CN101359176B - Curing composition, method for producing photospace material and liquid crystal display device - Google Patents
Curing composition, method for producing photospace material and liquid crystal display device Download PDFInfo
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- CN101359176B CN101359176B CN2008101316538A CN200810131653A CN101359176B CN 101359176 B CN101359176 B CN 101359176B CN 2008101316538 A CN2008101316538 A CN 2008101316538A CN 200810131653 A CN200810131653 A CN 200810131653A CN 101359176 B CN101359176 B CN 101359176B
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- liquid crystal
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
Abstract
The invention provides a solidification composite, at least comprising: resin containing radical having branch chain and/or alicyclic structure, radical having acidic group and radical having epoxy group; polymerizability compound; tiators for photopolymerization; and surface activity tiators for photopolymerization. The invention can obtain solidification composite with height deforming recoverability and liquid crystal display displaying unevenly.
Description
Technical field
The present invention relates to manufacture method, base plate for liquid crystal display device and the liquid crystal indicator of a kind of solidification compound, cured film, optical gap material.
Background technology
Liquid crystal indicator is widely used in showing the display device of high image quality image.Liquid crystal indicator disposes the liquid crystal layer that can show by the orientation of regulation image usually between a pair of substrate.The thickness that to keep equably this substrate interval be liquid crystal layer is one of key element that determines picture quality, remains on certain gap material so set for the thickness with liquid crystal layer.Thickness between this substrate is commonly called " element thickness ", the thickness of the described liquid crystal layer of element thickness ordinary representation, and in other words, expression applies 2 interelectrode distances of electric field to the liquid crystal of viewing area.
The gap material formed by scattering pearl in the past, in recent years, became gradually with solidification compound and utilized photoetching process to form the high gap material of position precision.The gap material that such use solidification compound forms is called as optical gap material (photo spacer, light beam).
Use solidification compound through a little less than forming pattern, alkali develops and curing the compression strenght of insulating point (spacer dot) of the optical gap material of making, when forming panel, have plastic yield and become large trend.The thickness that the image display requirement of high image quality does not become large liquid crystal layer because of its plastic yield becomes and can not keep the problem of homogeneity or the problem of image inequality occurs less than design load etc.In addition, from the point of the high precision of liquid crystal indicator, the alkali development residue that does not produce solidification compound is also very important.
About described problem, remain certain optical gap material formations technology as the thickness (element thickness) that is used for liquid crystal layer, disclose the optical gap material form with in use have allylic resin (for example with reference to JP 2003-207787 communique).
In addition, also disclose the solidification compound (for example with reference to JP 2005-62620 communique) that the outstanding optical gap material of easy manufacturing and storage-stable is used.
And then, also disclose the outstanding composition of cold-hot impact (for example with reference to JP 2002-287354 communique).
And then, as solidification compound, also disclose the solidification compound (for example with reference to the public table of patent (special table) 2004-515611 communique, special table 2004-522819 communique, special table 2004-525994 communique) of the surface-active photoinitiators of the surface strength that contains the cured film that can improve formation.
It is restorative that the optical gap material that uses in liquid crystal cells is required to have high distortion always.In order to realize this requirement, although can improve the cross-linking reaction rate of monomer etc. Recovery to be brought up to a certain degree, this raising effect exists becomes maximum trend, needs further to improve.
Summary of the invention
The present invention is just in view of described and propose, its purpose is to provide that the distortion that has height after the curing is restorative for example can eliminate the manufacture method that shows uneven solidification compound and cured film, optical gap material and prevent from showing that thereby inequality can carry out base plate for liquid crystal display device and the liquid crystal indicator of the demonstration of high image quality image when forming liquid crystal indicator, to realize that this purpose is as problem.
As described below for the concrete means that solve described problem.
＜1〉a kind of solidification compound wherein, comprises at least: resin, and it contains the base with side chain and/or alicyclic structure, the base that has the base of acidic groups and have epoxy radicals; Polymerizable compound; Photoepolymerizationinitiater initiater; With the surfactivity Photoepolymerizationinitiater initiater.
＜2〉according to described＜1〉the middle solidification compound of putting down in writing, wherein, described surfactivity Photoepolymerizationinitiater initiater be have from can substituted carbon number more than 3 and below 30 alkyl, can substituted siloxy group and can substituted fluorinated alkyl at least a compound selected.
＜3〉according to described＜1〉or＜2〉the middle solidification compound of putting down in writing, wherein, described surfactivity Photoepolymerizationinitiater initiater is to contain from trihalomethyl-s-triaizine compounds, San halogen Jia oxadiazole compound, alpha-amido ketonic compound, alpha-hydroxyacetone compounds or oxime compound to derive and next substituent compound.
＜4〉according to described＜1 〉～＜3 in the solidification compounds of any one record, wherein, described base with alicyclic structure is that derive from can substituted carbon number 6 or more and the base of the ring compound below 25.
＜5〉a kind of cured film, it is to make described＜1 〉～＜4 in the solidification compounds of any one record solidify the cured film that forms.
＜6〉a kind of manufacture method of optical gap material wherein, has:＜1 described by applying 〉～＜4 in any one record solidification compounds and form the operation of solidification compound layer at supporter.
＜7〉a kind of base plate for liquid crystal display device wherein, possesses and utilizes described＜6〉in the optical gap material that forms of the manufacture method manufacturing of optical gap material of record.
＜8〉a kind of liquid crystal indicator wherein, possesses described＜7〉the middle base plate for liquid crystal display device of putting down in writing.
If utilize the present invention, the distortion that has height after the curing is restorative for example can be eliminated the manufacture method that shows uneven solidification compound and cured film, optical gap material and prevent from showing that inequality can carry out base plate for liquid crystal display device and the liquid crystal indicator of the demonstration of high image quality image when forming liquid crystal indicator thereby can provide.
Embodiment
Below the manufacture method of solidification compound of the present invention and cured film, optical gap material and base plate for liquid crystal display device and liquid crystal indicator are elaborated.
The manufacture method of＜solidification compound and optical gap material 〉
Solidification compound of the present invention contains at least: contain base with side chain and/or alicyclic structure, have the base of acidic groups and have resin (A) at least a of the base of epoxy radicals; Polymerizable compound (B) at least a; Photoepolymerizationinitiater initiater (C) at least a; At least a with surfactivity Photoepolymerizationinitiater initiater (D).The distortion that has height owing to the optical gap material that utilizes solidification compound manufacturing of the present invention is restorative, so the demonstration that can eliminate in the display device is uneven.
In addition, the manufacture method of optical gap material of the present invention be make possess at least 2 supporters, at the liquid crystal that arranges between described supporter, apply 2 electrodes of electric field and be used for controlling the method for described optical gap material of liquid crystal indicator of the optical gap material of the element thickness between described supporter to described liquid crystal, have the layer that a side at described 2 supporters forms the solidification compound layer that uses solidification compound of the present invention and form operation.
If utilize the manufacture method of optical gap material of the present invention, can easily make the restorative optical gap material of distortion with height.
Below the manufacture method of optical gap material of the present invention is described, by this explanation, the concrete condition of solidification compound of the present invention also is described.
[layer forms operation]
It is to form by applying the operation of the solidification compound layer (following also referred to as " curable resin layer ") that solidification compound of the present invention contains at supporter that layer among the present invention forms operation.
This curable resin layer can form operation and consist of the optical gap material that distortion is restorative well, element thickness can be remained homogeneous through pattern described later.By using this optical gap material, particularly occuring easily owing to the change of element thickness in the uneven display device of demonstration, effectively the inequality of the demonstration in the removal of images.
As the method that forms the curable resin layer at supporter, can preferably enumerate (a) utilize known coating process coating contain solidification compound of the present invention solution method and (b) utilize the transfer printing with the curable resin transfer materials to come stacked method.Below respectively explanation.
(a) coating process
The coating of solidification compound can utilize extrusion coating method (extrusion coating) that known coating process such as spin-coating method, curtain be coated with the use funnel (Port Star パ one) of putting down in writing in method, slit coating process, dip coating, air knife knife coating, rolling method, wire bar coating process, intaglio coating process or No. 2681294 instructions of United States Patent (USP) etc. to carry out.Wherein, the method for utilizing gap nozzle or slit coating machine of record in preferred (Japan) JP 2004-89851 communique, (Japan) JP 2004-17043 communique, (Japan) JP 2003-170098 communique, (Japan) JP 2003-164787 communique, (Japan) JP 2003-10767 communique, (Japan) JP 2002-79163 communique, (Japan) the JP 2001-310147 communique etc.
(b) transfer printing
Utilize in the situation of transfer printing, use has the curable resin transfer materials of solidification compound layer at least on the temporary supporting body, supporting on the dignity, utilize roller or the flat board of heating and/or pressurization, thereby carry out crimping or add thermo-compressed making its applying supporter to form membranaceous curable resin layer at the temporary supporting body, then by peeling off the temporary supporting body, transfer printing cured resin composition layer on supporter.Particularly, can enumerate laminating machine and the laminating method put down in writing in (Japan) Unexamined Patent 7-110575 communique, (Japan) Unexamined Patent 11-77942 communique, (Japan) JP 2000-334836 communique, (Japan) the JP 2002-148794 communique, from the viewpoint of low foreign matter, the preferred method of putting down in writing in (Japan) the Unexamined Patent 7-110575 communique of using.
Form at the temporary supporting body in the situation of curable resin layer, can between curable resin layer and temporary supporting body so that arrange oxidation prevention layer (below be also referred to as " oxygen-proof membrane " or " middle layer ".)。Like this, can improve exposure sensitivity.In addition, in order to improve transfer printing, also the thermoplastic resin with resiliency can be set.
For the temporary supporting body that consists of this curing property transfer film, oxidation prevention layer, thermoplastic resin, other layers maybe should curing property transfer film method for making, identical with structure, the method for making of record in paragraph numbering [0024]～[0030] of (Japan) JP 2006-23696 communique.
Utilizing (a) coating process, (b) transfer printing to apply together in the situation that forms the curable resin layer, its bed thickness is preferably 0.5～10.0 μ m, more preferably 1～6 μ m.If bed thickness in described scope, the generation of the bubble when coating in the time of can preventing from making forms, the development that can not need to carry out for a long time unexposed section is removed.
As the supporter that is formed with the curable resin layer, for example can enumerate transparency carrier (for example glass substrate or plastic base), nesa coating (for example ITO film), (be also referred to as colour filtering chip basic board with the substrate of color filter.), the driving substrate etc. of band driving element (such as thin film transistor (TFT) [TFT]).As the thickness of supporter, usually be preferably 700～1200 μ m.
～solidification compound～
Then, solidification compound is described.
Solidification compound contains at least: containing base with side chain and/or alicyclic structure, have the base of acidic groups and have the resin (A) of the base of epoxy radicals (following also can be referred to as " resin (A) ".); Polymerizable compound (B); Photoepolymerizationinitiater initiater (C); With surfactivity Photoepolymerizationinitiater initiater (D).In addition, as required, also can consist of with other compositions such as colorant or surfactant.
Described solidification compound is particularly preferred for the optical gap material and uses.
-resin (A)-
Resin (A) contains the base that has side chain and/or alicyclic structure at side chain: X, has the base of acidic groups: Y and the base with epoxy radicals: Z forms, and as required, also can have other bases (L).In addition, also can make up a plurality of X, Y and Z in the base in resin (A).
-have the base of side chain and/or alicyclic structure a: X-
Described " base with side chain and/or alicyclic structure " described.
At first, as the base with side chain, the alkyl that can show a chain of 3～12 of carbon numbers is such as enumerating isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl (isopentyl), neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, isopentyl (i-amyl), tertiary pentyl, 3-octyl group, uncle's octyl group etc.Wherein, preferred isopropyl, sec-butyl, the tert-butyl group, isopentyl (isopentyl) etc., and then preferred isopropyl, sec-butyl, the tert-butyl group etc.
Then, have alicyclic structure 5～25 of basis representation carbon numbers can substituted ester ring type alkyl.From the viewpoint of dissolubility, synthetic adaptability, the carbon number with base of alicyclic structure is preferably 6～20, and more preferably 6～17.
As the concrete example of the base with alicyclic structure, such as enumerating cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, adamantyl, three ring decyls, double cyclopentenyl, dicyclo amyl group, three cyclopentenyls and three cyclopentyl etc.Wherein, preferred cyclohexyl, norborny, isobornyl, adamantyl, double cyclopentenyl, dicyclo amyl group, three ring decyl, three cyclopentenyls and three cyclopentyl etc., and then preferred cyclohexyl, norborny, isobornyl, double cyclopentenyl and three cyclopentenyls etc.
As containing the monomer that has the base of side chain and/or alicyclic structure at side chain, can enumerate phenylethylene, (methyl) esters of acrylic acid, ethene ethers, vinyl esters, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl esters, (methyl) acrylic amide, and then preferred (methyl) esters of acrylic acid.
As the described concrete example of monomer that has the base of branched structure at side chain that contains, can enumerate (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) acrylic acid tert-pentyl ester, (methyl) acrylic acid second month in a season-different-pentyl ester, (methyl) acrylic acid 2-octyl group ester, (methyl) acrylic acid 3-octyl group ester, (methyl) acrylic acid uncle monooctyl ester etc., wherein, preferred (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, Tert-butyl Methacrylate etc., and then preferable methyl isopropyl acrylate, Tert-butyl Methacrylate etc.
Then, as the described concrete example of monomer that has the base of alicyclic structure at side chain that contains, be (methyl) acrylate with ester ring type alkyl of 5～20 of carbon numbers, 6～20 of preferred carbon numbers.As concrete example; can enumerate (methyl) acrylic acid (2-dicyclo [2.2.1]-heptyl) ester; (methyl) acrylic acid-1-adamantane esters; (methyl) acrylic acid-2-adamantane esters; (methyl) acrylic acid-3-methyl isophthalic acid-adamantane esters; (methyl) acrylic acid-3; 5-dimethyl-1-adamantane esters; (methyl) acrylic acid-3-ethyl adamantane esters; (methyl) acrylic acid-3-methyl-5-ethyl-1-adamantane esters; (methyl) acrylic acid-3; 5; 8-triethyl-1-adamantane esters; (methyl) acrylic acid-3; 5-dimethyl-8-ethyl-1-adamantane esters; (methyl) acrylic acid-2-methyl-2-adamantane esters; (methyl) acrylic acid-2-ethyl-2-adamantane esters; (methyl) acrylic acid-3-hydroxyl-1-adamantane esters; (methyl) acrylic acid octahydro-4; the inferior menthol (mentanoindene) of 7--5-acyl ester; (methyl) acrylic acid octahydro-4; the inferior menthol of 7--1-acyl group methyl ester; (methyl) acrylic acid-1-menthyl (menthyl) ester; (methyl) acrylic acid three ring decyl ester; (methyl) acrylic acid-3-hydroxyl-2; 6; 6-trimethyl-dicyclo [3.1.1] heptyl ester; (methyl) acrylic acid-3; 7; 7-trimethyl-4-hydroxyl-dicyclo [4.1.0] heptyl ester; (methyl) acrylic acid (falling) bornyl ester; (methyl) isobornyl acrylate; (methyl) acrylic acid fenchyl ester; (methyl) acrylic acid-2; 2,5-trimethylcyclohexyl; (methyl) cyclohexyl acrylate etc.In these (methyl) acrylate, the preferable methyl cyclohexyl acrylate, (methyl) acrylic acid (falling) bornyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid-1-adamantane esters, (methyl) acrylic acid-2-adamantane esters, (methyl) acrylic acid-2-methyl-2-adamantane esters, (methyl) acrylic acid-2-ethyl-2-adamantane esters, (methyl) acrylic acid-3-hydroxyl-1-adamantane esters, methacrylic acid fenchyl ester, methacrylic acid 1-menthyl ester, (methyl) acrylic acid three ring decyl ester etc., particularly preferably cyclohexyl methacrylate, methacrylic acid (falling) bornyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-adamantane esters.
And then, as the described concrete example of monomer that has the base of alicyclic structure at side chain that contains, can enumerate the compound by following general formula (1) or (2) expression.At this, in general formula (1), (2), x represent 1 or 2, R represent hydrogen atom or methyl.M and n represent 0～15 respectively independently.In general formula (1), (2), preferred x=1 or 2, m=0～8, n=0～4, more preferably m=1～4, n=0～2.As the preferred concrete example of the compound that is represented by general formula (1) or (2), can enumerate following Compound D-1～D-5, T-1～T-8.
The described monomer that has a base of alicyclic structure at side chain that contains can use the monomer of suitably making, and also can use commercially available product.
As described commercially available product, can enumerate Hitachi and change into industry (strain) system: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M etc.Wherein, the point outstanding from development, that Recovery is outstanding, preferred FA-512A (S), 512M.
-have the base of acidic groups a: Y-
As described acidic groups, be not particularly limited, can from known acidic groups, suitably select, such as enumerating carboxyl, sulfonic group, sulfoamido, phosphate, phenol hydroxyl etc.Wherein, from the outstanding point of the water tolerance of development and cured film, preferred carboxyl, phenol hydroxyl.
As the described monomer that has the base of acidic groups at side chain, be not particularly limited, can enumerate phenylethylene, (methyl) esters of acrylic acid, ethene ethers, vinyl esters, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl esters, (methyl) acrylic amide, and then preferred (methyl) esters of acrylic acid.
Concrete example as the monomer of the described base that has acidic groups at side chain, such as the addition reaction that can enumerate (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid one Arrcostab, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, alpha-cyano cinnamic acid, acrylic acid dimer, the monomer with hydroxyl and cyclic acid anhydride, ω-carboxyl-polycaprolactone one (methyl) acrylate etc. can suitably be selected from known monomer.The monomer that they can suitably use manufacturing also can use commercially available product.
As the monomer with hydroxyl that can in the addition reaction of described monomer with hydroxyl and cyclic acid anhydride, use, such as enumerating 2-hydroxyethyl (methyl) acrylate etc.As described cyclic acid anhydride, such as enumerating maleic anhydride, phthalic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride etc.
As commercially available product, can enumerate East Asia synthetic chemical industry (strain) system: ア ロ ニ Star Network ス M-5300, ア ロ ニ Star Network ス M-5400, ア ロ ニ Star Network ス M-5500, ア ロ ニ Star Network ス M-5600, Xin Zhong village chemical industry (strain) system: NK エ ス テ Le CB-1, NK エ ス テ Le CBX-1, common prosperity company oil chemical industry (strain) system: HOA-MP, HOA-MS, Osaka organic chemistry industry (strain) system: PVC ス コ one ト #2100 etc.Wherein, from development remarkably, point cheaply, preferred (methyl) acrylic acid etc.
-have the base of epoxy radicals a: Z-
Base as having epoxy radicals is not particularly limited, and for example can preferably enumerate the base that derives from by (methyl) acrylate compounds of following structural formula (1) or structural formula (2) expression.
Structural formula (1)
In structural formula (1), R
1Expression hydrogen atom or methyl, L
1The concatenating group of expression divalent.
In structural formula (2), R
2Expression hydrogen atom or methyl, L
2The concatenating group of expression divalent, W represents the aliphatic alkyl of 4～7 Yuans rings.
In described compound and the compound by structural formula (2) expression by structural formula (1) expression, compare the compound that is more preferably represented by structural formula (1) with structural formula (2).Reach in (2) at described structural formula (1), more preferably L
1And L
2Be the alkylidene of carbon number 1～4 independently respectively.
As described compound by structural formula (1) expression or by the monomer that has epoxy radicals at side chain of structural formula (2) expression, be not particularly limited, for example can enumerate following exemplary compounds (1)～(16).
As the monomer that has epoxy radicals at side chain among the present invention, from the viewpoint of dissolubility, synthetic adaptability, preferred diglycidyl (methyl) acrylate.In addition, these monomers can be used singly or in combination of two or more.
-other monomers-
As described other monomers, be not particularly limited, for example can enumerate (methyl) acrylate with side chain and/or alicyclic structure, styrene has the monomer of vinyl ether, dibasic acid anhydride base, vinyl ester, hydrocarbon chain thiazolinyl etc. etc.
As described vinyl ether, be not particularly limited, such as enumerating vinyl butyl ether etc.
As described dibasic acid anhydride base, be not particularly limited, such as enumerating maleic anhydride base, itaconic anhydride base etc.
As described vinyl ester, be not particularly limited, such as enumerating vinyl acetate base etc.
As described hydrocarbon chain thiazolinyl, be not particularly limited, such as enumerating butadienyl, isoprene base etc.
As the containing ratio of other monomers in the described resin (A), preferred mole ratio of components is 0～30mol%, more preferably 0～20mol%.
As the concrete example of (A) resin, can enumerate the compound that is represented by following compound structure P-1～P-7.Wherein, x, the y in the following structure, z and 1 represent respectively ratio of components (mol%).
-about manufacture method-
Described resin (A) can be by comprising at least described monomer (monomer) the operation of (being total to) polyreaction make.
Method to (being total to) polyreaction is not particularly limited, and can suitably select from the method for known copolymerization.For example, for the spike of polymerization, can suitably select free radical polymerization, cationic polymerization, anionic polymerisation, coordination polymerization etc.Wherein, from easy synthetic, point cheaply, preferably free radical polymerization.In addition, for polymerization, also be not particularly limited, can from known method, suitably select.For example, can suitably select mass polymerization, suspension polymerization, emulsion polymerization, solution polymerization process etc.Wherein, more preferably solution polymerization process.
-molecular weight-
Weight-average molecular weight as the preferred described multipolymer of resin (A) is preferably 10,000～100,000, and more preferably 12,000～60,000, be particularly preferably 15,000～4.5 ten thousand.From the manufacturing adaptability of multipolymer, the point of development, preferable weight-average molecular weight is in described scope.In addition, the point that the shape that forms from the reduction owing to melt viscosity is not easy to collapse, be not easy to become crosslinked bad point, can suppress the point of residue when developing, preferred.
In addition, weight-average molecular weight for example uses gel permeation chromatography (GPC) to measure.
-glass temperature-
Be preferably 40～180 ℃ as the preferred glass temperature (Tg) of resin (A), more preferably 45～140 ℃, be particularly preferably 50～130 ℃.Glass temperature (Tg) then can obtain having the optical gap material of good development, mechanical strength if in described preferred scope.
-acid number-
, but usually be preferably more than the 20mgKOH/g according to the preferred range changing of molecular structure institute that can obtain as the preferred acid number of resin (A), more preferably more than the 50mgKOH/g, be particularly preferably 70～130mgKOH/g.From the point of the optical gap material that can obtain having good development, mechanical strength, preferred acid number is in described preferable range.
From the point of the optical gap material that can obtain having good development, mechanical strength, the glass temperature (Tg) of described resin (A) is that 40～180 ℃ and weight-average molecular weight are 10,000～100,000.
And then the preference of described resin (A) is the various combinations of described molecular weight, glass temperature (Tg) and acid number more preferably.
From the viewpoint of Recovery, development residue, net, the resin among the present invention (A) is preferably the base that has respectively the described base that has side chain and/or alicyclic structure at side chain: X in different copolymerization unit, have acidic groups: the multipolymer more than at least 3 yuan of copolymerizations of Y and the base with epoxy radicals: Z.Particularly, the multipolymer that at least 1 each monomer generation copolymerization that consists of described X, Y, Z is formed.
Copolymerization ratio of components for described each composition of described resin (A), can consider that glass temperature and acid number determine, cannot treat different things as the same, " base with side chain and/or alicyclic structure " is preferably 10～70 % by mole, more preferably 15～65 % by mole, be particularly preferably 20～60 % by mole.If have the base of side chain and/or alicyclic structure at side chain in described scope, can obtain good development, also good to the patience of the developer solution of image section simultaneously.
In addition, " base with acidic groups " is preferably 5～70 % by mole, more preferably 10～60 % by mole, is particularly preferably 20～50 % by mole.If have the ratio of components of base of acidic groups at side chain in described scope, then can obtain good curing, development.
In addition, " base with epoxy radicals " is preferably 10～70 % by mole, more preferably 20～70 % by mole, is particularly preferably 30～70 % by mole.If have the ratio of components of base of epoxy radicals at side chain in described scope, then pigment-dispersing is outstanding, and development and curing property are also good.
As the content of described resin (A), all solids composition of relatively described photosensitive composite is preferably 5～70 quality %, more preferably 10～50 quality %.Solidification compound of the present invention also can contain resin (A) resin in addition, but preferably only contains resin (A).
In addition resin of-resin (A)-
As can with the resin of described resin (A) and usefulness, preferred relatively alkaline aqueous solution demonstrates the compound of swellability, more preferably alkaline aqueous solution is the compound of solubility relatively.
Demonstrate swellability or deliquescent resin as relative alkaline aqueous solution; for example can preferably enumerate the resin with acidic groups; particularly, preferably import the compound (epoxy acrylic ester compounds) of ethene unsaturated double-bond and acidic groups gained, have vinyl copolymer, the epoxy acrylic ester compounds and the potpourri that has the vinyl copolymer of (methyl) acryloyl group and acidic groups at side chain, maleamic acid based copolymer etc. of (methyl) acryloyl group and acidic groups at side chain to epoxy compound.
As described acidic groups, be not particularly limited, can suitably select according to purpose, such as enumerating carboxyl, sulfonic group, phosphate etc., wherein, from the viewpoint of the acquired grade of raw material, can preferably enumerate carboxyl.
The total content of-resin (A) and resin (A) resin in addition-
As the total content of described resin (A) and resin (A) resin in addition, all solids composition of relatively described solidification compound, preferred 5～70 quality %, more preferably 10～50 quality %.If this amount is less than 5 quality %, then the film strength of curable resin layer described later dies down easily, the stickability variation on the surface of this curable resin layer, if surpass 70 quality %, then exposure sensitivity may reduce.Wherein, described content represents solid component content.
-polymerizable compound (B), Photoepolymerizationinitiater initiater (C), other compositions-
In the present invention, can preferably use polymerizable compound (B), Photoepolymerizationinitiater initiater (C), consist of the composition of known composition as other compositions, for example can enumerate the composition of putting down in writing in paragraph numbering [0010]～[0020] of JP 2006-23696 communique, or the composition of record in the paragraph of JP 2006-64921 communique numbering [0027]～[0053].
-surfactivity Photoepolymerizationinitiater initiater (D)-
As the surfactivity Photoepolymerizationinitiater initiater (D) among the present invention, get final product so long as have the compound of surface activation and photopolymerization initiation, can use with being not particularly limited, for example can enumerate and in a part, contain the substituent at least a compound that has the substituent at least a of surface activation and have the photopolymerization initiation.
In solidification compound of the present invention, except Photoepolymerizationinitiater initiater (C), by further containing surfactivity Photoepolymerizationinitiater initiater (D), utilize the character of surface of the cured film of solidification compound formation to improve, can demonstrate good development patience.Like this, for example in the situation of making the optical gap material that consists of display device, the distortion that demonstrates height is restorative.
From the viewpoint of the character of surface of cured film, described substituting group with surface activation be preferably from can substituted carbon number more than 3 and below 30 alkyl, can substituted siloxy group and can substituted fluorinated alkyl select at least a.
Has substituting group in the substituent situation as these bases, such as the alkoxy of the alkyl that can enumerate carbon number 1～8, carbon number 1～8, halogen radical, amino, cyano group etc.
Described have substituent carbon number more than 3 and 30 following alkyl carbon number more than 4 and below 20 more preferably.Particularly, such as enumerating hexyl, octyl group, dodecyl, octadecyl, cetyl etc.
In addition, have a substituent siloxy group as described, for example preferably contain the structural unit by following general formula (3) expression.
General formula (3)
In the formula, R
31Expression hydrogen atom, alkyl or-OR
33, R
32Expression hydrogen atom, alkyl or-OR
34R
33And R
34Represent independently respectively alkyl.As by R
31～R
34The alkyl of expression can be enumerated the alkyl of carbon number 1～8, particularly, and preferable methyl, ethyl, propyl group etc.
As the repeat number of described structural unit by general formula (3) expression, the viewpoint from the character of surface of cured film is preferably 2～20, and more preferably 2～10.
In addition, described have that substituent fluorinated alkyl is preferably carbon number more than 1 and 16 following fluorinated alkyls, and more preferably carbon number is 3 or more and the fluorinated alkyls below 12.
In addition, can have substituting group in the substituent situation as fluorinated alkyl, such as the alkoxy of the alkyl that can enumerate carbon number 1～8, carbon number 1～8, halogen atom, amino, cyano group etc.
In the present invention, be preferably the fluorinated alkyl that is represented by following general formula (4).
General formula (4)
——(CH
2)
i-L
4-C
jF
2j+1
In the formula, L
4Expression oxygen atom or singly-bound, i represents 0～8 integer, j represents 1～12 integer.In the present invention, preferably i is that 0～6 integer, j are 1～10 integer, and more preferably i is that 1～4 integer, j are 2～8 integer.
Particularly, such as enumerating perfluoro hexyl oxygen ethyl, perfluoro capryl ethyl etc.
In addition, as the substituting group with photopolymerization initiation, can enumerate the substituting group of deriving and forming from the Photoepolymerizationinitiater initiater that illustrates as described Photoepolymerizationinitiater initiater (C).Wherein, from the viewpoint of photopolymerization initiating activity, be preferably from trihalomethyl-s-triaizine compounds, San halogen Jia oxadiazole compound, alpha-amido ketonic compound, alpha-hydroxyacetone compounds etc. and derive and next substituting group.
Surfactivity Photoepolymerizationinitiater initiater (D) among the present invention also can and have between the substituting group of photopolymerization initiation at the substituting group with surface activation and have concatenating group.As described concatenating group, be not particularly limited, for example can enumerate oxygen atom (O-), sulphur atom (S-), nitrogen-atoms, carbonyl, amido link, ester bond, alkylidene, alkenylene, arlydene and by their concatenating group that constitutes.In addition, be not limited to the concatenating group of divalent, also can be the concatenating group more than 3 valencys.
As the surfactivity Photoepolymerizationinitiater initiater (D) among the present invention, particularly, can enumerate compound or the following exemplary compounds 1～44 of record in (Japan) special table 2004-515611 communique, (Japan) special table 2004-522819 communique, (Japan) the special table 2004-525994 communique etc.
As the surfactivity Photoepolymerizationinitiater initiater (D) among the present invention, viewpoint from the character of surface of cured film, the substituting group that preferably has a surface activation is for from can substituted chain alkyl, can substituted siloxy group and can substituted fluorinated alkyl in select at least a, and the substituting group with photopolymerization initiation is from trihalomethyl-s-triaizine compounds, San halogen Jia oxadiazole compound, the alpha-amido ketonic compound, alpha-hydroxyacetone compounds is derived and next substituting group, the substituting group that more preferably has surface activation is the fluorinated alkyl of carbon number 1～16, the methyl polysilicone alkyl of silicon several 2～20 or the alkyl of carbon number 4～20, and the substituting group with photopolymerization initiation is trihalomethyl-s-triaizine compounds.Wherein, described exemplary compounds 9,30,31 etc. particularly preferably.
In solidification compound of the present invention, viewpoint from the character of surface of cured film, preferably as resin (A), use the base with alicyclic structure to be cyclohexyl, three cyclopentenyls or double cyclopentenyl and acidic groups are resin (the compound structure P-4 for example of carboxyl, P-6 etc.), as surface active cpd (D), derive and next base with having from trihalomethyl-s-triaizine compounds, the fluorinated alkyl of carbon number 1～16, (for example exemplary compounds 9 for the compound of the methyl polysilicone alkyl of silicon several 2～20 or the alkyl of carbon number 4～20,30,31 etc.), more preferably as resin (A), use base with alicyclic structure to be the resin of carboxyl (such as compound structure P-6 etc.) as double cyclopentenyl and acidic groups, derive and the compound of the fluorinated alkyl of the base that comes and carbon number 1～16 (such as exemplary compounds 30 etc.) with having from trihalomethyl-s-triaizine compounds as surface active cpd (D).
In solidification compound of the present invention, polymerizable compound (B) the relatively quality ratio of resin (A) ((B)/(A) than) is preferably 1.3～1.5, and more preferably 0.4～1.4, be particularly preferably 0.5～1.2.If (B)/(A) than in described preferable range, then can obtain having the optical gap material of good development, mechanical strength.
In addition, from the viewpoint of the mechanical strength of cured film, as the content of described Photoepolymerizationinitiater initiater (C), resin (A) is preferably 0.1～20 quality %, more preferably 0.5～10 quality % relatively.
In addition, from the viewpoint of the mechanical strength of cured film, as the content of described surfactivity Photoepolymerizationinitiater initiater (D), polymerizable compound (B) is preferably 0.1～10 quality %, more preferably 0.2～5 quality % relatively.
And then the quality ratio ((D)/(C) ratio) as the relatively described Photoepolymerizationinitiater initiater of described surfactivity Photoepolymerizationinitiater initiater (D) (C) is preferably 0.1～1.
-particulate-
Can in solidification compound of the present invention, further contain particulate.As described particulate, be not particularly limited, can suitably select according to purpose, for example can preferably use the filler pigment of record in (Japan) JP 2003-302639 communique [0035]～[0041].Wherein, from the viewpoint of the optical gap material that can obtain having good development, mechanical strength, preferred cataloid.
From the viewpoint of the optical gap material that can obtain having high mechanical strength, the mean grain size of described particulate is preferably 5～50nm, and more preferably 10～40nm is particularly preferably 15～30nm.
In addition, viewpoint from the optical gap material that can obtain having high mechanical strength, the quality ratio of all solids composition in the solidification compound among the relative the present invention of the content of described particulate is preferably 5～50 quality %, more preferably 10～40 quality % are particularly preferably 15～30 quality %.
[pattern formation operation]
In the present invention, exposure can further be set and be developed in the curable resin layer that forms on the supporter, thereby form the operation of pattern.Form the concrete example of operation as pattern, can preferably enumerate in the present invention such as the operation of record in paragraph numbering [0040]～[0051] of the formation example of record in paragraph numbering [0071]～[0077] of (Japan) JP 2006-64921 communique or (Japan) JP 2006-23696 communique etc.
Cured film of the present invention is owing to being to make described solidification compound solidify the film that forms, so be the good cured film of character of surface.Cured film of the present invention is after utilizing described layer formation operation formation curable resin layer, utilizes the irradiation of actinic energy ray that it is solidify to form.Except the curing of the irradiation that utilizes active energy beam, also can further utilize the curing of heating.In addition, also can utilize described formation pattern operation to form pattern.
The character of surface of cured film of the present invention is good, so the plastic yield of external force recovers good relatively, such as the formation that can preferably be applicable to optical gap material, dyed layer, protective seam etc.
Optical gap material among the present invention can contain in formation formation after the color filter of the painted sections such as the black shielding portion such as black matrix and colored pixels.
Described black shielding portion and painted and optical gap material can at random make up the coating process of coating curing composition and form with the transfer printing of the transfer materials with the photo-sensitive resin that is made of solidification compound.
Described black shielding portion and painted and described optical gap material can be formed by solidification compound respectively, particularly, for example, can form the curable resin layer by the described solidification compound of direct application of liquid on substrate, then carry out exposure imaging, described black shielding portion and painted section are formed pattern-like, then, the described solidification compound of other liquid is set at other substrates (temporary supporting body) different from described substrate, form the curable resin layer, use the curable resin transfer materials of making thus, this curable resin transfer materials and the described substrate that is formed with described black shielding portion and painted section are adhered to, then transfer printing curable resin layer carries out exposure imaging, thus the optical gap material is formed pattern-like.Carry out in this wise, can make the color filter that is provided with the optical gap material.
In addition, black shielding portion and painted section are made after the curable resin transfer materials adheres to substrate and transfer printing curable resin layer, carry out respectively exposure imaging, described black shielding portion and painted section are formed pattern-like, then the solidification compound by direct application of liquid, form the curable resin layer at the described substrate that is formed with described black shielding portion and painted section, then by exposure imaging the optical gap material is formed pattern-like.Carry out in this wise, can make the color filter that is provided with the optical gap material.
In the manufacture method of optical gap material of the present invention, viewpoint from display quality, preferably include by being formed with the described solidification compound of supporter coating of black shielding portion and painted section, thereby form the operation of curable resin layer (solidification compound layer).
＜base plate for liquid crystal display device 〉
Base plate for liquid crystal display device of the present invention is the substrate that possesses the optical gap material that the manufacture method of utilizing described optical gap material of the present invention obtains.The optical gap material preferably the demonstration that is formed at black matrix on the supporter etc. with light shielding part on or the driving element such as TFT form.In addition, also can between the demonstrations such as black matrix are with the driving elements such as light shielding part or TFT and optical gap material, there be the liquid crystal orientation films such as the transparency conducting layers (transparency electrode) such as ITO or polyimide.
For example, arrange in the situation of optical gap material with light shielding part or driving element in demonstration, in order to cover demonstration light shielding part (black matrix etc.) or the driving element that is equipped in advance on this supporter, for example the photo-sensitive resin of photosensitive resin transfer film can be laminated to and support on the dignity, peel off transfer printing, form photo-sensitive resin, then to its expose, development, heat treated etc., form the optical gap material, make thus base plate for liquid crystal display device of the present invention.
Base plate for liquid crystal display device of the present invention also can arrange the colored pixels of redness (R), blue (B), green (G) 3 looks etc. as required.
＜liquid crystal display cells 〉
Described base plate for liquid crystal display device of the present invention can be set consist of liquid crystal display cells.As one of liquid crystal display cells, can enumerate at least one party and (comprise base plate for liquid crystal display device of the present invention for a pair of supporter of photopermeability.) between possess at least liquid crystal layer and liquid crystal drive mechanism (comprises simple matrix type of drive and driven with active matrix mode.) element.
In this case, base plate for liquid crystal display device of the present invention can constitute each pixel of having a plurality of rgb pixel groups, consisting of this pixel groups each other by the colour filtering chip basic board of black matrix isolation.Owing to arrange highly at this colour filtering chip basic board and to be homogeneous and to be out of shape restorative outstanding optical gap material, generating unit spacing uneven (element thickness change) between colour filtering chip basic board and the counter substrate can be suppressed at so possess the liquid crystal display cells of this colour filtering chip basic board, the look unequal generation that shows inequality can be effectively prevented.Like this, the liquid crystal display cells of making can show distinct image.
In addition, as another mode of liquid crystal display cells, be (to comprise base plate for liquid crystal display device of the present invention at least one party for a pair of supporter of photopermeability.) between possess at least liquid crystal layer and liquid crystal drive mechanism, described liquid crystal drive mechanism has active component (for example TFT), thereby and utilizes the height homogeneous between a pair of substrate and be out of shape restorative outstanding optical gap material and be controlled to the mode that Rack consists of.
In this case, base plate for liquid crystal display device of the present invention constitutes has a plurality of rgb pixel groups, consists of each pixel of this pixel groups each other by the colour filtering chip basic board of black matrix isolation.
As the liquid crystal that can use in the present invention, can enumerate nematic liquid crystal, cholesteryl liquid crystal, disc-like liquid crystal, ferroelectric liquid crystals.
In addition, the described pixel groups of the described colour filtering chip basic board pixel groups that 2 color pixels that are different colors from one another consist of of can serving as reasons, the pixel groups that also can consist of for 3 color pixels, pixel more than 4 looks.For example, be in the situation of 3 looks, consisted of by red (R), green (G) and blue (B) 3 kinds of form and aspect.In the situation of configuration RGB3 color pixel group, preferably inlay the configurations such as type, triangular form, dispose in the situation of 4 looks above pixel groups, can be arbitrary disposition.The making of colour filtering chip basic board for example can be formed as described above black matrix after the pixel groups more than forming 2 looks, also can form pixel groups on the contrary after forming black matrix.For the formation of rgb pixel, can be with reference to (Japan) JP 2004-347831 communique etc.
＜liquid crystal indicator 〉
Liquid crystal indicator of the present invention is described base plate for liquid crystal display device to be set and the device that consists of.In addition, liquid crystal indicator of the present invention also can arrange described liquid crystal display cells and consist of.That is, as mentioned above, utilize optical gap material of the present invention, be controlled to Rack between a pair of substrate with arranged opposite toward each other, enclose liquid crystal material in the gap of having controlled (will enclose the position and be called liquid crystal layer.) consist of, the thickness (element thickness) of liquid crystal layer can be held in the homogeneous thickness that needs.
As the liquid crystal display pattern in the liquid crystal indicator, can preferably enumerate STN type, TN type, GH type, ECB type, ferroelectric liquid crystals, anti ferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, other various patterns.Wherein, in liquid crystal indicator of the present invention, from bringing into play most effectively the viewpoint of effect of the present invention, preferred easily because the change of the element thickness of liquid crystal cells shows the display mode of inequality, preferably constituting element thickness is VA type display mode, IPS type display mode, the OCB type display mode of 2～4 μ m.
Basic comprising mode as liquid crystal indicator of the present invention, can enumerate (a) arranges driving elements such as forming thin film transistor (TFT) (TFT) and pixel electrode (conductive layer) across optical gap material arranged opposite driving side substrate and the counter substrate that possesses opposite electrode (conductive layer), thereby enclose the mode that liquid crystal material consists of to its clearance portion; (b) drive substrate and the counter substrate that possesses opposite electrode (conductive layer) across optical gap material arranged opposite, thereby enclose the mode of liquid crystal material formation etc. to its clearance portion, liquid crystal indicator of the present invention can preferably be applicable to various liquid crystal display instruments.
For liquid crystal indicator, for example be described in " LCD Technology of future generation (Uchida Tatsuo compiles, and the side census of manufacturing can be issued in 1994) ".Liquid crystal indicator of the present invention except possessing liquid crystal display cells of the present invention, is not particularly limited, and for example goes for the liquid crystal indicator of the variety of way of record in described " LCD Technology of future generation ".Effective to the liquid crystal indicator that consists of colored TFT mode especially in these.Liquid crystal indicator for colored TFT mode for example is described in " color TFT-LCD display (altogether vertical publication (strain) distribution in 1996) ".
Liquid crystal indicator of the present invention can use the various members such as electrode base board, polarized light film, phase-contrast film, backlight, gap material (spacer), viewing angle compensation film, antireflective film, light diffusion film, anti-dazzle film to consist of except possessing the liquid crystal display cells of the present invention of having stated usually.For these members, for example be recorded in the market (island Itou Kentaro; (strain) シ one エ system シ one (CMC) distribution in 1994) of " ' 94 liquid crystal display peripheral material chemicalss (chemicals) ", " present situation of 2003 liquid crystal relevant markets is always ground 2003 distribution such as grade with prospect in future (last volume) (table is good lucky; (strain) Ji Meile of Fuji (キ メ ラ))) ".
[embodiment]
Below illustrate in greater detail the present invention with embodiment, but the present invention is not limited by following examples in the scope that does not exceed its main idea.In addition, so long as not concluding especially, " part " reaches " % " and is quality standard.
As the resin among the present invention (A), below show the synthesis example of the compound that is represented by compound structure P-1～P-5.
(synthesis example 1)
In reaction vessel, add in advance 1-methoxy-2-propanol (MFG, ダ イ セ Le chemical industry (strain) system) 203.9 part, under nitrogen atmosphere, be warming up to 70 ℃, be that polymerization initiator is (with the pure medicine of light company system, V-65) 9.5 parts with 12.5 parts of 2 hours instillation styrene, 76.8 parts of epihydric alcohol methylpropenoic acid esters, 66.1 parts of methacrylic acid double cyclopentenyl esters, 46.5 parts of methacrylic acids, azo.After the instillation, make its reaction 4 hours, obtain the solution (28.6% solution) of the resin that represented by compound structure P-1.
Utilize gel permeation chromatography to ask the weight-average molecular weight Mw of the described resin that is represented by compound structure P-1, the result is 31,500.
(synthesis example 2)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use methacrylic acid 2-adamantane esters, in addition, similarly carry out with synthesis example 1, obtain the solution (28.0% solution) of the resin that represented by compound structure P-2.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-2 is 28,700.
(synthesis example 3)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use IBOMA, in addition, similarly carry out with synthesis example 1, obtain the solution (28.6% solution) of the resin that represented by compound structure P-3.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-3 is 34,200.
(synthesis example 4)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use methacrylic acid three cyclopentenyl esters, in addition, similarly carry out with synthesis example 1, obtain the solution (28.2% solution) of the resin that represented by compound structure P-4.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-4 is 30,700.
(synthesis example 5)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use cyclohexyl methacrylate, in addition, similarly carry out with synthesis example 1, obtain the solution (28.6% solution) of the resin that represented by compound structure P-5.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-6 is 28,100.
(synthesis example 6)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use methacrylic acid double cyclopentenyl oxygen ethyl ester (Hitachi changes into the Off ア Application Network リ Le FA-512M of industry (strain) system), in addition, similarly carry out with synthesis example 1, obtain the solution (28.2% solution) of the resin that represented by compound structure P-6.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-6 is 29,800.
(synthesis example 7)
In synthesis example 1, replace the methacrylic acid double cyclopentenyl ester, use methacrylic acid three cyclopentenyl oxygen ethyl esters (Hitachi changes into the TCPD-M of industry (strain) system), in addition, similarly carry out with synthesis example 1, obtain the solution (28.5% solution) of the resin that represented by compound structure P-7.
The weight-average molecular weight Mw of the described resin that is represented by compound structure P-7 is 31,800.
The making of-colour filtering chip basic board-
Utilize the method for putting down in writing in paragraph numbering [0084]～[0095] of JP 2005-3861 communique, make the color filter with black matrix, R pixel, G pixel, B pixel.Then, on the R of colour filtering chip basic board pixel, G pixel and B pixel and black matrix, utilize sputter further to form the transparency electrode of ITO (indium tin oxide (Indium Tin Oxide)).
(embodiment 1)
Be formed with in the sputter of above-mentioned middle making on the ITO film of colour filtering chip basic board of ITO film, utilization has the glass substrate of slot-shaped nozzle with coating machine (coater) MH-1600 (FAS Asian company system), applies the curable resin layer coating liquid that is made of the prescription 5 shown in the following table 1.Then, with vacuum drier VCD (Tokyo Ying Hua company system), the part of dry solvent 30 seconds, the flowability of coated film is disappeared, then 120 ℃ of lower prebake (prebake) 3 minutes, obtain the curable resin layer (layer forms operation) of thickness 3.8 μ m.
Then, with the プ ロ キ シ ミ テ イ one type exposure machine (Hitachi's Ha イ テ Network electronic engineering (strain) system) with ultrahigh pressure mercury lamp, under the vertical state that erects in colour filtering chip basic board almost parallel ground that makes mask (the quartzy exposed mask with picture pattern) and this mask and curable resin layer are relatively disposed, distance between the plane of exposure of setting mask and curable resin layer is 40 μ m, across mask, from curable resin layer side, with exposure 300mJ/cm
2Carry out close induction type (プ ロ キ シ ミ テ イ one) exposure.
Then, using sodium carbonate is developer solution (sodium bicarbonate, the sodium carbonate of 0.47 mol/L, the nekal of 5 quality %, anionic surfactant, defoamer, the stabilizing agent that contain 0.38 mol/L with 10 times of dilutions of pure water; The liquid that trade name: T-CD1 (Fujiphoto (strain) system) forms), under 29 ℃, pyramid type nozzle pressure 0.15MPa, to spray development 30 seconds, form the pattern image of optical gap material.
Then, with pure water washing agent (is contained phosphate, silicate, non-ionic surfactant, defoamer, stabilizing agent, trade name: T-SD3 (Fujiphoto (strain) system)) is diluted to 10 times, use the liquid of gained, under 33 ℃, pyramid type nozzle pressure 0.02MPa, blow with spray with 20 seconds kinds, remove the residue of the pattern image periphery of formation, form the spacer pattern that needs.
Then, be provided with the colour filtering chip basic board 30 minutes (heat treatment step) of optical gap material 230 ℃ of lower heat treated, make thus the optical gap material.
The optical gap material that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.In addition, to 1000 optical gap materials that obtain, use three-dimensional surface structure analysis microscope (manufacturing plant: ZYGO Corporation, pattern: New View 5022), mensuration forms the extreme higher position (n=20) of the highest optical gap material of face from ito transparent electrode, thereby draws average height.
The making of＜liquid crystal indicator 〉
In addition, prepare again glass substrate as counter substrate, form with pattern on the transparency electrode of colour filtering chip basic board obtained above and counter substrate, implementing respectively the PVA pattern, the alignment films that polyimide consists of further is set thereon.
Then, the position of the housing of the black matrix that arranges around in the mode of the pixel groups of surrounding color filter, utilize dispenser (dispenser) mode, the sealant of coating ultraviolet curable resin, instillation PVA pattern liquid crystal, itself and counter substrate are fitted after, carry out the UV irradiation to the substrate of having fitted, then heat-treat, make sealant cures.On the two sides of the liquid crystal cells that obtains like this, stick the polarization plates HLC2-2518 of (strain) three vertical magnetic (サ Application リ Star Star) systems.
Then, use FR1112H (chip (chip) the type LED of Stanley's (ス タ Application レ one) electric (strain) system) as red (R) LED, use DG1112H (chip-type LED of Stanley's electric (strain) system) as green (G) LED, use DB1112H (chip-type LED of Stanley's electric (strain) system) as blue (B) LED, consist of the backlight (back light) of side lamp mode, be configured in a side that becomes the back side of the liquid crystal cells that is provided with above-mentioned polarization plates, as liquid crystal indicator.
(embodiment 2～embodiment 4, embodiment 7～embodiment 11, comparative example 2～comparative example 4, comparative example 6, comparative example 7)
In embodiment 1, replace the curable resin layer coating liquid of prescription 5, use respectively the prescription shown in following table 1-1 and the table 1-2, in addition, carry out similarly to Example 1, make the colour filtering chip basic board that is provided with the optical gap material.The gap material pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
Then, the colour filtering chip basic board that replacement obtains in embodiment 1 uses respectively the colour filtering chip basic board that obtains in above-mentioned, in addition, carries out similarly to Example 1, makes liquid crystal indicator.
(embodiment 5)
In embodiment 1, replace the curable resin layer coating liquid of prescription 5, use the prescription 8 shown in the following table 1, with exposure 300mJ/cm
2Be altered to 100mJ/cm
2, in addition, carry out similarly to Example 1, make and be provided with the colour filtering chip basic board of optical gap material, and use it to make liquid crystal indicator.The gap material pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
(embodiment 6)
In embodiment 1, with exposure 300mJ/cm
2Be altered to 100mJ/cm
2, in addition, carry out similarly to Example 1, make and be provided with the colour filtering chip basic board of optical gap material, and use it to make liquid crystal indicator.The gap material pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
(comparative example 1)
In embodiment 1, replace the curable resin layer coating liquid of prescription 5, use the prescription 1 shown in the following table 1, with exposure 300mJ/cm
2Be altered to 100mJ/cm
2, in addition, carry out similarly to Example 1, make and be provided with the colour filtering chip basic board of optical gap material, and use it to make liquid crystal indicator.The gap material pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
(comparative example 5)
In embodiment 1, replace the curable resin layer coating liquid of prescription 5, use the prescription 4 shown in the following table 1, with exposure 300mJ/cm
2Be altered to 100mJ/cm
2, in addition, carry out similarly to Example 1, make and be provided with the colour filtering chip basic board of optical gap material, and use it to make liquid crystal indicator.The gap material pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
Table 1-1
Unit: weight portion
Table 1-2
| Prescription-11 | Prescription-12 | Prescription side-13 | Prescription-14 | Prescription-15 | |
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
| 1-methoxyl-2-propyl-acetic acid ester | 26 | 26 | 26 | 26 | 26 |
| Methyl ethyl ketone | 28 | 28 | 28 | 28 | 28 |
| ソ Le ス パ one ス 2000 | 0.42 | 0.42 | 0.42 | 0.42 | 0.42 |
| DPHA liquid (erythrite six acrylate: 76 parts, 1-methoxyl-2-propyl-acetic acid ester: 24 parts) | 11.7 | 11.7 | 11.7 | 11.7 | 11.7 |
| The 28.2%1-methoxy-2-propanol solution of resin (P-6) | 25.5 | 0 | 0 | 0 | 0 |
| The 28.5%1-methoxy-2-propanol solution of resin (P-7) | 0 | 25.5 | 0 | 0 | 0 |
| The 28.0%1-methoxy-2-propanol solution of resin (P-2) | 0 | 0 | 25.5 | 0 | 0 |
| The 28.6%1-methoxy-2-propanol solution of resin (P-3) | 0 | 0 | 0 | 25.5 | 0 |
| The 28.2%1-methoxy-2-propanol solution of resin (P-4) | 0 | 0 | 0 | 0 | 25.5 |
| Two (the trichloromethyl)-6-[4-(N, N-diethoxy carbonyl methylamino) of 2,4--3-bromophenyl]-the s-triazine | 0.227 | 0.227 | 0.227 | 0.227 | 0.227 |
| Surface living initiator agent (exemplary compounds 31) | 0.114 | 0.114 | |||
| Surface living initiator agent (exemplary compounds 38) | 0.114 | 0 | 0 | 0 | 0 |
| Surface living initiator agent (exemplary compounds 40) | 0 | 0.114 | 0 | 0 | 0 |
| Surface living initiator agent (exemplary compounds 44) | 0 | 0 | 0.114 | 0 | 0 |
| The quinhydrones monomethyl ether | 0.0036 | 0.0036 | 0.0036 | 0.0036 | 0.0036 |
| Surfactant 1 (メ ガ Off ア Star Network F-780-F, large Japanese ink (イ Application キ) chemical industry Co., Ltd. system) | 0.032 | 0.032 | 0.032 | 0.032 | 0.032 |
Unit: weight portion
[evaluation]
To at optical gap material obtained above and liquid crystal indicator, carry out following evaluation.The result of evaluation of measuring is as shown in table 2.
-Recovery-
To the optical gap material that obtains, utilize respectively micro-hardness tester (DUH-W201, (strain) Shimadzu Seisakusho Ltd. system), followingly measure above-mentionedly, estimate.Measure to adopt the frustum of a cone pressure head of 50 μ m Ф, peak load is 50mN, and the retention time is 5 seconds, utilizes load-carry out except carrying a test method(s).From this measured value, utilize following formula, try to achieve Recovery [%], according to following standard, estimate.Mensuration is carried out under 22 ± 1 ℃, 50%RH environment.
(formula) Recovery (%)=
(increasing the weight of the deflection [μ m] of the amount of recovery [μ m]/when increasing the weight of after open) * 100
＜evaluation criterion 〉
5: Recovery is more than 90%.
4: Recovery is more than 87%, less than 90%.
3: Recovery is more than 85%, less than 87%.
2: Recovery is more than 80%, less than 85%.
1: Recovery is more than 75%, less than 80%.
0: Recovery is less than 75%.
-development-
In above-mentioned " making of optical gap material-", carry out after the exposure of プ ロ キ シ ミ テ イ one type, develop with the method identical with the development conditions of each embodiment, the SEM of the optical gap material peripheral part that forms observes, and confirms at periphery residual residue whether.
＜evaluation criterion 〉
5: have no residue fully.
4: at the visible some residues of pattern periphery.
3: in pattern periphery visible residue.
2: visible residue near the substrate pattern periphery and the pattern.
1: on substrate, can confirm residue everywhere.
-lamination adaptability＜lamination bubble〉estimate-
Use the curable resin transfer materials at colour filtering chip basic board, under the state with the transfer printing of curable resin layer, after peeling off the temporary supporting body, utilize optical microscope, observe laminated state, observe having or not of lamination bubble.
＜evaluation criterion 〉
3: do not have the lamination bubble fully.
2: sentence the outer lamination bubble that occured in pattern formation.
1: in the pattern forming portion lamination bubble has occured.
-net-
Placed 24 hours under 45 ℃/75%RH environment, the surface of then using microscopic examination curable resin transfer materials according to following standard, utilizes visual the evaluation.
＜evaluation criterion 〉
4: have no the generation of thin " wrinkle " etc. fully.
3: although the generation of slightly visible thin " wrinkle " etc. be the practical operable degree that.
2: the generation of less visible thin " wrinkle " etc.
1: the generation on quite a lot of ground visible thin " wrinkle " etc.
-demonstration inequality-
To liquid crystal indicator, utilize ash visual and that magnifier is observed when inputting grey test signal to show respectively, show having or not of uneven generation according to following evaluation criterion evaluation.
＜evaluation criterion 〉
1: it is uneven to have no demonstration fully.
2: the slightly visible inequality that shows.
3: the significantly visible inequality that shows.
Table 2
As known from Table 2, the optical gap material of making of solidification compound of the present invention demonstrates high Recovery.And then, even making in the situation of optical gap material with low exposure, demonstrate similarly high Recovery, so supposition has alleviated from the effect of oxygen on the surface of curable resin layer, promoted the effective polymerization of curable resin layer integral body.
Claims (7)
1. solidification compound, wherein,
At least comprise:
Resin, it contains the ester ring type alkyl of 5～25 of carbon numbers, the base that has the base of acidic groups and have epoxy radicals;
Polymerizable compound;
Photoepolymerizationinitiater initiater; With
The surfactivity Photoepolymerizationinitiater initiater;
Described surfactivity Photoepolymerizationinitiater initiater contains in same molecule and has the substituent at least a of surface activation and have the substituent at least a of photopolymerization initiation,
Described substituting group with surface activation be from can substituted carbon number more than 3 and below 30 alkyl, can substituted following general formula (3) expression siloxy group and can the fluorinated alkyl of substituted following general formula (4) expression select at least a
General formula (3)
In the formula, R
31The alkyl of expression hydrogen atom, carbon number 1～8 or-OR
33, R
32The alkyl of expression hydrogen atom, carbon number 1～8 or-OR
34, R
33And R
34The alkyl that represents independently respectively carbon number 1～8,
General formula (4)
——(CH
2)
i-L
4-C
jF
2j+1
In the formula, L
4Expression oxygen atom or singly-bound, i represents 0～8 integer, j represents 1～12 integer,
Described carbon number is alkyl, the alkoxy of carbon number 1～8, halogen radical, amino, the cyano group of carbon number 1～8 more than 3 and the substituting group that has of 30 following alkyl,
The substituting group that described siloxy group has is alkyl, the alkoxy of carbon number 1～8, halogen radical, amino, the cyano group of carbon number 1～8,
The substituting group that described fluorinated alkyl has is alkyl, the alkoxy of carbon number 1～8, halogen radical, amino, the cyano group of carbon number 1～8.
2. solidification compound according to claim 1, wherein,
Described resin contains the base of the ester ring type alkyl of 5～25 of the alkyl of the chain with 3～12 of carbon numbers and carbon numbers, the base that has the base of acidic groups and have epoxy radicals.
3. according to claim 1 or 2 described solidification compounds, wherein,
Described ester ring type alkyl is to derive from carbon number more than 6 and the base of 25 following ring compounds.
4. cured film, it is to make each the described solidification compound in the claim 1～3 solidify the cured film that forms.
5. the manufacture method of an optical gap material, wherein,
Have:
Form the operation of solidification compound layer at supporter by each the described solidification compound in the coating claim 1～3.
6. base plate for liquid crystal display device, wherein,
Possesses the optical gap material that the manufacture method manufacturing that utilizes optical gap material claimed in claim 5 forms.
7. liquid crystal indicator, wherein,
Possesses base plate for liquid crystal display device claimed in claim 6.
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| JP2007-201754 | 2007-08-02 | ||
| JP2007201754 | 2007-08-02 | ||
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| JP (1) | JP5207837B2 (en) |
| KR (1) | KR20090013685A (en) |
| CN (1) | CN101359176B (en) |
| TW (1) | TW200918594A (en) |
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| JP5432456B2 (en) * | 2008-01-23 | 2014-03-05 | 出光興産株式会社 | Adamantane copolymer resin, resin composition and use thereof |
| JP5340198B2 (en) * | 2009-02-26 | 2013-11-13 | 富士フイルム株式会社 | Dispersion composition |
| JP5220664B2 (en) * | 2009-03-17 | 2013-06-26 | 富士フイルム株式会社 | Ink composition and inkjet recording method |
| JP5437027B2 (en) * | 2009-03-31 | 2014-03-12 | 東京応化工業株式会社 | Photosensitive resin composition and liquid crystal panel |
| JP2010282180A (en) * | 2009-05-08 | 2010-12-16 | Fujifilm Corp | Radiation-sensitive resin composition for forming spacer, spacer, method for forming spacer, and liquid crystal display element |
| KR101618897B1 (en) * | 2010-01-20 | 2016-05-09 | 후지필름 가부시키가이샤 | Process for producing cured film, photosensitive resin composition, cured film, organic electro-luminescence display and liquid crystal display |
| TWI510860B (en) * | 2010-09-01 | 2015-12-01 | Sumitomo Chemical Co | Photosensitive resin composition |
| JP5978583B2 (en) * | 2011-10-04 | 2016-08-24 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP5834327B2 (en) * | 2012-01-16 | 2015-12-16 | 東洋インキＳｃホールディングス株式会社 | Light scattering resin composition, light scattering layer formed from the light scattering resin composition, and organic EL display device or organic EL lighting device including the light scattering layer |
| WO2014038576A1 (en) | 2012-09-05 | 2014-03-13 | 株式会社日本触媒 | Photosensitive resin composition for photo spacer, and photo spacer |
| JP6640007B2 (en) * | 2016-04-13 | 2020-02-05 | Ｄｉｃグラフィックス株式会社 | Varnish for printing ink, printing ink, and printed matter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147868A (en) * | 1995-03-13 | 1997-04-16 | 互応化学工业株式会社 | Photosensitive resin composition, and coating film, resist ink, resist protective film solder protective resist film and substrate of printed circuit |
| CN1991584A (en) * | 2005-12-28 | 2007-07-04 | 富士胶片电子材料有限公司 | Light solidification pigmentation composition and color filter, and liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05281747A (en) * | 1992-04-03 | 1993-10-29 | Fuji Photo Film Co Ltd | Photosensitive transfer sheet |
| US6376568B1 (en) * | 1999-07-29 | 2002-04-23 | Ciba Specialty Chemicals Corporation | Surface-active photoinitiators |
| SG97168A1 (en) * | 1999-12-15 | 2003-07-18 | Ciba Sc Holding Ag | Photosensitive resin composition |
| WO2002040602A1 (en) * | 2000-11-20 | 2002-05-23 | Ciba Specialty Chemicals Holding Inc. | Fluorinated-photoinitiators in dual cure resins |
| AU2002234551A1 (en) * | 2000-12-13 | 2002-06-24 | Ciba Specialty Chemicals Holding Inc. | Surface-active photoinitiators |
| JP2005121940A (en) * | 2003-10-17 | 2005-05-12 | Toyo Ink Mfg Co Ltd | Polymerizable composition, negative resist using same, and method for forming image pattern by using the resist |
| JP4380359B2 (en) * | 2004-02-20 | 2009-12-09 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition for spacer formation, spacer, method for forming the spacer, and liquid crystal display element |
| JP4678271B2 (en) * | 2005-09-26 | 2011-04-27 | Ｊｓｒ株式会社 | Photosensitive resin composition, protective film for liquid crystal display panel and spacer, and liquid crystal display panel comprising them |
| JP2007171767A (en) * | 2005-12-26 | 2007-07-05 | Chisso Corp | Photosetting polymer composition and display element using the same |
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2008
- 2008-06-11 JP JP2008153208A patent/JP5207837B2/en active Active
- 2008-07-16 KR KR1020080069280A patent/KR20090013685A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147868A (en) * | 1995-03-13 | 1997-04-16 | 互応化学工业株式会社 | Photosensitive resin composition, and coating film, resist ink, resist protective film solder protective resist film and substrate of printed circuit |
| CN1991584A (en) * | 2005-12-28 | 2007-07-04 | 富士胶片电子材料有限公司 | Light solidification pigmentation composition and color filter, and liquid crystal display device |
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| CN101359176A (en) | 2009-02-04 |
| JP2009053663A (en) | 2009-03-12 |
| JP5207837B2 (en) | 2013-06-12 |
| KR20090013685A (en) | 2009-02-05 |
| TW200918594A (en) | 2009-05-01 |
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