moral (ア ト ラ イ ダ one), super mixer, dissolving machine, homo-mixer, puddle mixer.And it is broken that the friction force that can utilize the described mechanical crushing of " encyclopaedia of pigment " 310 to produce is carried out micro mist.
Consider that from the viewpoint of dispersion stabilization the particle diameter of colorant (particularly pigment) is preferably counted 0.001～0.1 μ m with number average bead diameter, more preferably 0.01～0.08 μ m.Need to prove, " particle diameter " be meant with particle use with electron micrograph in the area of this particle diameter when representing with the circle of area, " number average bead diameter " is meant 100 mean value of the particle diameter of a plurality of particles.
-bonding agent-
Photo-sensitive resin or dark composition that the next door forms usefulness can use at least a bonding agent to constitute.
Bonding agent preferably has the polymkeric substance of carboxylic acid group and carboxy acid alkali's isopolarity base on side chain.The example can be enumerated: the spy opens clear 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, the spy opens clear 59-53836 communique and the spy opens the described methacrylic acid copolymer of clear 59-71048 communique, acrylic copolymer, itaconic acid copolymer, butenoic acid multipolymer, maleic acid, partial esterification maleic acid etc.
In addition, can also exemplify the cellulose derivative that on side chain, has the carboxylic acid group.And can preferably use having addition on the polymkeric substance of hydroxyl has the material of cyclic acid anhydride.
Particularly preferred example can be enumerated: the multiple copolymer of No. 4139391 instructions of United States Patent (USP) described (methyl) benzyl acrylate and (methyl) acrylic acid multipolymer, (methyl) benzyl acrylate and (methyl) acrylic acid and other monomer.Bonding agent with these polar groups can be used alone, and also can use forming under the state of composition of the polymkeric substance of property and usefulness with common film.
The content of the bonding agent in photo-sensitive resin or the dark composition, with respect to the total solid composition (quality) of layer or composition, preferred 20～50 quality %, more preferably 25～45 quality %.
-solvent-
The dark composition that uses during next door in making the present invention except that described composition, generally can use the solvent formation.The example of solvent can be enumerated: butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methylisobutylketone, ethyl lactate, methyl lactate, caprolactam etc.
In addition, in in the present invention the dark composition or photo-sensitive resin, can further contain following compositions, for example surfactant, ultraviolet light absorber and known adjuvant, for example: plastifier, filling agent, stabilization agent, polymerization inhibitor, solvent, driving fit promoter etc.And preferred dark composition softens under the temperature below at least 150 ℃ or becomes cohesive, is preferably thermoplasticity.Consider from described viewpoint, can carry out modification by the plastifier that adds intermiscibility.
-surfactant-
Be coated in dark composition on the substrate or the false support of photosensitive transfer printing material described later on the time, by in dark composition, containing surfactant, can control uniform thickness, can prevent effectively that coating is uneven.Surfactant can enumerate suitably that the spy opens the 2003-337424 communique, the spy opens the described surfactant of flat 11-133600 communique.Need to prove, the content of the surfactant in the dark composition, the total solid composition (quality) with respect to said composition is generally 0.001～1 quality %, preferred 0.01～0.5 quality %, preferred especially 0.03～0.3 quality %.
-ultraviolet light absorber-
In dark composition, can contain ultraviolet light absorber as required.
Ultraviolet light absorber for example has: the spy opens the described compound of flat 5-72724 communique and salicylate system, benzophenone series, benzotriazole system, cyanoacrylate system, nickel chela and compounds such as system, hindered amine system.
When using UVA, the content with respect to the ultraviolet light absorber of the total solid composition of dark composition is generally 0.5～15 quality %, preferred 1～12 quality %, preferred especially 1.2～10 quality %.
-thermal polymerization inhibitor-
In dark composition, preferably contain thermal polymerization inhibitor.The example of thermal polymerization inhibitor for example has: p-dihydroxy-benzene, monomethyl ether of hydroquinone, p methoxy phenol, two-tert-butyl group-paracresol, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-sulphur two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, phenothiazine etc.
When using thermal polymerization inhibitor, the content with respect to the thermal polymerization inhibitor of the total solid composition of dark composition is generally 0.01～1 quality %, preferred 0.02～0.7 quality %, preferred especially 0.05～0.5 quality %.
In addition, in dark composition, except that described composition, also can contain the spy and open flat 11-133600 communique described " bonding auxiliary agent " and other adjuvant etc.
～photosensitive transfer printing material～
Below, the photosensitive transfer printing material that is used for described transfer printing is described in detail.
Photosensitive transfer printing material can use the material that the photo-sensitive resin that uses described dark composition to constitute is set at least constitutes, preferably support the side that the material that oxygen blocking layer and photo-sensitive resin constitute is set from vacation on false support.When the use photo-sensitive resin is provided with the material of oxygen blocking layer, because the photo-sensitive resin that is made of dark composition is not subjected to influence from the oxygen in the atmosphere by the protection of oxygen blocking layer, so automatically become anoxia condition.Therefore, following advantage is arranged, need under inert gas and decompression, not carry out exposure process, can directly utilize existing operation.In addition, can be easily and to form at low cost aspect the next door also be effective.
Photosensitive transfer printing material can further be provided with thermoplastic resin and diaphragm as required and wait and constitute.
-false support-
False support can suitably be selected from the material of chemically stable and heat-staple flexible material formation.Specifically, thin sheet material or film or these duplexer such as preferably polytetrafluoroethylene (registered trademark), polyethylene terephthalate, polycarbonate, tygon, polypropylene, polyester.Wherein, preferred especially two-way stretch pet film.
The thickness of false support is suitably for 5～300 μ m, is preferably 20～150 μ m.In the time of in thickness is described scope, breaking in the time of can avoiding false support to peel off can be avoided the reduction of the sharpness when exposing by false support.
-photo-sensitive resin-
Characteristics such as photo-sensitive resin uses the dark composition of having stated and constitutes, its shape and formation method etc. are identical with the layer that applies formation with the coating process of having stated, and preferred mode is also identical.
-oxygen blocking layer-
Preferably oxygen blocking layer is being set further between false support and the photo-sensitive resin or between thermoplastic resin and the photo-sensitive resin.So-called oxygen blocking layer is meant to have 2000cm 3/ (m 2Dayatm) layer of Yi Xia oxygen permeability, oxygen permeability is preferably 100cm 3/ (m 2Dayatm) below, more preferably 50cm 3/ (m 2Dayatm) below.At oxygen permeability greater than 2000cm 3/ (m 2Dayatm) time, oxygen can not be interdicted effectively sometimes, the next door of desired shape can not be obtained.
It preferably is the layer of principal ingredient (particularly being principal ingredient) with PVA with tygon, Vingon, polyvinyl alcohol (PVA) (PVA) etc., can add polymkeric substance such as polyvinylpyrrolidone, polyacrylamide as required, the combination of the special pure and mild polyvinylpyrrolidone of preferably polyethylene.The preferred saponification rate of PVA is the material more than 80%, and the content of polyvinylpyrrolidone is preferably 1～75 quality % of the total solid composition of oxygen blocking layer, more preferably 1～50 quality %, further preferred 10～40 quality %.
Preferred 25～99 quality % of content of PVA in the oxygen blocking layer, more preferably 50～90 quality %, preferred especially 50～80 quality %.The addition of these polymkeric substance is 1～40 whole quality % of layer, more preferably 10～35 quality %.Need to prove that when the addition of polyvinylpyrrolidone was too much, the oxygen barrier property was insufficient sometimes.
-thermoplastic resin-
Between false support and photo-sensitive resin, thermoplastic resin can be set as required.By thermoplastic resin is set, be effective to the adaptation of the substrate that improves next door and formation.
Thermoplastic resin contains resinous principle at least and constitutes, and the preferred bases solubility constitutes.Resinous principle is preferably alkali-soluble, the essence softening point is the thermoplastic resin below 80 ℃.
Softening point is the thermoplastic resin of the alkali-soluble below 80 ℃, for example has: saponified, the vinyltoluene of saponified, the styrene of ethene and acrylate copolymer and (methyl) acrylate copolymer and (methyl) acrylate copolymers such as saponified, poly-(methyl) acrylate, (methyl) butyl acrylate and vinyl acetate of (methyl) acrylate copolymer etc. saponified etc.
Except that above-mentioned, softening point in " plastics performance handbook " (Japan Plastics Industry Federation, all Japan plastics forming industrial combination can be write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution) is about in the organic polymer below 80 ℃, also can further use soluble material in aqueous alkali.
In addition, softening point is the various plastifier that the organic polymer material more than 80 ℃ also can have intermiscibility by interpolation and this polymer substance in its organic polymer, the essence softening point is reduced to below 80 ℃ uses.
In these organic polymer materials, in order to regulate the bonding force with false support, in the essence softening point is no more than 80 ℃ scope, also can add various polymkeric substance and supercooling material, driving fit modifying agent or surfactant, release agent etc.The concrete example of preferred plasticizer can be enumerated: polypropylene glycol, polyglycol, dioctyl phthalate, DHp, Dibutyl phthalate, trimethylphenyl phosphate, tolyl diphenyl phosphoester, biphenyl diphenyl phosphoester.
-diaphragm-
The surface of the photo-sensitive resin that forms on false support in order to protect pollution and the damage from when storage, preferably is provided with diaphragm.Diaphragm can be used identical with false support or materials similar constitutes, and is carrying out well aspect the transfer printing, and it is important can easily separating from photo-sensitive resin.
Constitute material preference such as silicon paper, polyolefin or the polytetrafluoroethylsheet sheet of diaphragm.The thickness of diaphragm is generally 4～40 μ m, is preferably 5～30 μ m, is preferably 10～25 μ m especially.
Photosensitive transfer printing material can followingly be made, for example, coating is dissolved with the coating liquid (thermoplastic resin is with applying liquid) of the constituent of thermoplastic resin and makes its drying on false support, thermoplastic resin is set thus, coating is used the solution that the solvent of heat of solution plastic resin layer not forms and is made its drying on this thermoplastic resin, stacked oxygen blocking layer, and then the formulated as mentioned above dark composition of the solvent that on oxygen blocking layer, uses dissolved oxygen DO blocking layer not and make its drying, stacked photo-sensitive resin.
Need to prove, can utilize above-mentioned known coating process to apply, but preferred the use there is the applying device (slit coating machine) of slit-shaped nozzle to apply.
Except that said method, photosensitive transfer printing material also can be made by the following method: prepare false support and be provided with the sheet material of thermoplastic resin and oxygen blocking layer and the sheet material that diaphragm is provided with photo-sensitive resin, make its stickup with oxygen blocking layer and photo-sensitive resin ways of connecting; In addition, prepare on false support, to have the sheet material of thermoplastic resin and on diaphragm, have photo-sensitive resin and the sheet material of oxygen blocking layer, make its stickup with thermoplastic resin and oxygen blocking layer ways of connecting.
-substrate-
Substrate (permanent support) for example has: the base material of metal, the base material that makes the metal stickup, glass, pottery, film of synthetic resin etc.Preferably clear, dimensional stability good substrate, particularly glass and film of synthetic resin.
[exposure, development]
Photo-sensitive resin for forming as mentioned above can use the mask that is provided with desirable pattern, by mask photo-sensitive resin is carried out rayed, exposes thus.At this moment, preferred exposure is carried out under anoxia condition.Anoxia condition can form by the following method, for example: the layer that can interdict oxygen (for example when using oxygen blocking layer or photosensitive transfer printing material, not removing when exposure and residual false support etc.) is being set on the photo-sensitive resin; Or be set at inert gas environment or reduced pressure atmosphere.Wherein, preferably under the anoxia condition that is adjusted into the formation of inert gas environment or reduced pressure atmosphere, expose.
Anoxia condition is meant under inert gas environment, under the decompression, the layer that can interdict oxygen is inferior.
Described inert gas is meant N 2, H 2, CO 2Etc. rare gas classes such as general gas and He, Ne, Ar.Wherein, from security and obtain easily, the cost aspect considers, preferred N 2
Be meant the following state of following, the preferred 100hPa of 500hPa under the described decompression.
In addition, the described layer that can interdict oxygen can be used oxygen blocking layer and the various film in the photosensitive transfer printing material of having stated, and preference is as being the polyesters of representative with polyethylene terephthalate (PET), being polyamide-based, the ethylene-vinyl acetate copolymer (EVA class) of representative with nylon.These films can be to have carried out the film that stretches as required, and thickness is that 5～300 μ m are suitable, is preferably 20～150 μ m.When making the next door,, form anoxia condition by being set at the state that photo-sensitive resin is provided with false support and/or oxygen blocking layer with photosensitive transfer printing material.
In exposure, can use proximity printing machine (for example, the Hitachi's Ha イ テ Network Electricity エ Application ジ ニ ア リ Application グ (strain) System) etc. that for example has extra-high-pressure mercury vapour lamp.In addition, light source can exemplify middle pressure～extra-high-pressure mercury vapour lamp, xenon lamp, metal halide lamp etc.
The preferred 25mW/cm of illumination 2More than, preferred especially 80mW/cm 2More than.Obtaining on the viewpoint of effect of the present invention, the higher limit of illumination is not particularly limited, and the obstacle on short of device, the equipment just can be brought up to desirable illumination.It is described scope that the methods such as distance that can utilize the output power that improves light source, increase the number of light source and dwindle light source and be exposed body are adjusted this illumination.
The exposure back uses developer solution to carry out development treatment, forms pattern image on photo-sensitive resin.Then, wash processing as required.
Before development, preferably, got wet equably in the surface of photo-sensitive resin with the spray spout pure water of on photo-sensitive resin, spraying.Be used for the developer solution of development treatment, preferably using the thin aqueous solution of alkaline matter, and can be to be added with the solution that blended solvent is arranged with glassware for drinking water on a small quantity.
Described alkaline matter for example has: alkali metal hydroxide (for example, NaOH, potassium hydroxide), the alkali carbonate class (for example, sodium carbonate, sal tartari), the alkali metal hydrogencarbonate class (for example, sodium bicarbonate, saleratus), the alkali metal silicate salt (for example, sodium silicate, potassium silicate), the alkali metal silicate class (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetra-alkyl ammonium hydroxide class (for example, Tetramethylammonium hydroxide), tertiary sodium phosphate etc.The concentration of alkaline matter is preferably 0.01～30 quality %, and pH is preferably 8～14.
Described " blended solvent being arranged with glassware for drinking water " can for example suitably enumerate: methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, butanone, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl sulfonamide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone etc.With glassware for drinking water preferred 0.1～30 quality % of concentration of blended solvent is arranged.
And, can add known surfactant, surfactant concentrations is preferably 0.01～10 quality %.
Described developer solution can be used as body lotion or uses as spray liquid.
When removing the uncured portion of photo-sensitive resin, can in developer solution, will combine with methods such as rotating brush and wetting sponge wipings.The temperature of developer solution is preferably near the room temperature usually～and 40 ℃.Development time during because of the alkalescence of the composition of photo-sensitive resin, developer solution and temperature, interpolation solvent its kind and concentration etc. different, be generally 10 seconds～about 20 minutes.In this scope, obtain the next door that shape is fit to.In other words, when development time was too short, the development in the zone of removing of will developing sometimes was insufficient, and simultaneously, ultraviolet absorbance is also insufficient, on the contrary, when it is long, corrodes to solidified portion sometimes.After development treatment, can enter washing step.
The height in the next door among the present invention with the altitude gauge in the substrate normal direction, is preferably 1.0～6.0 μ m, more preferably 1.5～5.0 μ m.When it highly is in the described scope time, as mentioned above, when splashing into formation painted areas (pixel) with ink-jet method, printing ink is difficult to cross the next door, prevent that printing ink from oozing out and overflowing, the colour mixture between the pixel adjacent pattern and the white point in the pattern of pixels etc., be effective forming aspect the color filter that color is good and display quality is high.
The width in the next door among the present invention with the width gauge in the direction vertical with the normal direction of substrate, is preferably below the above 50 μ m of 5.0 μ m.And, be preferably below the 0.5 μ m with the change width of the thickness of the substrate normal direction of interior painted areas (R pixel, G pixel, B pixel etc.) apart from end (for example end face) the 10 μ m in next door with the real estate parallel direction.When this change width is in the described scope time, can effectively prevents to carry out image and produce irregular colour etc. when showing in the image and show uneven in display device such as the liquid crystal indicator of for example packing into.This change width is preferably below the 0.4 μ m, can contain surfactant adjustment by making in the printing ink that forms colored pixels.
Below, the example that forms the next door is specifically described.
1) utilize use to have the coating of dark composition to form the next door
After the substrate washing, this substrate is heat-treated, make the surface state stabilization.Then, substrate is carried out temperature adjustment, the dark composition of coating on the good substrate of temperature adjustment.After the coating, make a part of solvent seasoning in the overlay, lose the flowability of layer after, remove substrate useless coating liquid on every side with EBR (side washing liquid), carry out preroast, obtain photo-sensitive resin.Can use the known glass substrate that has the slit-shaped nozzle to apply with coating machine (for example MH-1600 of エ Off エ one エ ス ア ジ ア She System) etc.In addition, can utilize known drying device (for example VCD (Minton dryer: East capital ying chemical industry She System) etc.) to carry out drying, can for example 120 ℃ down heating carry out preroast in 3 minutes.About the bed thickness of photo-sensitive resin as mentioned above.
Then, under the substrate that will be formed with photo-sensitive resin and the vertical state that erects of the mask with pattern (for example quartzy exposure mask), suitably (for example 200 μ m) set the distance between mask face and the photo-sensitive resin, carry out nitrogen purification, the control partial pressure of oxygen is exposed under nitrogen environment.For example, can (for example, the Ha イ テ of Hitachi Network Electricity エ Application ジ ニ ア リ Application グ (strain) System) etc. exposes, exposure can be suitably (300mJ/cm for example with the proximity printing machine that has extra-high-pressure mercury vapour lamp 2) select.The partial pressure of oxygen of this moment can be used oxymeter, and (for example Rice Island Electricity industry (the G-102 type of strain) System) is measured.After the exposure, carry out development treatment, obtain pattern image, wash processing as required, obtain the next door with developer solution.
2) utilize use to have the transfer printing of photosensitive transfer printing material to form the next door
At first, peel off the diaphragm of removing photosensitive transfer printing material, the surface of the good photo-sensitive resin of exposure is overlapped on the real estate, overlapping machine etc. is passed through, heat and/or pressurize, make duplexer.Stacked machine can suitably be selected from known stacked machine, vacuum laminated machine etc., considers from the productive viewpoint of further raising, also can use the stacked machine of automatic cut-out.Then, from duplexer false support is peeled off and removed.Then, remove false support, (for example dispose desirable photomask in the top of exposing face (oxygen blocking laminar surface) of exposing, quartzy exposure mask), be set at anoxia condition by decompression, by mask with the pattern-like irradiation ultraviolet radiation, after the irradiation, use predetermined process liquid to carry out development treatment, obtain the next door.At this moment, implementing washing as required handles.Developer solution and the light source of the light source that is used for the developer solution of development treatment and is used to expose when utilizing described coating process is identical.
-plasma treatment operation-
In manufacturing method of color filter of the present invention,, implement plasma treatment in order to give anti-printing ink to the substrate that has formed the next door as mentioned above.By giving anti-printing ink above the next door, can prevent the generation of " colour mixture " effectively.This plasma treatment can exemplify: the method (decompression plasma treatment) that reduces pressure, handles with batch (-type); The methods (atmospheric plasma processes) that do not reduce pressure, handle with continous way etc. are considered from viewpoints such as processing speeds, and special preferred atmosphere is pressed plasma treatment.
(1) decompression plasma treatment
The gas that contains fluorine atom at least that imports in this operation preferably uses more than a kind and is selected from CF 4, CHF 3, C 2F 6, SF 6, C 3F 8, C 5F 8In halogen gas.C particularly 5F 8The ozone layer destroying of (octafluoro cyclopentene) can be 0, and simultaneously, atmospheric lifetime is compared (CF with existing gas 4: 50,000 years, C 4F 8: 3200) very short, be 0.98.Therefore, the greenhouse effects of the earth coefficient is 90 (to be set at CO 2100 years aggregate-values of=2), compare (CF with existing gas 4: 6500, C 4F 8: 8700) very little, very effective to ozonosphere and earth environment protection, preferably use in the present invention.
And, can use gases such as oxygen, argon gas, helium as importing gas as required simultaneously.In this operation, be selected from above-mentioned CF more than a kind when using 4, CHF 3, C 2F 6, SF 6, C 3F 8, C 5F 8In halogen gas and during the mixed gas of oxygen, can be controlled at the ink-repellant degree on surface, next door processed in this operation.But, in this mixed gas, owing to work as O 2Mixture ratio surpass at 30% o'clock, utilize O 2The oxidation reaction subject, hinder anti-printing ink raising effect, and, owing to work as O 2Mixture ratio surpass at 30% o'clock, the loss of resin is remarkable relatively, thus when this mixed gas of use, must be at O 2Mixture ratio be to use in the scope below 30%.
In addition, isoionic production method can use modes such as low frequency discharge, high-frequency discharge, microwave discharge.Conditions such as the pressure during plasma treatment, gas flow, output power, processing time can be set arbitrarily, but in order to realize effect of the present invention, more preferably Yi Xia condition.
Preferred 10～the 100Pa of pressure during plasma treatment, more preferably 20～80Pa, further preferred 30～50Pa.Preferred 40～the 300sccm of gas flow, more preferably 50～200sccm, further preferred 60～100sccm.Preferred 10～the 100W of output power, more preferably 20～90W, further preferred 30～80W.Processing time depends on above-mentioned pressure and output power, preferred 20～200sec, more preferably 20～100sec, further preferred 20～50sec.
(2) atmospheric plasma processes
Described atmospheric plasma processes is meant at normal temperatures mixes inert gases such as the appropriate hydrocarbon gas isoreactivity gas of gas and helium, under atmospheric pressure carries out excitation of plasma, and handled object is carried out the surface-treated method, is using ethene and CF 4Deng and so on normal temperature during down for the reactant gas of the compound of gas, be under atmospheric pressure to utilize highly stable light emitting discharge plasma to carry out the surface-treated method.
In above-mentioned atmospheric plasma processes, rare gas (inert gas) also can use known any inert gas, can enumerate helium, neon, nitrogen, argon gas, lower aliphatic hydrocarbon etc., and is wherein, preferred also with argon gas and lower aliphatic hydrocarbon.
Above-mentioned lower aliphatic hydrocarbon with argon gas and usefulness, be preferably the methane hydrocarbon of carbon number 1～6, for example have: methane, ethane, propane, normal butane, isobutane, pentane, isopentane and neopentane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane etc., wherein, preferably use methane, propane, normal butane and n-pentane.The above-mentioned aliphatic hydrocarbon that uses with argon gas can use mixing more than 2 kinds.
In addition, the reactant gas that in above-mentioned atmospheric plasma processes, uses, be meant under the state that excitation of plasma is crossed the gas that forms the film of polymkeric substance on the handled object surface, or carrying out chemical reaction forms the film of resultant of reaction on this surface gas etc. with the surface of handled object under the state that excitation of plasma is crossed.
Form the reactant gas of the film of polymkeric substance on handled object surface, can illustration: the α of ethene, propylene, styrene and so on, β-unsaturated hydrocarbon and can cause the aromatic hydrocarbons such as benzene, toluene etc. of the free radical polymerization that excitation of plasma is crossed.
Form the gas of the film of resultant of reaction on the handled object surface, can illustration: CF 4, C 3F 6, CHF 3And so on the silicon compound etc. of halogenated hydrocarbon, a silane, disilane, trimethyl chlorosilane and so on.
Above-mentioned reactant gas can use mixing more than 2 kinds as required.
Can carry out above-mentioned atmospheric plasma processes by utilizing light emitting discharge provocative reaction gas, formation high-energy plasma.Form this plasma by applying high voltage, the value of the voltage that applies is according to suitably decision such as the surface texture of handled object and surface-treated time, and is for example preferred 1,000～8 generally speaking, 000V, more preferably 1,000～5,000V.
Need to prove that the frequency of power supply can be selected suitable frequency according to the kind of the material of handled object, for example plastics, cotton, paper, metal, glass, pottery etc., for example, handled object with respect to plastics, be fit to use 1,000Hz～10Gz is with respect to the handled object of metals such as silicon, be fit to use 3,000Hz～10Gz, and, with respect to the handled object of natural materials such as cotton, be fit to use 1,000Hz～10Gz.
Above-mentioned atmospheric plasma processes does not need the helium of high price, can use with the inert gas composition of comparatively cheap argon gas, play the excellent results of highly carrying out stable light emitting discharge, carrying out the processing of hydrophobic property at the surface energy of handled object as principal ingredient.
Above-mentioned atmospheric plasma processes also has following strong point, is not subjected to the influence of oxygen fully, can easily form the tunicle of hydrophobic polymkeric substance or the tunicle of hydrophobic resultant of reaction.
In addition, to atmospheric plasma processes, open in paragraph sequence number [0010]～[0024] of flat 6-41755 the spy and to describe in detail.
-pixel formation operation-
Pixel forms operation: the gap between next door (recess), give the drop of the ink composition for ink jet of having stated of the present invention with ink-jet method, form painted areas.This painted areas becomes the redness (R) that constitutes color filter, green (G), blue color pixels such as (B).
The formation of painted areas can followingly be carried out, as mentioned above, the next door that forms on substrate surrounds the recess that forms, as the pigmented fluids composition that is used to form colored pixels (for example 3 kinds of color pixel patterns of RGB), described ink composition for ink jet is invaded, form in the mode that constitutes with 2 kinds of a plurality of pixels more than the color.
With regard to ink-jet method, can use the printing ink heat curing method, make the method for its photocuring, forming the known method such as method that splash into behind the transparent image receiving layer on the substrate in advance.
In this operation, in order to obtain desirable color, concentration, can suitably select to surround the spray volume of the recess ejection that forms with the next door, but the big or small preferred 0.1～100pl of preferred 1 drop (micromicro liter), more preferably 1～50pl.
Shape to color filter is not particularly limited, and as next door (black matrix) shape, can be general linear, also can be lattice-like, can also be the rounded projections arranged shape.
As ink-jet method, can adopt the method for spraying charged printing ink continuously, utilizing electric field to control; Use the piezoelectric element method of ink jet off and on; With the printing ink heating, the whole bag of tricks such as method that utilize its foaming to spray off and on.
The ejaculation condition of printing ink is considered from penetrating stable aspect, preferably printing ink is heated to 40～70 ℃, reduces ink viscosity and penetrates.Because mostly than the viscosity height of water color ink, therefore the viscosity amplitude of fluctuation that is caused by temperature change is big for ink composition for ink jet.Because the viscosity change is directly given and very big influence drop size, drop issuing velocity, causes the image quality deterioration easily, be important so make ink temperature keep constant as far as possible.
Ink gun (below, also abbreviate shower nozzle as) can application of known shower nozzle, can use continuous type, discontinuous type.In discontinuous type, hot shower nozzle preferably has the type of opening flat 9-323420 number described operating valve as the spy in order to spray.Pressure nozzle can use for example European patent A277, No. 703, European patent A278, described shower nozzles such as No. 590.In order to manage the temperature of printing ink, preferred sprinkler has temperature adjustment function.Viscosity when penetrating in order to make is 5～25mPas, sets and penetrates temperature, for the amplitude of fluctuation that makes viscosity is in ± 5%, preferably controls ink temperature.In addition, be to work under 1～500kHz preferably in driving frequency.
Color filter of the present invention is preferably coated the printing ink of RGB3 kind color at least, the mode that is made of the painted areas (dyed layer) of 3 kinds of colors.Except RGB, can also suit to form V (purple), W (transparent), C (green grass or young crops), Y (Huang), M pixels such as (fuchsins).
-curing process-
Below, carry out following explanation to forming the operation that can be provided with after the operation in pixel.The situation of the painted areas that forms the RGB3 look is described.
＜＜the 1 curing process〉〉
Can be arranged on the painted areas irradiation active energy ray of at least a kind of color that described pixel curing process forms and the operation (the 1st curing process) that is cured.In the 1st curing process, can form the painted areas (pixel) that is cured by making the curable ink solidification of all kinds that contains redness (R), green (G) and blue (B).Curing can be carried out in the painted areas that forms a kind of color, also can carry out after the painted areas that has formed multiple color.
Use the energy of the active energy ray that produces the corresponding wavelength region may of wavelength photoreceptor that has with printing ink, implement to promote the exposure-processed of polymerization, can carry out the curing of curable printing ink of the present invention such as R, G, B thus.
The energy can suitably select to use the energy of the polymerization initiator induction of having stated, for example ultraviolet ray of 450～200nm, far ultraviolet, g line, h line, i line, KrF excimer laser, ArF excimer laser, electron beam, X-ray, molecular line and ion beam etc.Specifically, can preferably use send the wavelength region may that belongs to 250～450nm, preferred 365 ± 20nm the light source of active ray carry out for example LD, LED (light emitting diode), fluorescent light, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, metal halide lamp, carbon arc lamp, xenon lamp, chemical lamp etc.Optimized light source can exemplify LED, high-pressure mercury-vapor lamp, metal halide lamp.
The irradiation time of active energy ray can suitably be set according to the combination of polymerizable compound and polymerization initiator, for example, and with illumination 20mW/cm 2During exposure, can be set at 1～750 second.
In addition, can carry out the irradiation of above-mentioned active energy ray, but, preferably shine from the surface (face of giving the printing ink side of substrate) of substrate can effectively giving aspect the printing ink energy from which face of substrate.
＜＜the 2 curing process〉〉
In manufacturing method of color filter of the present invention, the operation (the 2nd curing process) that the painted areas of utilizing heat will contain the desirable color of redness (R), green (G) and blue (B) all is cured can be set.By when described the 1st curing process is set, the 2nd curing process being set, manufacturing efficient and display characteristic that can balanced color filter.
In this operation, form the painted areas and the next door that constitute by desirable color, after carrying out described the 1st curing process, further carry out heat treated (so-called calcination process), implement to utilize the curing of heat.That is, with the substrate that utilizes rayed to carry out photopolymerisable painted areas and to form the next door put into electric furnace, exsiccator heats, or the irradiation infrared lamp heats.
The size of the painted areas (pixel) that forms with manufacturing method of color filter of the present invention, the length on one side of preferred pixel is 50～300 μ m, more preferably 70～300 μ m, preferred especially 100～300 μ m.In addition, homochromy pixel can be the linear that does not separate arrangement with vertical shape.
The heating-up temperature of this moment and the thickness of composition that depends on ink composition for ink jet heat time heating time and painted areas, in general, consider from the viewpoint of guaranteeing sufficient solvent resistance, alkali resistance and ultraviolet absorbance, preferably heated 10 minutes～120 minutes down at 120 ℃～250 ℃.
The surface smoothness (Ra value) that the painted areas (dyed layer) of ink composition for ink jet formation of the present invention is given in preferred ink-jet is below the 5nm, more preferably below the 4nm.This Ra value utilizes contact film thickness gauge (the contact pin type surfagauge P10 of the System of Tencor society) to measure.
-other operation-
In manufacturing method of color filter of the present invention, other operation such as calcining process (following thermal treatment and post-exposure) that next door that further heating (roasting) forms and painted areas make its curing and the OC operation that forms diaphragm (OC) layer can be set.
～thermal treatment～
By reactions such as the monomer implementing thermal treatment (being also referred to as the back roasting), make to contain in dark composition or the photo-sensitive resin and crosslinking chemicals, can guarantee the hardness in next door.
The scope that heat treated temperature is preferred 150～250 ℃.When temperature was lower than 150 ℃, hardness was insufficient sometimes, when it surpasses 250 ℃, and coloring resin, excitation variation sometimes.In addition, heat treatment period is preferred 10～150 minutes.When the time is lower than 10 minutes, hardness deficiency sometimes, when it surpasses 150 minutes, coloring resin, excitation variation sometimes.Thermal treatment can change according to color.In addition, utilize described ink-jet method to form whole colors after, can further carry out final thermal treatment and make the hardness stabilization.At this moment, aspect hardness, preferably implement thermal treatment with high temperature (for example 240 ℃).
～post-exposure～
When forming the next door, can between development and thermal treatment, implement post-exposure (being also referred to as exposure again).
Consider from the section configuration in control next door, the hardness in control next door, the concave-convex surface in control next door, the viewpoints such as film decrement in control next door, preferably implement post-exposure.The light source that is used for post-exposure for example has: the spy opens described extra-high-pressure mercury vapour lamp of paragraph sequence number [0074], high-pressure mercury-vapor lamp, metal halide lamp of 2005-3861 communique etc.The simplification of slave unit and the viewpoint of saving electric power consider, post-exposure preferably will be from the light of light sources such as extra-high-pressure mercury vapour lamp and metal halide lamp not by direct irradiations such as exposure masks on substrate.As required, can implement from the two sides of substrate, at this moment, exposure side in the above is 100～5000mJ/cm 2, following side is 100～5000mJ/cm 2Scope in, suitably adjust according to described control purpose.
After forming painted areas (colored pixels) and next door, making color filter as mentioned above, in order to improve patience, can form protective film, so that it covers the comprehensive of painted areas and dark next door.
Protective film can make to have an even surface in painted zone such as protection R, G, B and dark next door.But, consider from process number increase aspect, preferably be not provided with.
Protective film can use resin (OC agent) to constitute, and resin (OC agent) for example has: acrylic resin composition, composition epoxy resin, polyimide resin composition etc.Wherein, from being that principal ingredient, adaptation are considered preferred acrylic resin composition aspect good with the resinous principle of Photocurable composition with common acrylic resin at transparent good, the color filter of visible region.The example of protective film can exemplify paragraph sequence number [0018]～[0028] described protective film that the spy opens the 2003-287618 communique, and the commercially available product of protection film can exemplify オ Block ト マ-SS6699G of the System of JSR society.
Utilize the manufacturing method of color filter of having stated of the present invention can make color filter of the present invention, can be preferably applied to for example purposes such as portable terminal devices such as televisor, notebook computer, liquid crystal projector, game machine, mobile phone, digital camera, navigational system with being not particularly limited.
＜display device 〉
As mentioned above, display device of the present invention (liquid crystal indicator etc.) is characterised in that, use color filter of the present invention to form, have the suitable property aspect of good ITO sputter from color filter and consider, can obtain the contrast height, suppress high-grade display device of the generation of irregular colour with the invention described above.
Except having described color filter, display device of the present invention is not particularly limited, and can use the inscape of using in known display device.
Except color filter, can use various parts such as electrode base board, polarizing film, phase-contrast film, backlight, spacer, field angle compensation film to constitute.About these parts, for example " market of `94 LCD periphery material chemicals (island Itou Kentaro, (strain) シ one エ system シ one, distribution in 1994) ", " present situation of the related visual field of 2003 liquid crystal and in the future prospect (last volume) (table good lucky, (strain) Fuji chimera always grinds, distribution in 2003 " in put down in writing.
Display device of the present invention adopts ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric LiquidCrystal), OCB (Optically Compensatory Bend), STN (Supper TwistedNematic), VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), GH plurality of display modes such as (Guest Host).
Can possess following formation as display device of the present invention, for example liquid crystal indicator, be provided with clamping liquid crystal layer between 2 substrates of conductive layer on the mutual surface of opposite side, make liquid crystal aligning control with projection and space bar from becoming protruding to liquid crystal layer side on the conductive layer on the substrate.In addition, also can form oriented film with its covering on conductive layer.
The basic comprising form of display device of the present invention for example has: (1) with arrangement be formed with thin film transistor (TFT) (below, sometimes be also referred to as " TFT ") etc. the driving side substrate and the color-filter layer side group plate that has color filter and opposite electrode (conductive layer) of driving element and pixel electrode (conductive layer), make space bar and laminated section between middle arranged opposite, betwixt the form of crack portion encapsulated liquid crystals material formation; (2) color filter-one-piece type driving substrate that will on above-mentioned driving side substrate, directly form color filter and the counter substrate that has opposite electrode (conductive layer), make space bar and laminated section between middle arranged opposite, betwixt the form that constitutes of crack portion encapsulated liquid crystals material etc.
Above-mentioned conductive layer for example has: the ITO film; Metal films such as Al, Zn, Cu, Fe, Ni, Cr, Mo; SiO 2Deng metal oxide film etc., wherein, the film of preferably clear, preferred especially ITO film.
Above-mentioned driving side substrate, color-filter layer side group plate, counter substrate can use described substrate as its base material.
Driving side substrate as arrange forming driving element such as TFT and pixel electrode for example has: will intersect and be arranged to TFT that rectangular data bus and door bus connect, and the substrate of the conductive layer that is connected with data bus by TFT etc. mutual vertically.
In any of above-mentioned form, on two substrates that constitute liquid crystal display cells, form conductive layer, between this two conductive layer, apply voltage, be clamped in therebetween liquid crystal material according to the directed state of its change in voltage, show.Therefore, the liquid crystal aligning control of having stated can form with desirable shape, form on any conductive layer with projection.
Specific embodiment
Below, illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to these embodiment.In addition, unless otherwise specified, " part " expression " mass parts " in the following examples, " % " expression " quality % ", " molecular weight " expression " weight-average molecular weight ".
[embodiment 1]
The formation in-next door-
(next door forms the preparation of the dark composition of usefulness)
At first, measure the K pigment dispersing thing 1 of the described amount of following table 2, propylene glycol monomethyl ether acetate, under 24 ℃ of temperature (± 2 ℃), mix, stirred 10 minutes with 150rpm, then, measure the butanone (methyl ethyl ketone) of the described amount of table 2, bonding agent 2, monomethyl ether of hydroquinone, DPHA liquid, 2,4-two (trichloromethyl)-6-[4 '-(N, N-diethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine, phenothiazine, surfactant 1, under 25 ℃ of temperature (± 2 ℃), add successively, under 40 ℃ of temperature (± 2 ℃), stirred 30 minutes, obtain dark composition K1 thus with 150rpm.
[table 2]
Dark composition K1
K pigment dispersing thing (carbon black) 30
Propylene glycol monomethyl ether acetate 7.3
Butanone 34
Cyclohexanone 8.6
Bonding agent 2 8.6
Monomethyl ether of hydroquinone 14
DPHA liquid 5.8
2, amino-the 3 '-bromophenyl of 4-two (trichloromethyl)-6-[4 '-(N, N-diethoxy carbonyl methyl)]-the s-triazine 0.22
Phenothiazine 0.006
Surfactant 1 0.058
(unit: mass parts)
Need to prove that in detail, the described composition of table 2 is following composition.
＜K pigment dispersing thing 1 〉
Carbon black (デ グ Star サ She System Nipex35) 13.1%
Spreading agent 1 (following compound 1) 0.65%
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72%
Propylene glycol monomethyl ether acetate 79.53%
[changing 2]
Figure G200710100977020070514D000441
＜bonding agent 2 〉
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand) 27%
Propylene glycol monomethyl ether acetate 73%
＜DPHA liquid 〉
Dipentaerythritol acrylate
(contain polymerization inhibitor MEHQ 500ppm, Japanese chemical drug (strain) System, trade name: KAYARADDPHA) 76%
Propylene glycol monomethyl ether acetate 24%
＜surfactant 1 〉
Following works 130%
(n=6, x=55, y=5, Mw=33940, Mw/Mn=2.55, PO: epoxypropane, EO: oxirane)
Butanone 70%
[changing 3]
Works 1
Figure G200710100977020070514D000451
(formation in next door)
After the washing of alkali-free glass substrate usefulness UV wash mill, use washing agent to scrub, carry out ultrasonic washing with ultra-pure water again.Substrate 120 ℃ of following thermal treatments 3 minutes, is made the surface state stabilization.
With after the substrate cooling, temperature adjustment to 23 ℃, with glass substrate with slit-shaped nozzle with coating machine (the エ Off エ one エ ス ア ジ ア System of society, trade name: MH-1600), apply formulated as mentioned above dark composition K1.Next use VCD (Minton dryer, East capital ying chemical industry She System) with dry 30 seconds of the part of solvent, lose the flowability of overlay after, 120 ℃ of following preroasts 3 minutes, obtain the dark photo-sensitive resin K1 of thickness 2.3 μ m.
Then, with mirror projector type exposure machine (MPA-8800CF, Canon's (strain) system), according to exposure 200mJ/cm 2Carry out pattern exposure.
Then, with the spray spout pure water of spraying, after making the surface of dark photo-sensitive resin K1 wetting equably, with KOH be developer solution (will contain non-ionic surfactant, trade name: CDK-1, Fuji's thin film electronic material (strain) System dilutes 100 times of materials that form) sprays development with flat nozzle pressure 0.04MPa under 23 ℃, obtain pattern and form image.Next use the pressure injection pure water of UHV (ultra-high voltage) Washing spray nozzle, remove residue, under atmospheric pressure with exposure 2500mJ/cm with 9.8MPa 2Carry out post-exposure from above.In addition, 230 ℃ of oven for baking 30 minutes, obtain the next door (black matrix) of thickness 2.0 μ m and optical concentration 4.0.
(anti-printing ink plasma treatment)
Forming on the septate substrate, using negative electrode connected mode parallel plate-type plasma treatment appts, carrying out anti-printing ink plasma treatment under the following conditions.
Using gases: CF 4
Gas flow: 80sccm
Pressure: 40Pa
RF electric power: 50W
Processing time: 30sec
The preparation of one ink for inking-
(preparation of dispersible pigment dispersion)
At first, utilize following method to obtain G dispersible pigment dispersion (G1).
In bromination phthalocyanine green (C.I.Pigment Green36), with spreading agent 1 (described compound 1) with as 1 of solvent, 3-butylene glycol diacetate (1,3-BGDA) shown in following table 3, cooperate, after mixing,, use the zirconium oxide bead of diameter 0.65mm with electronic mixer M-50 (the ア イ ガ one ジ ヤ パ Application System of society), disperseed 9 hours with peripheral speed 9m/s, be mixed with G dispersible pigment dispersion (G1).
Then, utilize following method to obtain other dispersion liquid.
Use in the preparation of dispersible pigment dispersion at G, except that cooperation pigment as shown in table 3 and other composition, operate equally with the preparation of dispersible pigment dispersion (G1) with G, be mixed with G dispersible pigment dispersion (G2), R dispersible pigment dispersion (R1), (R2), B dispersible pigment dispersion (B1), (B2).
[table 3]
Figure G200710100977020070514D000461
(mass parts)
(preparation of ink for inking)
At first, utilize following method to obtain the G jetted ink.
As described in the prescription of following table 4, with propylene glycol monomethyl ether acetate (PGMEA, 146 ℃ of boiling points), hexanediyl ester, described surfactant 1, thermal polymerization (V-40, azo two (cyclohexane-1-nitrile) and the pure medicine of light (strain) system) composition mixes, 25 ℃ stir 30 minutes after, confirming does not have insolubles, is mixed with monomer liquid.
Then, limit stirring G dispersible pigment dispersion (G1), G dispersible pigment dispersion (G2), described monomer liquid is slowly added on the limit, stirs 30 minutes down at 25 ℃, is mixed with G jetted ink (printing ink G-1).
Then, except that change prescription as described in Table 4, similarly operate preparation R jetted ink (printing ink R-1) and B jetted ink (printing ink B-1) with the preparation of printing ink G-1.In addition, " 1,3-BGDA " that is used for the preparation of (printing ink R-1) and (printing ink B-1) is " 1,3 butylene glycol a diacetate (232 ℃ of boiling points).
[table 4]
Figure G200710100977020070514D000471
(mass parts)
-utilize the formation of the pixel portions of ink-jetting style-
Use aforesaid printing ink R-1, G-1, B-1 then, in the zone that the next door with the above-mentioned filter substrate that obtains distinguishes (with the recess of protuberance encirclement), utilize Dimatix She System ink gun (28 ℃ of SE-128, nozzle temperatures) ejection printing ink to desirable concentration, went up dry 5 minutes at 100 ℃ heating plates (hot plate).And, by roasting in 230 ℃ of baking ovens 30 minutes, make all full solidification of next door, pixel, make the color filter that the pattern by R, G, B constitutes.
[contrast of color filter/red pixel is measured]
At this, utilize described method to measuring (contrast 1) by the contrast of the red pixel of the following color filter that obtains.
Use three-wavelength cold-cathode tube light source (on Toshiba's ラ イ テ Star Network (strain) corporate system FWL18EX-N diffuser plate to be set as back light unit, between two polaroids (day eastern electrician (strain) corporate system G1220DUN), sample is set, measure polaroid when parallel and the light transmission capacity when vertical, this ratio is spent as a comparison (with reference to " nineteen ninety the 7th color reversion glory association discuss, 512 looks demonstration 10.4 " size TFT-LCD with color filter, plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).The mensuration of brightness is used chroma-luminance meter ((strain) ト プ コ Application corporate system BM-7A, annex lens straps AL-11).This chroma-luminance meter is provided with third in the following manner and measures: the position that is provided with of two polaroids, sample, chroma-luminance meter is, from the position of 20mm backlight polaroid is set, the cylinder of diameter 11mm length 20mm is set in the position of 40～60mm, wherein pass through light, be radiated at the polaroid of the position setting of 65mm, central focus in the 88mm position in red pixel.The mensuration angle of chroma-luminance meter is 0.1 °.Light quantity backlight is, be not provided with under the state of sample, and the brightness when two polaroids being set being parallel nicol is 36000cd/m2.In addition, with the glass of filter substrate towards setting backlight.
[evaluation of color filter/colour mixture, white point]
In addition, use the above-mentioned color filter of observation by light microscope, whether 3000 pixel observations are arbitrarily had white point and colour mixture, utilize following standard to estimate.What be allowed to is to be the scope of A level, B level or C level for whole projects.
A level: do not have fully
B level: 1～2 place is arranged
C level: 3～4 places are arranged
D level: 5～10 places are arranged
E level: have more than 11 places
[evaluation of color filter/pixel fragment difference]
Below, carry out the evaluation of primitive shape (protruding or smooth).
Measure the surface configuration of red pixel arbitrarily with the surfagauge P-10 of Tencor She System, obtain height poor of lowermost portion in the abyss of the part of protuberance of pixel central portion and pixel.The section difference that allows is below the 0.1 μ m.
The manufacturing of-liquid crystal indicator-
On R pixel, G pixel and B pixel and next door (black matrix), further form the transparency electrode of ITO (Indium Tin Oxide) by sputter by the above-mentioned filter substrate that obtains.
Then, the embodiment 1 according to the spy opens the 2006-64921 communique forms space bar in the part that is equivalent to the top, next door (black matrix) on the ITO film of described formation.
Prepare glass substrate in addition as counter substrate,, make it be used for PVA model usefulness, the oriented film that is made of polyimide further is set thereon implementing composition respectively on the transparency electrode of filter substrate and on the counter substrate.
Then, utilize the divider mode to apply the sealant of ultraviolet curable resin in the position that is equivalent to be arranged on next door on every side (black matrix) housing as the pixel group that surrounds color filter, PVA model liquid crystal drips, after itself and counter substrate are glued together, the substrate that composes is carried out the UV irradiation, heat-treat, make sealant cures.Paste the polaroid HLC2-2618 of (strain) サ Application リ ツ System on the two sides of the liquid crystal cells that obtains thus.Then, (((ス タ Application レ one (the sheet type LED of strain) System) is as blueness (B) LED as green (G) LED, use DB1112H for ス タ Application レ one (the sheet type LED of strain) System) for red (R) LED of ス タ Application レ one (the sheet type LED of strain) System) conduct, use DG1112H to use FR1112H, constitute the backlight of sidelight daylighting mode, be configured in the side at the back side that becomes the liquid crystal cells that is provided with described polaroid, make liquid crystal indicator.
[display device/visual valuation]
At this, utilize visual valuation by the above-mentioned liquid crystal indicator that obtains display image whether normally.According to following standard evaluation.
Excellent: various pixels normally show, and image has innervation.
Very: each pixel shows normal.
Difficulty: confirm color spot by visual, perhaps pixel bleaches, and it is poor to show.
[contrast of display device/red pixel is measured]
Then, carefully decompose, take out color filter, utilize the contrast (contrast 2) of measuring red pixel with above-mentioned same method.
[synthetic determination]
From above evaluation, utilize following standard determination comprehensive evaluation.
◎ does not have that colour mixture and white point, pixel are smooth, the contrast of color filter, display device is all very good
Zero: do not have colour mixture and white point, pixel is smooth, and the contrast of color filter, display device is all good, the display device of high display quality
Zero ': do not become the colour mixture and the white point of problem, pixel is smooth, and the contrast of color filter, display device is all good, the display device of high display quality
*: difficult in each of the contrast of the colour mixture of color filter and white point, contrast, display device, the display device of low display quality
Above evaluation result is shown in following table 5 and table 6.
[embodiment 2～7, comparative example 1～3]
In embodiment 1, monomer in the printing ink and surfactant are changed to following table 5 and the described material of table 6, in addition, color filter and liquid crystal indicator are made in operation similarly to Example 1, estimate.
EF802: contain the perfluoroalkyl of carbon number 8, the fluorine of polyethylene/polypropylene oxides structure is a surfactant.
ノ イ ゲ Application EA80: the non-fluorine that contains the polyethylene/polypropylene oxides structure is a surfactant.
[embodiment 8]
In the preparation of the ink for inking (printing ink B-1, R-1 and G-1) of embodiment 5, the addition (the described amount of described table 4) of surfactant 1 is changed to 0.1 part, in addition, operation similarly to Example 5, make color filter and liquid crystal indicator, estimate.
[embodiment 9]
In the preparation of the ink for inking (printing ink B-1, R-1 and G-1) of embodiment 5, the addition (the described amount of described table 4) of surfactant 1 is changed to 0.4 part, in addition, operation similarly to Example 5, make color filter and liquid crystal indicator, estimate.
[embodiment 10]
Anti-printing ink disposal route is changed to the method for the following stated, and in addition, color filter and liquid crystal indicator are made in operation similarly to Example 5, estimate.
(anti-printing ink plasma treatment)
The described atmos plasma device of Fig. 1 that use is opened flat 7-111195 with the spy is expanded into the device of volume 1200L, carries out the anti-printing ink in next door and handles.As condition, importing gas is argon gas as inert gas, is mixed with propane gas in order further to make the light emitting discharge stabilization.With respect to argon gas 600L/ minute, the blending ratio of propane gas was 2.4L/ minute.After air being replaced fully, import CF with 18L/ minute ratio with this mixed gas 4Gas (4 methyl fluoride) applies the high-frequency voltage of 5000V between upper/lower electrode.In addition, frequency setting is 3000Hz, and irradiation time is set at 20 seconds.Cause orange light emitting discharge, highly stable.
[embodiment 11]
The formation method in next door is changed to the method for the following stated, and in addition, color filter and liquid crystal indicator are made in operation similarly to Example 5, estimate.
The formation in-next door-
(making of photosensitive transfer printing material)
On the false support of the pet film of thick 75 μ m, use the slit-shaped nozzle, coating makes its drying by the thermoplastic resin coating liquid that following prescription C constitutes.Then, coating makes its drying by the oxygen blocking layer coating liquid that following prescription P1 constitutes.Further the described dark composition K1 of the described table 2 of coating makes its drying.The oxygen blocking layer and the dry film thickness that thermoplastic resin, dry film thickness that dry film thickness is 14.6 μ m are set thus are 1.6 μ m on false support are the photo-sensitive resin of 2.5 μ m, last crimping diaphragm (polypropylene films of thick 12 μ m).
The photosensitive transfer printing material K1 that the photo-sensitive resin of making false support, thermoplastic resin, oxygen blocking layer, black (K) like this becomes one.
＜thermoplastic resin is with applying liquid: prescription C 〉
11.1 parts of methyl alcohol
6.36 parts of propylene glycol monomethyl ethers
52.4 parts of butanone
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000,
Figure G200710100977020070514D000511
)
5.83 part
Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)=63/37, molecular weight=10,000,
Figure G200710100977020070514D000512
) 13.6 parts
In bisphenol-A, 2 equivalent five ethylene glycol monomethyl acrylate are carried out 9.1 parts of the compounds (Xin Zhong village chemistry (strain) System BPE-500) that dehydrating condensation forms
10.54 parts in described surfactant
＜oxygen blocking layer is with applying liquid: prescription P1 〉
PVA205 (32.2 parts of polyvinyl alcohol (PVA), Network ラ レ (strain) System, saponification degree=88%, the degree of polymerization 550)
14.9 parts of polyvinylpyrrolidones (BASF She System, K-30)
524 parts of distilled water
429 parts of methyl alcohol
(formation in next door)
On alkali-free glass substrate, utilize spray to coat 20 seconds of glass washing agent liquid that are adjusted into 25 ℃ on one side, wash with rotating brush on one side with nylon hair, behind the pure water spray washing, utilize spray to blow to be coated with 20 seconds of silane coupling agent (N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane 0.3% aqueous solution, trade name: KBM603, SHIN-ETSU HANTOTAI's chemistry), carry out the pure water spray washing.With the basal plate preheating device this substrate was heated 2 minutes down at 100 ℃.
After the diaphragm of described photosensitive transfer printing material K1 peeled off; use stacked machine (イ of Co., Ltd. Hitachi Application ダ ス ト リ イ ズ System (Lamic II type)); heating under described 100 ℃ on 2 minutes the substrate, minute carrying out stacked with 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transporting velocity 2.2m/.
Then, with the interface peel of the false support of PET, remove false support from thermoplastic resin.
After peeling off interim false support, with mirror projector type exposure machine (MPA-8800CF, Canon's (strain) system), according to exposure 90mJ/cm 2Carry out pattern exposure.
Then, with the spray spout pure water of spraying, after making the surface of this photo-sensitive resin K1 wetting equably, with KOH is that developer solution (it is rare to 100 times of materials that form with pure water to contain KOH, non-ionic surfactant, trade name: CDK-1 (the film ア Yi チ System of Fuji)) sprays 80 seconds of developing with flat nozzle pressure 0.04MPa under 23 ℃, obtains pattern and forms image.Next, spray, remove residue, obtain the image of rectangular black (K) with the pressure of UHV (ultra-high voltage) washing nozzle with 9.8MPa.Then, further use extra-high-pressure mercury vapour lamp with 1000mJ/cm from the side of this resin bed to this substrate 2Light carry out post-exposure, further from relative this substrate and this resin bed opposition side usefulness extra-high-pressure mercury vapour lamp with 1000mJ/cm 2Light carry out post-exposure, then, under 220 ℃, heat-treated 30 minutes, form the next door.
[embodiment 12]
In the preparation of the ink for inking (printing ink B-1, R-1 and G-1) of embodiment 5, (V-40) changes to 2 with thermal polymerization, 4-two (trichloromethyl)-6-[4 '-(N, N-diethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine, and the curing of pixel is changed to following method from " roasting is 30 minutes 230 ℃ of baking ovens ", in addition, operation similarly to Example 5, make color filter and liquid crystal indicator, estimate.
The curing of-pixel (exposure)-
Operation similarly to Example 5 after (at the recess that protuberance surrounds) is ejected to desirable concentration in the zone that the next door with filter substrate distinguishes with above-mentioned ink for inking (printing ink B-1, R-1 and G-1), uses extra-high-pressure mercury vapour lamp with 110mJ/cm 2Exposure carry out blanket exposure from substrate surface (face of giving the printing ink side of substrate), pixel portions is solidified.Then, by with color filter roasting 30 minutes in 230 ℃ of baking ovens, make all full solidification of next door, pixel.
[embodiment 13]
Except the method for making with liquid crystal indicator changes to following mode, adopted the evaluation method identical with embodiment 5.
[manufacturing of display device]
On the R of filter substrate pixel, G pixel and B pixel and next door (black matrix), further form the transparency electrode of ITO (Indium Tin Oxide) by sputter.In addition, prepare glass substrate in addition, form the transparency electrode of ITO equally by sputter as counter substrate.And, on the described ito transparent electrode with the next door above suitable part the light spacer is set, the alignment films that is made of polyimide is set thereon again.
-liquid crystal aligning cut apart with the formation of projection-
To be used with photo-sensitive resin by the projection that following prescription A constitutes and apply liquid, the slit coating machine by same as described above applies ito transparent electrode on color filter, form the projection photo-sensitive resin by drying.
Then, projection with photo-sensitive resin on, use the middle layer that constitutes by described prescription P1 with coating liquid, the diaphragm that dry film thickness is 1.6 μ m is set.
＜projection is used with photo-sensitive resin and is applied liquid: prescription A 〉
53.3 parts of eurymeric etching solutions
(the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) system, FH-2413F)
46.7 parts of butanone
1 0.04 parts in described surfactant
Then, with mirror projector type exposure machine (MPA-8800CF, Canon's (strain) system), according to exposure 200mJ/cm 2Carry out pattern exposure.
After this,, utilize the shower type developing apparatus with 2.38% tetramethyl-ammonium hydroxide aqueous solution, 33 ℃ following 30 seconds, on one side develop on one side with photo-sensitive resin spraying to projection, develop and remove the part do not wanted (exposure portion) of projection with photo-sensitive resin.Like this, the part of the top that is positioned at R pixel, G pixel and B pixel on the ito transparent electrode of color filter form pattern form desired shape projection.Then, following 50 minutes at 240 ℃, the filter substrate that will be formed with this projection bakes processing, and the orientation that can form height 1.5 μ m, vertical section shape (shape of the face parallel with the normal direction of glass substrate face) breaded fish stick appearance on filter substrate is cut apart and used projection.
After this, utilize the divider mode to apply the sealant of ultraviolet curable resin in the position that is equivalent to be arranged on the next door housing on every side as the pixel group that surrounds color filter, MVA model liquid crystal drips, after itself and counter substrate are glued together, the substrate that composes is carried out the UV irradiation, heat-treat, make sealant cures.Obtain liquid crystal cells thus.Paste the polaroid HLC2-2518 of (strain) サ Application リ ツ System on the two sides of this liquid crystal cells.Then, constitute the backlight of cold-cathode tube, be configured in the side at the back side that becomes the liquid crystal cells that is provided with described polaroid, make liquid crystal indicator.
[embodiment 14]
It is that surfactant ペ イ Application タ Star De 32 (eastern レ ダ ウ コ one ニ Application グ corporate system) in addition, carries out identical manufacturing and evaluation with embodiment 5 that surfactant is changed into the silicon that contains the epoxyalkane structure.Specifically be, the surfactant in the table 41 is changed into ペ イ Application タ Star De 32, addition is changed into 0.3 (form branch admittedly as surfactant, have equal in quality part with embodiment 5) from 1.0.
[embodiment 15]
With printing ink change into following beyond, carry out identical manufacturing and evaluation with embodiment 5.
(Production Example A: polymkeric substance (A-1) synthetic) is in the four-hole boiling flask with thermometer, reflux cooler, stirring machine, the parts that drip, according to the cooperation ratio in the Table A, add solvent diethylene glycol single-butyl ether acetate (another name: Block チ Le カ Le PVC ト one Le ア セ テ one ト, BCA) 41.0 weight portions that do not contain hydroxyl, be heated to 140 ℃ while stirring.Then, under 140 ℃ temperature with single amount body of the composition of Table A record and, potpourri (composition drips) 54.7 weight portions of polymerization initiator, dripped from the parts constant speed of dripping through 2 hours.Drip finish after, be cooled to 110 ℃, potpourri (appending catalyst component) 4.6 weight portions that add polymerization initiator and do not contain the solvent diethylene glycol single-butyl ether acetate (BCA) of hydroxyl kept 2 hours under 110 ℃ temperature and finish reaction, obtained host polymer (A-1) thus.Weight-average molecular weight is 4200.
[Table A]
(mass parts)
Abbreviation in the table is explained as follows:
GMA: glycidyl methacrylate (glycidyl methacrylate)
MMA: methyl methacrylate
PERBUTYL zero: t-butyl peroxy 2 ethyl hexanoic acid ester (Japanese grease (strain) system trade name)
Weight-average molecular weight: gel soaks into the value that chromatography is carried out polystyrene conversion.
(Production Example B: consolidated block carboxylic acid compound (B-1) synthetic) is in the four-hole boiling flask with thermometer, reflux cooler, stirring machine, the parts that drip, according to the cooperation ratio among the table B, add solvent, raw material (polybase yl carboxylic acid), consolidated block agent (vinethene), be heated to 70 ℃ while stirring.Then, under 70 ℃ temperature, continue to stir,, obtain consolidated block carboxylic acid compound (B-1) thus when the acid number of potpourri becomes 5 to finish reaction when following.Acid number be 1.3 and the consolidated block rate be 99.5%.
[table B]
B-1
Cyclohexanone 18.0
Trihemellitic acid 31.5
The n-butyl vinyl ether 54.0
(mass parts)
The acid number of solution: in the 0.1NKOH ethanolic solution, drip and calculate.
Block (block) change rate:, convert and calculate solid formation branch by the acid number of solution.
Solid formation divided in block acid: utilize gas chromatography (GC) to measure.
(modulation of dispersible pigment dispersion)
With prescription change to following table beyond, adjusted dispersible pigment dispersion (G3, G4, R3, R4, B3, B4) in the same manner with embodiment 1.
Figure G200710100977020070514D000561
Figure G200710100977020070514D000571
(1) modulation of printing ink
According to the cooperation ratio shown in the table C, consolidated block carboxylic acid (B), polyfunctional epoxy resin (EP#157) and halogen-free acidic catalyst (LC-1) with the polymkeric substance (A-1) of described Production Example A record, described Production Example B record, at room temperature abundant stirring and dissolving obtains printing ink.
[table C]
Figure G200710100977020070514D000572
Suspension points in the table is as follows:
EP#157:4 official can epoxy resin (trade name エ ピ コ one ト 157S70, ジ ヤ パ Application エ Port キ シ レ ジ Application corporate system)
LC-1: trade name ノ Off キ ユ ア one LC-1 (Nof Corp.'s system)
In addition, the section of measuring the red pixel of contrast 2 color filter is afterwards taken with SEM (40000 times), the result who measures the number average bead diameter of pigment (PR254) is 55nm.
[embodiment 16]
It is outside the surfactant Off タ one ジ エ Application ト 251 (ネ オ ス corporate system) that surfactant is changed into the fluorine that contains the epoxyalkane structure, carries out identical manufacturing and evaluation with embodiment 5.Specifically be, the surfactant in the table 41 is changed into Off タ one ジ エ Application ト 251, addition is changed into 0.3 (form branch admittedly as surfactant, have equal in quality part with embodiment 5) from 1.0.
[embodiment 17]
With surfactant change into the fluorine that contains the epoxyalkane structure be surfactant Port リ Off オ Star Network ス 652 (オ system ノ バ corporate system, PF652) outside, carry out identical manufacturing and evaluation with embodiment 5.Specifically be, the surfactant in the table 41 is changed into Off タ one ジ エ Application ト 251, addition is changed into 0.6 (form branch admittedly as surfactant, have equal in quality part with embodiment 5) from 1.0.
Figure G200710100977020070514D000601

Claims (10)

1. manufacturing method of color filter, described color filter be in the next door that has on the substrate between a plurality of pixels and pixel adjacent, described manufacturing method of color filter have at least successively following a), b) and c) operation:
A) on substrate, form the operation in the next door that constitutes by resin combination;
B) implement the operation of plasma treatment to forming septate substrate;
C) in the gap that is formed at the described next door on the substrate, give ink for inking with ink-jet method and form the operation of pixel, described ink for inking contains C.I paratonere 254, solvent, surfactant at least and has the monomer of 2 above polymerism bases, wherein, described surfactant contains fluorine
Described surfactant has at least 1 structural unit a and at least 1 structural unit b that comes the monomer of free following general formula (b) expression of coming the monomer of free following general formula (a) expression, and the mass ratio a/b that contains at least a structural unit a and structural unit b is 20/80～80/20 multipolymer
General formula (a)
General formula (b)
Figure FSB00000446360400012
In general formula (a), R 1Expression hydrogen atom or methyl, in addition, in the general formula (a)-C mF 2m + 1Be straight or branched, m represents 2～14 integer, and n represents 1～18 integer,
In general formula (b), R 2And R 3Represent hydrogen atom or methyl independently of one another, R 4The alkyl of expression hydrogen atom or carbon number 1～5, p and q represent 0～18 integer independently of one another, p and q be expression simultaneously zero not.
2. manufacturing method of color filter as claimed in claim 1 is characterized in that described plasma treatment is an atmospheric plasma processes.
3. as claim 1 or 2 described manufacturing method of color filter, it is characterized in that described monomer with 2 above polymerism bases is the monomer with 3 above polymerism bases.
4. manufacturing method of color filter as claimed in claim 1 is characterized in that, described polymerism base is the base with the two keys of ethene.
5. manufacturing method of color filter as claimed in claim 1 is characterized in that, described polymerism base is an epoxy radicals.
6. manufacturing method of color filter as claimed in claim 1 is characterized in that, described polymerism base is selected from least a kind in acryloyl group and the methacryl.
7. manufacturing method of color filter as claimed in claim 1 is characterized in that, described ink for inking contains at least a kind that is selected from Photoepolymerizationinitiater initiater and the thermal polymerization.
8. manufacturing method of color filter as claimed in claim 1 is characterized in that, at described c) after the operation, further through being selected from following d) and e) at least one operation, make the ink composite polymerization and form pixel,
D) operation of irradiation active energy ray behind the solvent in removing removal ink;
E) operation that heats.
9. color filter utilizes that any described manufacture method is made in the claim 1～8.
10. a display device possesses the described color filter of claim 9.
CN 200710100977 2006-05-02 2007-04-28 Method of manufacturing color filter, color filter and displaying device Expired - Fee Related CN101067668B (en)

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