CN101114124A - Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device - Google Patents
Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device Download PDFInfo
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- CN101114124A CN101114124A CNA2007101363905A CN200710136390A CN101114124A CN 101114124 A CN101114124 A CN 101114124A CN A2007101363905 A CNA2007101363905 A CN A2007101363905A CN 200710136390 A CN200710136390 A CN 200710136390A CN 101114124 A CN101114124 A CN 101114124A
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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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
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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
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Liquid Crystal (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a photosensitive composition, a photosensitive resin transfer film comprising the photosensitive composition, a method for making the photosensitive partition column using the material, a liquid crystal display device substrate comprising the photosensitive partition column, and a liquid crystal display device comprising the liquid crystal display device, the photosensitive composition at least includes the resin (A), the polymerized compound (B), and the photopolymerization initiating agent (C), the resin (A) includes the group which comprises branched chain and/or alicyclic structure at the side chain, the group which comprises acidic groups at the side chain, and the group which comprises the ethylenically unsaturated groups at the side chain. According to the invention a photosensitive composition which has a high deformation recovery character and can eliminate the display nonuniformity in the liquid crystal display device and the photosensitive resin transfer film, the method for making the photosensitive partition column using the material, the liquid crystal display device substrate which prevents the display nonuniformity and can do high-image quality display, and the liquid crystal display device are provided.
Description
Technical field
The present invention relates to the manufacture method of a kind of photosensitive composite, photosensitive resin transfer film and photonasty spacer (photo spacer) and have the liquid crystal indicator that utilizes the photonasty spacer that this method makes with substrate and liquid crystal indicator, described photosensitive composite is applicable to makes the chock insulator matter that constitutes display device, and this display device shows inhomogeneous because of the thick change of the box of liquid crystal cell easily.
Background technology
At present, liquid crystal indicator is widely used in the display device that shows high resolution image.Liquid crystal indicator disposes the orientation that can utilize regulation usually and carries out the liquid crystal layer that image shows between a pair of substrate, keep equably this substrate at interval, be that the thickness of liquid crystal layer is one of key element of decision image quality.Therefore, set the thickness that is used for liquid crystal layer usually and keep constant chock insulator matter.Thickness between this substrate is commonly referred to as " box is thick ".The thickness of the thick ordinary representation foregoing liquid crystal of box layer, in other words, expression applies the distance between 2 plate electrodes of electric field to the liquid crystal of viewing area.
Form chock insulator matter by scattering beaded glass at present, but in recent years, utilize the photoetching process of using photosensitive composite, can form the high chock insulator matter of positional precision.The chock insulator matter that uses this photosensitive composite to form is called as the photonasty spacer.
Use photosensitive composite, through the photonasty spacer that pattern forms, alkali develops and baking is made, a little less than the compression strenght in its each spacer site, when forming panel, the tendency that exists plastic yield to increase.In images with high image quality shows, require not take place to diminish to wait than design load to keep homogeneity, the inhomogeneous this problem of generation image by the thickness that above-mentioned reason causes because of liquid crystal layer.In addition, aspect the high precision int of liquid crystal indicator, the alkali development residue that does not produce photosensitive composite also is important.
With respect to the problems referred to above, keep constant chock insulator matter formation technology as the thickness that is used to make liquid crystal layer (box is thick), the method (for example, opening the 2003-207787 communique with reference to the spy) that will have allylic resin and be used to form chock insulator matter is disclosed.
In addition, disclose a kind of be easy to make and photonasty spacer that storage-stable is good with photosensitive composite (for example, please refer to the spy and open the 2005-62620 communique).
And, the good composition of a kind of cold-resistant thermal shock (for example, please refer to the spy and open the 2002-287354 communique) is also disclosed.
Summary of the invention
Originally, to being used for the photonasty spacer of liquid crystal cell, it was restorative to require it to have a high distortion.In order to satisfy this requirement, by cross-linking reaction rates such as raising monomers, can improve the distortion recovery rate to a certain extent, still, it improves effect and has the tendency that reaches capacity, and needs further to improve.
The present invention In view of the foregoing finishes, its purpose is, provide the distortion with height restorative and can eliminate the uneven photosensitive composite of demonstration, photosensitive resin transfer film in the liquid crystal indicator, use the manufacture method and can preventing of the photonasty spacer of these materials show inhomogeneous, can carry out liquid crystal indicator that high resolution image shows with substrate and liquid crystal indicator, and to finish this purpose as problem.
The present invention obtains following understanding and finishes based on described understanding, promptly, when use contains the resin of the group that has the olefinic unsaturated group on the group that has acidic groups on the group that has side chain and/or alicyclic structure on the side chain, the side chain and the side chain, its distortion is restorative to improve greatly, and effective especially to showing uneven improvement.
The concrete way that is used to finish aforementioned problems is as described below.
(1) a kind of photosensitive composite, it is characterized in that, at least comprise resin (A), polymerizable compound (B), Photoepolymerizationinitiater initiater (C), described resin (A) contains the group that has the olefinic unsaturated group on the group that has acidic groups on the group that has side chain and/or alicyclic structure on the side chain, the side chain and the side chain.
As (1) described photosensitive composite, it is characterized in that (2) glass transition temperature (Tg) of aforementioned resin (A) is that 40～180 ℃ and weight-average molecular weight are 10,000～100,000.
As (1) or (2) described photosensitive composite, it is characterized in that (3) aforementioned polymerizable compound (B) is 0.5～2 with respect to the quality ratio ((B)/(A)) of resin (A).
As each described photosensitive composite in (1) to (3), it is characterized in that (4) it also comprises particulate (D).
As (4) described photosensitive composite, it is characterized in that (5) mean grain size of aforementioned particulate (D) is 5～50nm and this particulate (D) with respect to the quality ratio of the total solid composition in (4) described photosensitive composite is 5～50 quality %.
As (4) or (5) described photosensitive composite, it is characterized in that (6) aforementioned particulate (D) is a cataloid.
(7) a kind of photosensitive resin transfer film, it has photo-sensitive resin at least on interim stilt, it is characterized in that, and this photo-sensitive resin uses each described photosensitive composite in (1) to (6) and forms.
(8) as (7) described photosensitive resin transfer film, it is characterized in that, between aforementioned photo-sensitive resin and aforementioned interim stilt, be provided with oxygen barrier layers and/or thermoplastic resin.
(9) a kind of manufacture method of photonasty spacer is characterized in that, it has following operation: use as each described photosensitive composite in (1) to (6) to apply, form photo-sensitive resin thus on stilt.
(10) a kind of manufacture method of photonasty spacer, it is characterized in that, it has following operation: use (7) or (8) described photosensitive resin transfer film, come the transfer printing photo-sensitive resin by heating and/or pressurization, form photo-sensitive resin thus on stilt.
(11) a kind of liquid crystal indicator substrate is characterized in that, the photonasty spacer that its manufacture method manufacturing with utilization (9) or (10) described photonasty spacer forms.
(12) a kind of liquid crystal indicator is characterized in that, it has (11) described liquid crystal indicator substrate.
The effect of invention
According to the present invention, can provide the distortion with height restorative and can eliminate the uneven photosensitive composite of demonstration, the photosensitive resin transfer film in the liquid crystal indicator and use the manufacture method and can preventing of the photonasty spacer of these materials show inhomogeneous, can carry out liquid crystal indicator that high resolution image shows with substrate and liquid crystal indicator.
Embodiment
Below, manufacture method, the liquid crystal indicator of photosensitive composite of the present invention, photonasty insulated column at length described with substrate and liquid crystal indicator.
The manufacture method of＜photosensitive composite and photonasty spacer 〉
Photosensitive composite of the present invention comprises resin (A), polymerizable compound (B), Photoepolymerizationinitiater initiater (C) at least, and described resin (A) contains the group that has the olefinic unsaturated group on the group that has acidic groups on the group that has side chain and/or alicyclic structure on the side chain, the side chain and the side chain.The distortion that has height owing to the photonasty spacer that utilizes photosensitive composite manufacturing of the present invention is restorative, so the demonstration that can eliminate in the display device is inhomogeneous.
In addition, the manufacture method of photonasty spacer of the present invention is to make the method for the aforementioned photonasty spacer in the liquid crystal indicator, described liquid crystal indicator possesses 2 stilts at least, be arranged on liquid crystal between the aforementioned stilt, foregoing liquid crystal is applied 2 plate electrodes of electric field and is used to set the thick photonasty spacer of box between the aforementioned stilt, and the manufacture method of described photonasty spacer is included in the layer that forms the photo-sensitive resin that contains photosensitive composite of the present invention on a slices of aforementioned 2 stilts and forms operation.
According to the manufacture method of photonasty spacer of the present invention, can easily make the restorative photonasty spacer of distortion with height.
Below, the manufacture method of photonasty spacer of the present invention is described, by this explanation the details of photosensitive composite of the present invention is also narrated.
[layer forms operation]
Layer among the present invention forms operation and is meant the operation that forms the photo-sensitive resin that contains photosensitive composite of the present invention (below, also abbreviate " photosensitive polymer combination layer " as) on stilt.
This photo-sensitive resin is through manufacturing process described later, and it is restorative good and can keep the thick photonasty spacer of box equably to constitute distortion.By using this photonasty spacer, especially can eliminate the image that takes place easily in the uneven display device of demonstration because of the thick change of box effectively and show inhomogeneous.
For the method that on stilt, forms photo-sensitive resin, can suitably enumerate: (a) utilize method that solution that known coating process will contain photosensitive composite of the present invention applies, and (b) utilize and use the transfer printing of photosensitive resin transfer film to carry out stacked method.Below, the whole bag of tricks is narrated.
(a) coating process
Can utilize known coating process to carry out the coating of photosensitive composite, for example: spin-coating method, curtain coating method, slit coating method, dip coating method, air knife coating process, rolling method, metal thread bar are coated with the extrusion coating method of method, photogravure coating process or No. 2681294 described use funnel of instructions of United States Patent (USP) etc.Wherein, preferred spy opens 2004-89851 communique, spy and opens 2004-17043 communique, spy and open 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 opens the described methods of utilizing gap nozzle or slit coating machine to apply such as 2001-310147 communique.
(b) transfer printing
When utilizing transfer printing, use the photosensitive resin transfer film on interim stilt, to form membranaceous photo-sensitive resin, and the roller by heating and/or pressurization or flat board carry out crimping or add thermo-compressed sticking on and supporting on the object plane, then, peel off interim stilt, make the transfer printing of photosensitive polymer combination layer on stilt.As an example, specifically can exemplify: the spy opens flat 7-110575 communique, spy and opens that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens described stacked machine of 2002-148794 communique and laminating method.Consider from the viewpoint of low impurity, preferably use the spy to open the described method of flat 7-110575 communique.
When forming photo-sensitive resin, can between photo-sensitive resin and interim stilt, further be provided with oxygen barrier layers (below, be also referred to as " oxygen screened film " or " middle layer ".)。Can improve exposure sensitivity thus.In addition, in order to improve transfer printing, the thermoplastic resin with resiliency can be set.
Manufacture method for the interim stilt, oxygen barrier layers, thermoplastic resin, other layer and this photosensitive transfer film that constitute this photosensitive transfer film can exemplify paragraph sequence number [0024]～[0030] described formation, method for making that the spy opens the 2006-23696 communique.
When utilizing (a) coating process, (b) transfer printing coating formation photo-sensitive resin, all preferred 0.5～10.0 μ m of its bed thickness, more preferably 1～6 μ m.When bed thickness is in aforementioned range, can in manufacture process, prevent to apply the generation of the pin hole when forming, the development that can not need long-time (that is, at short notice) just can carry out unexposed portion is removed.
The stilt that forms photo-sensitive resin for example has: the substrate (being also referred to as the color filter substrate) of the substrate of transparent substrates (for example glass substrate or plastic), band nesa coating (for example ITO film), band color filter, the driving substrate of band driving element (for example thin film transistor (TFT) [TFT]) etc.The thickness of stilt generally is preferably 700～1200 μ m.
～photosensitive composite～
Below, photosensitive composite is described.
Photosensitive composite comprises at least: contain the resin (A) that has the group of olefinic unsaturated group on the group that has acidic groups on the group that has side chain and/or alicyclic structure on the side chain, the side chain and the side chain (below, also abbreviate " resin (A) " as), polymerizable compound (B), Photoepolymerizationinitiater initiater (C).In addition, as required, can also use other constituents such as colorant and surfactant.
Aforementioned photosensitive composite is particularly preferred for the photonasty spacer and uses.
-resin (A)-
The group Z (z mole %) that resin (A) contains the radicals X (x mole %) that has side chain and/or alicyclic structure on the side chain, the group Y (y mole %) with acidic groups and has the olefinic unsaturated group.As required, can also have other group (L) (1 mole of %).In addition, a plurality of X, Y and Z can be combined in the group in resin (A).
The group that has side chain and/or alicyclic structure on-the side chain: X-
Aforementioned " group that has side chain and/or alicyclic structure on the side chain " described.
At first, group with side chain can exemplify the alkyl that carbon number is a chain of 3～12, for example has: isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl (isopentyl), neopentyl, 2-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 etc., further preferred isopropyl, sec-butyl, the tert-butyl group.
It is 5～20 ester ring type alkyl that the group that has alicyclic structure on the side chain can exemplify carbon number, for example has: cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, adamantyl, three ring decyls etc.Wherein, preferred cyclohexyl, norborny, isobornyl, adamantyl, three ring decyls etc., further preferred cyclohexyl, norborny, isobornyl etc.
Containing the monomer that has the group of side chain and/or alicyclic structure on the aforementioned side chain for example has: phenylethylene, (methyl) esters of acrylic acid, vinyl ethers, vinyl ester, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl ester, (methyl) acrylic amide, further preferred (methyl) esters of acrylic acid.
Contain the monomer that has the group of branched structure on the aforementioned side chain, concrete example is if any (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-isopentyl ester, (methyl) acrylic acid 2-monooctyl ester, (methyl) acrylic acid 3-monooctyl ester, (methyl) acrylic acid uncle monooctyl ester etc., wherein, preferred (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, metering system tert-butyl acrylate etc., further preferable methyl isopropyl acrylate, metering system tert-butyl acrylate etc.
Secondly, containing the concrete example of the monomer of the group that has alicyclic structure on the aforementioned side chain, is to have (methyl) acrylate that carbon number is 5～20 an ester ring type alkyl.Concrete example is if any: (methyl) acrylic acid (dicyclo [2.2.1] heptan-2-ester), (methyl) acrylic acid-1-diamantane ester, (methyl) acrylic acid-2-diamantane ester, (methyl) acrylic acid-3-methyl isophthalic acid-diamantane ester, (methyl) acrylic acid-3,5-dimethyl-1-diamantane ester, (methyl) acrylic acid-3-ethyl diamantane ester, (methyl) acrylic acid-3-methyl-5-ethyl-1-diamantane ester, (methyl) acrylic acid-3,5,8-triethyl-1-diamantane ester, (methyl) acrylic acid-3,5-dimethyl-8-ethyl-1-diamantane ester, (methyl) acrylic acid-2-methyl-2-diamantane ester, (methyl) acrylic acid-2-ethyl-2-diamantane ester, (methyl) acrylic acid-3-hydroxyl-1-diamantane ester, (methyl) acrylic acid octahydro-4,7-
Support indenes-5-ester, (methyl) acrylic acid octahydro-4,7-
Support indenes-1-base methyl esters, (methyl) acrylic acid-1-
Ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (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) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid turnip ester, (methyl) acrylic acid-2,2,5-3-methyl cyclohexanol ester, (methyl) cyclohexyl acrylate etc.In these (methyl) acrylate, preferred (methyl) cyclohexyl acrylate, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid-1-diamantane ester, (methyl) acrylic acid-2-diamantane ester, (methyl) acrylic acid-2-methyl-2-diamantane ester, (methyl) acrylic acid-2-ethyl-2-diamantane ester, (methyl) acrylic acid-3-hydroxyl-1-diamantane ester, (methyl) acrylic acid turnip ester, (methyl) acrylic acid-1-
Ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems etc., preferred especially (methyl) cyclohexyl acrylate, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-diamantane ester.
In addition, contain the concrete example of the monomer of the group that has alicyclic structure on the aforementioned side chain, can exemplify the compound of following general formula (1) or (2) expression.Wherein, in general formula (1), (2), x represents 1 or 2, and R represents hydrogen or methyl.The independent respectively expression 0～15 of m and n.In general formula (1), (2), preferred x=1 or 2, m=0～8, n=0～4, preferred especially m=1～4, n=0～2.The preference of the compound of general formula (1) or (2) expression can exemplify following Compound D-1～D-5, T-1～T-8.
General formula (1)
The monomer that contains the group that has alicyclic structure on the aforementioned side chain both can use the monomer that obtains by the proper method manufacturing, also can use commercially available product.
Aforementioned commercially available product for example has Hitachi to change into that industry (strain) makes: 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 preferred FA-512A (S), 512M, its developing performance is good, the distortion recovery rate is good.
The group that has acidic groups on the-side chain: Y-
Aforementioned acidic groups is not particularly limited, can from known acidic groups, suitably selects, for example have: carboxyl, sulfonic group, sulfoamido, phosphate, phenol hydroxyl etc.Wherein, consider preferred carboxyl, phenol hydroxyl from the water tolerance aspect of good development and cured film.
The monomer that has the group of acidic groups on the aforementioned side chain is not particularly limited, for example have: phenylethylene, (methyl) esters of acrylic acid, vinyl ethers, vinyl ester, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl ester, (methyl) acrylic amide, further preferred (methyl) esters of acrylic acid.
The concrete example of monomer that has the group of acidic groups on the aforementioned side chain, can from known material, suitably select, for example have: the addition reaction of (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, monomer and cyclic acid anhydride, ω-carboxyl-polycaprolactone one (methyl) acrylate etc. with hydroxyl.These materials that can use suitable manufacturing to form also can use commercially available product.
Be used for the monomer with hydroxyl of the addition reaction of aforementioned monomer with hydroxyl and cyclic acid anhydride, (methyl) acrylic acid 2-hydroxyl ethyl ester etc. is for example arranged.Aforementioned cyclic acid anhydride for example has: maleic anhydride, fumaric acid anhydride, cyclohexane dicarboxylic acid acid anhydride etc.
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 that aforementioned commercially available product for example has: East Ami synthetic chemical industry (strain) to make; NK エ ス テ Le CB-1, NK エ ス テ Le CBX-1 that Xin Zhong village chemical industry (strain) is made; Be total to HOA-MP, HOA-MS that Sakae society oil chemistry industry (strain) is made; The PVC ス コ one ト #2100 that Osaka You Machine chemical industry (strain) is made etc.Wherein, from good, the with low cost aspect of development, preferred (methyl) acrylic acid etc.
The group that has the olefinic unsaturated group on the-side chain: Z-
Aforementioned " the olefinic unsaturated group on the side chain " is not particularly limited preferred (methyl) acryloyl group of olefinic unsaturated group.In addition, for being connected of olefinic unsaturated group and monomer, so long as the linking group of divalents such as ester group, amide group, carbamyl just is not particularly limited.To on side chain, introducing the method for olefinic unsaturated group, can be from known method suitably select, for example have: have the method for (methyl) acrylate of isocyanate group in addition on the group that has method that addition on the group of acidic groups has (methyl) acrylate of epoxy radicals, has hydroxyl, have the method etc. that addition on the group of isocyanate group has (methyl) acrylate of hydroxyl.
Wherein, consider that most preferably addition has the method for (methyl) acrylate of epoxy radicals on the repetitive of acidic groups having from easy manufacturing, aspect with low cost.
To being not particularly limited as aforementioned (methyl) acrylate with ethylenic unsaturated bond and epoxy radicals, as long as it has ethylenic unsaturated bond and epoxy radicals, but the compound of the compound of preferred following structural formula (1) expression and following structural formula (2) expression.
Wherein, in aforementioned structural formula (1), R
1Expression hydrogen atom or methyl.L
1The expression organic group.
Wherein, in aforementioned structural formula (2), R
2Expression hydrogen atom or methyl.L
2The expression organic group.W represents the aliphatic alkyl of 4～7 yuan of rings.
In the compound that the compound and the aforementioned structural formula (2) of aforementioned structural formula (1) expression are represented, compare the compound of preferred structure formula (1) expression with the compound of structural formula (2) expression.In aforementioned structural formula (1) and (2), more preferably L
1And L
2Independent respectively is the compound of the alkylidene of carbon number 1～4.
To the compound of aforementioned structural formula (1) expression or the compound of aforementioned structural formula (2) expression, be not particularly limited, for example can be following exemplary compounds (1)～(10).
-other group: L-
Monomer with aforementioned other group (L) is not particularly limited, for example has: do not have the monomer with (methyl) acrylate, styrene, vinyl ether, dibasic acid anhydride base, vinyl ester group, alkenyl group etc. of side chain and/or alicyclic structure etc.
To aforementioned vinyl ether group is not particularly limited, for example have: butylethylene ether etc.
Aforementioned dibasic acid anhydride base is not particularly limited, for example has: maleic anhydride base, itaconic anhydride base etc.
Aforementioned vinyl ester group is not particularly limited, vinyl acetate base ester group etc. is for example arranged.
Aforementioned alkenyl group is not particularly limited, for example has: butadienyl, prenyl etc.
About the monomer with other group (L) in the aforementioned resin (A), its mole ratio of components content is preferably 0～30mol%, more preferably 0～20mol%.
As the concrete example of resin (A), the compound that for example has following compound structure P-1～P-35 to represent.
The manufacture method of-resin (A)-
Aforementioned resin (A) is made by (being total to) polyreaction operation of monomer and this two-stage procedure of operation of introducing olefinic unsaturated group.
At first, (being total to) polyreaction is undertaken by various monomers (being total to) polyreaction, can suitably select from known (being total to) polyreaction with being not particularly limited.For example, with regard to the active group kind of polymerization, can from free radical polymerization, cationic polymerization, anionic polymerisation, coordination polymerization etc., suitably select.Wherein, consider preferred free radical polymerization from easy synthetic, aspect with low cost.In addition, polymerization also is not particularly limited, can from known polymerization, suitably selects.Can suitably select mass polymerization, suspension polymerization, emulsion polymerization, solution polymerization process etc.Wherein, more preferably solution polymerization process.
-molecular weight-
Preferred 10,000～100,000 as the weight-average molecular weight of the suitable aforementioned multipolymer of resin (A), further preferred 12,000～60,000, preferred especially 15,000～4.5 ten thousand.When weight-average molecular weight was in aforementioned range, this multipolymer was preferred aspect manufacturing adaptability, development.In addition, reduce and formed shape is not easy to destroy and be not easy to form crosslinked spacer shape bad, when developing and does not have to consider that this multipolymer is preferred aspect the residue at melt viscosity.
-glass transition temperature-
The suitable glass transition temperature (Tg) of resin (A) is preferably 40～180 ℃, more preferably 45～140 ℃, is preferably 50～130 ℃ especially.When glass transition temperature (Tg) is in aforementioned preferred range, can obtain having the photonasty spacer of good development, mechanical strength.
-acid number-
The acid number that is fit to of resin (A) because of the also change of different its preferable range of molecular structure, but generally is preferably more than the 20mgKOH/g, more preferably more than the 50mgKOH/g, is preferably more than 70～130mgKOH/g especially.When acid number is in aforementioned preferred range, can obtain having the photonasty spacer of good development, mechanical strength.
Consider that from the photonasty spacer aspect that can obtain having good development, mechanical strength the glass transition temperature (Tg) of preferred aforementioned resin (A) is that 40～180 ℃ and weight-average molecular weight are 10,000～100,000.
And, with preferred aforementioned molecular weight, preferred aforementioned glass transition temperature (Tg) and preferred aforementioned acid number combination, be the preferred example of aforementioned resin (A).
Consider that from distortion recovery rate, development residue, wrinkle aspect the resin among the present invention (A) is preferably respectively at the multipolymer of at least 3 yuan of copolymerizations of the group Z (z mole %) that has the radicals X (x mole %) that has side chain and/or alicyclic structure on the aforementioned side chain, the group Y (y mole %) with acidic groups on the different copolymerization monomers, has the olefinic unsaturated group.Particularly, the multipolymer that is formed by at least 1 each monomer copolymerizable that constitutes aforementioned X, Y, Z respectively is preferred.
With regard to the copolymerization ratio of components of aforementioned each composition of aforementioned resin (A), by glass transition temperature and acid number and determine, cannot treat different things as the same, but " group that has side chain and/or alicyclic structure on the side chain " is preferably 10～70 moles of %, further preferred 15～65 moles of %, preferred especially 20～60 moles of %.When the copolymerization ratio of components of the group that has side chain and/or alicyclic structure on the side chain is in aforementioned range, can obtain good development, simultaneously, image section is also good to the tolerance of developer solution.
In addition, preferred 5～70 moles of % of the copolymerization ratio of components of " group that has acidic groups on the side chain ", further preferred 10～60 moles of %, preferred especially 20～50 moles of %.When the copolymerization ratio of components of the group that has acidic groups on the side chain is in aforementioned range, can obtain good curable and development.
In addition, preferred 10～70 moles of % of the copolymerization ratio of components of " group that has the olefinic unsaturated group on the side chain ", further preferred 20～70 moles of %, preferred especially 30～70 moles of %.When the copolymerization ratio of components of the group that has the olefinic unsaturated group on the side chain was in aforementioned range, pigment-dispersing was good, and simultaneously, development and curable are also good.
With respect to the total solid composition of aforementioned photosensitive composite, preferred 5～70 quality % of the content of aforementioned resin (A), more preferably 10～50 quality %.Resin (A) can comprise resin (A) resin described later in addition, but preferably only is made of resin (A).
In addition resin of-resin (A)-
Resin (A) resin in addition that can use simultaneously with aforementioned resin (A), preferably those demonstrate the compound of swellability with respect to alkaline aqueous solution, more preferably are the compound of solubility with respect to alkaline aqueous solution.
Demonstrate swellability or deliquescent resin with respect to alkaline aqueous solution; can suitably enumerate the resin that for example has acidic groups; specifically, preferably in epoxy compound, introduce the potpourri that has the ethylenic copolymer of (methyl) acryloyl group and acidic groups on ethylenic copolymer, epoxy acrylic ester compounds and the side chain that has (methyl) acryloyl group and acidic groups on compound (epoxy acrylic ester compounds) that ethylenical unsaturated double bonds and acidic groups are arranged, the side chain, maleamic acid based copolymer etc.
Aforementioned acidic groups is not particularly limited, can suitably selects, for example have according to purpose: carboxyl, sulfonic group, phosphate etc., wherein, consider from acquired grade of raw material, preferably exemplify carboxyl.
The ratio of-resin (A) and resin (A) resin in addition-
The total content of the aforementioned resin (A) and the resin that can use simultaneously with it with respect to aforementioned photosensitive composite total solid composition, is preferably 5～70 quality %, more preferably 10～50 quality %.When this solid component content was lower than 5 quality %, the film strength of photographic layer described later died down easily, the tackiness deterioration on this photographic layer surface, and when it surpassed 70 quality %, exposure sensitivity reduced.Need to prove that aforementioned content is represented solid component content.
-polymerizable compound (B), Photoepolymerizationinitiater initiater (C), other composition-
In the present invention, polymerizable compound (B), Photoepolymerizationinitiater initiater (C), other composition can preferably use those compositions that constitute known composition, and this composition for example has: the spy opens paragraph sequence number [0010]～[0020] described composition and special paragraph sequence number [0027]～[0053] described composition of opening the 2006-64921 communique of 2006-23696 communique.
For with the relation of aforementioned resin (A), polymerizable compound (B) is preferably 0.5～2.0 with respect to the quality ratio of resin (A) ((B)/(A) than), more preferably 0.6～1.4, preferred especially 0.7～1.2.When (B)/(A) ratio is in aforementioned preferable range, can obtain having the photonasty spacer of good development, mechanical strength.
With respect to resin (A), the content of aforementioned lights polymerization initiator (C) is preferably 0.1～20 quality %, more preferably 0.5～10 quality %.
-particulate (D)-
In aforementioned photosensitive composite, preferably add particulate.Aforementioned particulate (D) is not particularly limited, can suitably select according to purpose, for example preferred spy opens 2003-302639 communique [0035]～[0041] described filler pigment, wherein, consider preferred cataloid from the viewpoint of the photonasty spacer that can obtain having good development, mechanical strength.
Consider that from the viewpoint of the photonasty spacer that can obtain having high mechanical strength the mean grain size of aforementioned particulate (D) is preferably 5～50nm, more preferably 10～40nm is preferably 15～30nm especially.
In addition, consider from the viewpoint of the photonasty spacer that can obtain having high mechanical strength, aforementioned particulate (D) is preferably 5～50 quality % with respect to the quality ratio of the total solid composition in the photosensitive composite among the present invention, more preferably 10～40 quality % are preferably 15～30 quality % especially.
[pattern formation operation]
Pattern among the present invention forms operation and will be formed at photo-sensitive resin on the stilt and expose and develop and form pattern.Pattern forms the object lesson of operation, for example be special described example and special paragraph sequence number [0040]～[0051] described operation of opening the 2006-23696 communique etc. of forming in paragraph sequence number [0071]～[0077] of opening the 2006-64921 communique, these also can be used as preferred embodiment of the present invention.
＜liquid crystal indicator substrate 〉
Liquid crystal indicator substrate of the present invention is the substrate with photonasty spacer that the manufacture method of utilizing aforementioned photonasty spacer of the present invention obtains.The photonasty spacer preferably be formed at demonstrations such as black matrix on the stilt with shading light part on and form on the driving element such as TFT.In addition, between black matrix etc. shows with driving element such as shading light part and TFT and photonasty spacer, can there be liquid crystal orientation films such as transparency conducting layers such as ITO (transparency electrode) and polyimide.
For example, when on showing, the photonasty spacer being set with shading light part and driving element, the demonstration that is provided in advance on this stilt is covered by photo-sensitive resin with shading light part (black matrix etc.) and driving element, for example, the photo-sensitive resin of photosensitive resin transfer film is laminated on the support object plane, peel off transfer printing and after forming photo-sensitive resin, it is implemented exposure, development, heat treated etc. and forms the photonasty spacer, can make liquid crystal indicator substrate of the present invention thus.
With in the substrate, can also be provided with the colored pixels of redness (R), blue (B), green (G) these 3 kinds of colors etc. at liquid crystal indicator of the present invention as required.
＜liquid crystal display cells 〉
Aforementioned liquid crystal indicator of the present invention can be set constitute liquid crystal display cells with substrate.1 example as liquid crystal display cells, can exemplify: at least one has between a pair of stilt (comprising liquid crystal indicator substrate of the present invention) of photopermeability therein, has liquid crystal layer and the liquid crystal drive unit liquid crystal display cells of (comprising simple matrix type of drive and driven with active matrix mode) at least.
At this moment, liquid crystal indicator of the present invention can be used as the color filter substrate with substrate and constitutes, and described color filter substrate has a plurality of rgb pixel groups, and each pixel that constitutes this rgb pixel group is divided with black matrix mutually.On this color filter substrate, be provided with highly evenly and be out of shape restorative good photonasty spacer.Therefore, have the liquid crystal display cells of this color filter substrate, can suppress generating box thickness ununiformity even (the thick change of box) between color filter substrate and the opposed substrate, prevent the inhomogeneous grade of form and aspect effectively and show inhomogeneous.The liquid crystal display cells that is made thus can clear display image.
In addition, formation as other form of liquid crystal display cells, at least one has between a pair of stilt (comprising liquid crystal indicator substrate of the present invention) of photopermeability therein, at least have liquid crystal layer and liquid crystal drive means, the foregoing liquid crystal driving means has active component (for example TFT), and utilizes between a pair of substrate and to utilize highly evenly and be out of shape the width that restorative good photonasty spacer is set regulation.
At this moment, liquid crystal indicator of the present invention also can be used as the color filter substrate with substrate and constitutes, and described color filter substrate has a plurality of rgb pixels, and each pixel that constitutes this rgb pixel group is divided with black matrix mutually.
Among the present invention for example there be operable liquid crystal: nematic liquid crystal, cholesteric crystal, disc-like liquid crystal, strong dielectricity liquid crystal.
In addition, the aforementioned pixel group of aforementioned color filter substrate can be made of 2 kinds of color pixel that present different mutually colors, also can be made of 3 kinds of color pixel, 4 kinds of pixels more than the color.For example under the situation of 3 kinds of colors, constitute by color among red (R), green (G) and blue (B) this three.At configuration RGB3 kind color pixel group time, configurations such as preferred mosaic type (Mosaic), triangular form when pixel group more than the color of 4 kinds of configurations, can be the configurations of arbitrary form.For the making of color filter substrate, for example, can after forming 2 kinds of pixel groups more than the color, form black matrix as mentioned above, on the contrary, also can after forming black matrix, form pixel group.For the formation of rgb pixel, can open 2004-347831 communique etc. with reference to the spy.
＜liquid crystal indicator 〉
Be provided with foregoing liquid crystal display device substrate in the liquid crystal indicator of the present invention.In addition, liquid crystal indicator of the present invention also is provided with the foregoing liquid crystal display element.Promptly, the following formation of liquid crystal indicator of the present invention: the gap between a pair of substrate that disposes opposite to each other in mutual opposed mode, as mentioned above, set with the photonasty spacer that the manufacture method of utilizing photonasty spacer of the present invention is made, in the gap of setting, enclose liquid crystal material (will enclose the position and be called liquid crystal layer), the thickness (box is thick) of liquid crystal layer is remained on desirable uniform thickness.
Liquid crystal display pattern in the liquid crystal indicator can suitably have been enumerated: STN type, TN type, GH type, ECB type, strong dielectricity liquid crystal, anti-strong dielectricity liquid crystal, VA type, IPS type, OCB type, ASM type, other various types of liquid crystal.Wherein, in liquid crystal indicator of the present invention, consider from the viewpoint that reaches effect of the present invention most effectively, preferably take place easily to show uneven those display modes that because of the thick change of the box of liquid crystal cell preferred cartridge is thick to be VA type display mode, IPS type display mode, the OCB type display mode of 2～4 μ m.
The basic comprising form of liquid crystal indicator of the present invention, for example have: (a) will arrange driving side substrate that forms and opposed substrate and dispose opposite to each other by thin film transistor (TFT) driving elements such as (TFT) and pixel electrode (conductive layer) with opposite electrode (conductive layer), the photonasty spacer is between between these two substrates that dispose in opposite directions, and the crack part is enclosed liquid crystal material and the form that constitutes betwixt; (b) will drive substrate disposes opposite to each other with the opposed substrate with opposite electrode (conductive layer), the photonasty spacer is between between these two substrates that dispose in opposite directions, and the crack part is enclosed liquid crystal material and the form that constitutes etc. betwixt, and liquid crystal indicator of the present invention can be preferably applied to various liquid crystal displays.
With regard to liquid crystal indicator, for example on the books in " LCD Technology of future generation (Uchida Tatsuo edits, the census of manufacturing is understood, 1994 distribution) ".In liquid crystal indicator of the present invention, except that having liquid crystal display cells of the present invention, be not particularly limited, the liquid crystal indicator that for example can be used as the variety of way that is recorded in " LCD Technology of future generation " constitutes.Wherein, the formation of the liquid crystal indicator of special effectively colored TFT mode.With regard to the liquid crystal indicator of colored TFT mode, it is for example " on the books in the colored TFT LCD (upright publication (strain) altogether, distribution in 1996).
Liquid crystal indicator of the present invention, except that liquid crystal display cells, can use various members such as electrode substrate, polarization film, phase-contrast film, backlight, chock insulator matter, field angle compensation film, antireflective film, light diffusion film, anti-dazzle film to constitute usually with the invention described above.With regard to these members, for example the market of " ' 94 LCD peripheral material ケ ミ カ Le ズ (island Itou Kentaro, (strain) シ one エ system シ one, distribution in 1994) ", " present situation in the related market of 2003 liquid crystal and vision of the future (last volume) (and table good lucky, (strain) Fuji キ メ ラ Gross grinds, distribution in 2003) " on the books.
Embodiment
Below, utilize embodiment to be described more specifically the present invention, but only otherwise surmount its main idea, the present invention is not limited to the following examples.Need to prove, unless otherwise specified, " % " reach " part " with quality as benchmark.
The resin (A) that aforesaid compound structure P-1 is represented synthetic is shown in following synthesis example 1.
(synthesis example 1)
In reaction vessel, add 8.57 parts of 1-methoxyl-2-propyl alcohol (ダ イ セ Le chemical industry (strain) manufacturing) in advance, be warming up to 90 ℃, will be by as 6.27 parts of isopropyl methacrylates, as the mixed solution of 1 part of 5.15 parts of methacrylic acid, azo class polymerization initiator with monomer of the group Y that has acidic groups on the side chain (V-601 that makes with light Pure medicine society) and 1-methoxyl-8.57 parts of formations of 2-propyl alcohol with monomer of the radicals X that has side chain and/or alicyclic structure on the side chain, under nitrogen environment, with splashing in 2 hours in 90 ℃ the reaction vessel.Make its reaction 4 hours after splashing into, obtain acrylic resin soln.
Then, in aforementioned acrylic resin soln, after adding 0.084 part of 0.025 part of monomethyl ether of hydroquinone and tetraethylammonium bromide, have 5.41 parts of the glycidyl methacrylate of the monomer of the group Z that has the olefinic unsaturated group on the side chain with splashing into conduct in 2 hours.After splashing into, be blown into air on one side, it was reacted 4 hours down at 90 ℃, add solvent (MMPGAC) then, so that its solid component concentration is 45%, prepare thus, obtain having the x that the aforesaid compound structure P-1 of unsaturated group represents: y: z is the resin solution of 45mol%: 20mol%: 35mol%.
Need to prove that the molecular weight Mw of the resin that aforesaid compound structure P-1 represents represents weight-average molecular weight, the assay method of this molecular weight uses gel permeation chromatograph (GPC) to measure.
Then, the synthetic following synthesis example 2～synthesis example 22 and the synthesis example 24～synthesis example 32 of being shown in of the resin that aforesaid compound structure P-2, P-3, P-7, P-8, P-10, P-12～P-15 and P-24～P-35 are represented.
(synthesis example 2)
It is following that what carry out is the synthesis example 2 of the resin represented of aforesaid compound structure P-2.
The resin that aforesaid compound structure P-2 is represented, its synthon is changed to metering system tert-butyl acrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-2: y: z is 40mol%: 25mol%: 35mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-2 of unsaturated group represents.
(synthesis example 3)
It is following that what carry out is the synthesis example 3 of the resin represented of aforesaid compound structure P-3.
The resin that aforesaid compound structure P-3 is represented, its synthon is changed to isobutyl methacrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-3: y: z is 40mol%: 20mol%: 40mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-3 of unsaturated group represents.
(synthesis example 4)
It is following that what carry out is the synthesis example 4 of the resin represented of aforesaid compound structure P-7.
Resin for aforesaid compound structure P-7 represents changes to isopropyl methacrylate, methacrylic acid and サ イ Network ロ マ one ((CYCLOMER) M-200 with its synthon; ダ イ セ Le chemical industry (strain) is made) and change its addition, so that the x among the aforesaid compound structure P-7: y: z is 40mol%: 25mol%: 35mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-7 of unsaturated group represents.
(synthesis example 5)
It is following that what carry out is the synthesis example 5 of the resin represented of aforesaid compound structure P-8.Resin for aforesaid compound structure P-8 represents changes to metering system tert-butyl acrylate, methacrylic acid and サ イ Network ロ マ one ((CYCLOMER) A-200 with its synthon; ダ イ セ Le chemical industry (strain) is made) and change its addition, so that the x among the aforesaid compound structure P-8: y: z is 35mol%: 30mol%: 35mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-8 of unsaturated group represents.
(synthesis example 6)
It is following that what carry out is the synthesis example 6 of the resin represented of aforesaid compound structure P-10.
The resin that aforesaid compound structure P-10 is represented, its synthon is changed to cyclohexyl methacrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-10: y: z is 30mol%: 30mol%: 40mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-10 of unsaturated group represents.
(synthesis example 7)
It is following that what carry out is the synthesis example 7 of the resin represented of aforesaid compound structure P-12.
Resin for aforesaid compound structure P-12 represents changes to cyclohexyl methacrylate, methacrylic acid and サ イ Network ロ マ one ((CYCLOMER) A-200 with its synthon; ダ イ セ Le chemical industry (strain) is made) and change its addition, so that the x among the aforesaid compound structure P-12: y: z is 30mol%: 30mol%: 40mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-12 of unsaturated group represents.
(synthesis example 8)
It is following that what carry out is the synthesis example 8 of the resin represented of aforesaid compound structure P-13.
Resin for aforesaid compound structure P-13 represents changes to isobornyl methacrylate, acrylic acid dimer and サ イ Network ロ マ one ((CYCLOMER) M-200 with its synthon; ダ イ セ Le chemical industry (strain) is made) and change its addition, so that the x among the aforesaid compound structure P-13: y: z is 45mol%: 15mol%: 40mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-13 of unsaturated group represents.
(synthesis example 9)
It is following that what carry out is the synthesis example 9 of the resin represented of aforesaid compound structure P-14.
Resin for aforesaid compound structure P-14 represents changes to isobornyl methacrylate, methacrylic acid and サ イ Network ロ マ one ((CYCLOMER) A-200 with its synthon; ダ イ セ Le chemical industry (strain) is made) and change its addition, so that the x among the aforesaid compound structure P-14: y: z is 35mol%: 30mol%: 35mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-14 of unsaturated group represents.
(synthesis example 10)
It is following that what carry out is the synthesis example 10 of the resin represented of aforesaid compound structure P-15.
The resin that aforesaid compound structure P-15 is represented, its synthon is changed to methacrylic acid norborneol ester, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-15: y: z is 45mol%: 30mol%: 25mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-15 of unsaturated group represents.
(synthesis example 11～14)
In aforementioned synthesis example 2, the addition of the composition that uses in the synthesis example 2 is adjusted, so that have table 2 listed solid constituent acid number, Mw, obtain having the resin solution that the aforesaid compound structure P-2 of unsaturated group represents.
(synthesis example 15～17)
In aforementioned synthesis example 1, the addition of the composition that uses in the synthesis example 1 is adjusted, so that have table 2 listed solid constituent acid number, Mw, obtain having the resin solution that the aforesaid compound structure P-1 of unsaturated group represents.
(synthesis example 18)
It is following that what carry out is the synthesis example 18 of the resin represented of aforesaid compound structure P-24.
The resin that aforesaid compound structure P-24 is represented, its synthon is changed to cyclohexyl methacrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-24: y: z is 44mol%: 16mol%: 40mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-24 of unsaturated group represents.
(synthesis example 19)
It is following that what carry out is the synthesis example 19 of the resin represented of aforesaid compound structure P-25.
The resin that aforesaid compound structure P-25 is represented, with its synthon change to cyclohexyl methacrylate, as monomer with other group L methyl methacrylate, methacrylic acid and glycidyl methacrylate and change its addition, so that the x among the aforesaid compound structure P-25: l: y: z is 46mol%: 2mo1%: 20mol%: 32mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-25 of unsaturated group represents.
(synthesis example 20)
It is following that what carry out is the synthesis example 20 of the resin represented of aforesaid compound structure P-26.
The resin that aforesaid compound structure P-26 is represented, with its synthon change to cyclohexyl methacrylate, as monomer with other group L methyl methacrylate, methacrylic acid and glycidyl methacrylate and change its addition, so that the x among the aforesaid compound structure P-26: l: y: z is 45.5mol%: 2mol%: 19mol%: 33.5mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-26 of unsaturated group represents.
(synthesis example 21)
It is following that what carry out is the synthesis example 21 of the resin represented of aforesaid compound structure P-27.
The resin that aforesaid compound structure P-27 is represented, its synthon is changed to cyclohexyl methacrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-27: y: z is 48mol%: 22mol%: 30mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-27 of unsaturated group represents.
(synthesis example 22)
It is following that what carry out is the synthesis example 22 of the resin represented of aforesaid compound structure P-28.
The resin that aforesaid compound structure P-28 is represented, its synthon is changed to cyclohexyl methacrylate, methacrylic acid and glycidyl methacrylate and changes its addition, so that the x among the aforesaid compound structure P-28: y: z is 51.5mol%: 18.5mol%: 30mol%, in addition, utilize with the same method of synthesis example 1 and synthesize, obtain having the resin solution that the aforesaid compound structure P-28 of unsaturated group represents.
(synthesis example 23): the preparation of alkali soluble resin (20)
The mixed solvent that in reaction vessel, adds 1-methoxyl-2-propyl alcohol 25g and 1-methoxyl-2-propyl-acetic acid ester 25g in advance, be warming up to 90 ℃, the mixed solution that will be made of styrene 32.1g, methacrylic acid 36.5g, azo class polymerization initiator (V-601 that makes with light Pure medicine society) 6.73g, 1-methoxyl-2-propyl alcohol 25g and 1-methoxyl-2-propyl-acetic acid ester 25g is under nitrogen environment, with splashing in 2 hours in 90 ℃ the reaction vessel.Make its reaction 4 hours after splashing into, obtain acrylic resin soln.
Then, in aforementioned acrylic resin soln, add monomethyl ether of hydroquinone 0.5g and tetraethylammonium bromide 0.015g after, with splashing into glycidyl methacrylate 31.3g in 2 hours.After splashing into,,, obtain alkali soluble resin (20) solution Yi Bian under 90 ℃, make its reaction 4 hours Yi Bian be blown into air.Solid constituent in this alkali soluble resin (20) solution is 50%.
(synthesis example 24)
It is following that what carry out is the synthesis example 24 of the resin represented of aforesaid compound structure P-25.
Except adjusting initiating agent dosage and temperature of reaction, use with the same method of synthesis example 19 syntheticly, obtain having the resin solution that the aforesaid compound structure P-25 of unsaturated group represents.
(synthesis example 25～31)
It is following that what carry out is the synthesis example 25～31 of the resin represented of aforesaid compound structure P-29～P-35.
Except in order to make the x among aforesaid compound structure P-29～P-35: y: z reaches mol% as described in Table 3, beyond the addition of each compound, methacrylic acid and the glycidyl methacrylate described in the x monomer of change table 3, according to the resin that the synthetic aforesaid compound structure P-29～P-35 of the method identical with synthesis example 1 represents, obtain having the resin solution that the aforesaid compound structure P-29～P-35 of unsaturated group represents.
(synthesis example 32)
It is following that what carry out is the synthesis example 32 of the resin represented of aforesaid compound structure P-21.
Except in order to make the x among the aforesaid compound structure P-21: y: z reaches 45mol%: 20mol%: 35mol%, change beyond the addition of ADMA (methacrylic acid 2-diamantane ester), methacrylic acid and glycidyl methacrylate, according to the resin that the synthetic aforementioned P-21 of the method identical with synthesis example 1 represents, obtain having the resin solution that the aforesaid compound structure P-21 of unsaturated group represents.
(embodiment 1): transfer printing
The making of-chock insulator matter usefulness photosensitive transfer film-
At thickness is on the interim stilt of pet film (the interim stilt of PET) of 75 μ m, and the thermoplastic resin that coating is made of following prescription A forms the thermoplastic resin of dry bed thickness 15.0 μ m with applying liquid and making its drying.
[the thermoplastic resin prescription A of coating liquid]
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer ... 25.0 parts
(=55/11.7/4.5/28.8[mol ratio], matter average molecular weight 90,000)
Styrene/acrylic acid co-polymer ... 58.4 parts
(=63/37[mol ratio], matter average molecular weight 8,000)
2,2-two [4-(methacryloxy polyethoxy) phenyl] propane ... 39.0 parts
Surfactant 1 (containing following works 1) ... 10.0 parts
Methyl alcohol ... 90.0 parts
1-methoxyl-2-propyl alcohol ... 51.0 parts
Butanone ... 700 parts
Then, on the thermoplastic resin that forms, the middle layer of dry bed thickness 1.5 μ m is made with applying liquid and making its drying in the middle layer that coating is made of following prescription B.
*The composition of surfactant 1
Following works 1 ... 30%
Butanone ... 70%
Works 1
(n＝6、x＝55、y＝5、Mw＝33940、Mw/Mn＝2.55
PO: epoxypropane, EO: oxirane)
[the middle layer prescription B of coating liquid]
Polyvinyl alcohol (PVA) ... 3.22 parts
(PVA-205, saponification rate 80%, (strain) Network ラ レ makes)
Polyvinylpyrrolidone ... 1.49 parts
(PVA K-30, ア イ エ ス ピ one ジ ヤ パ Application Co., Ltd. makes)
Methyl alcohol ... 42.3 parts
Distilled water ... 524 parts
Then, on the middle layer that forms, further the photo-sensitive resin that is made of the prescription 1 shown in the following table 1 of coating is made the photosensitive polymer combination layer of dry bed thickness 4.1 μ m with applying liquid and making its drying.
Operate as mentioned above, form the stepped construction (total bed thickness of 3 layers is 11.6 μ m) of the interim stilt/thermoplastic resin of PET/middle layer/photosensitive polymer combination layer.Then, will be that the polypropylene made membrane of 12 μ m sticks on the surface of photosensitive polymer combination layer as the thickness of diaphragm further in the mode of heating and pressurizing, obtain chock insulator matter with photosensitive transfer film (1).
The making of-color filter substrate-
Open paragraph sequence number [0084]～[0095] described method of 2005-3861 communique with the spy, make color filter with black matrix, R pixel, G pixel, B pixel.Then, on the R of color filter substrate pixel, G pixel and B pixel and black matrix, further form ITO (Indium Tin Oxide) transparency electrode by sputter.
The making of-photonasty spacer-
The chock insulator matter that the obtains diaphragm with photosensitive transfer film (1) is peeled off; the surface of the photosensitive polymer combination layer that will expose is superimposed upon on the ITO film of color filter substrate that the above-mentioned sputter of making is formed with the ITO film; use the stacked machine of Lamic II type [(strain) イ of Hitachi Application ダ ス ト リ イ ズ manufacturing], under line pressure 100N/cm, 130 ℃ pressurized, heated condition to make its stickup in transporting velocity 2m/ minute.Then, remove the interim stilt of PET, the photosensitive polymer combination layer is carried out transfer printing (layer forms operation) with thermoplastic resin and middle layer from peeling off with the interface of thermoplastic resin.
Then, use has the proximi-ty printing machine (the Ha イ テ Network Electricity エ Application ジ ニ ア リ Application グ of Hitachi (strain) manufacturing) of extra-high-pressure mercury vapour lamp, with under mask (quartzy exposed mask) and the vertical state that erects in color filter substrate almost parallel ground with picture pattern, wherein this mask is to dispose opposite to each other with the opposed mode of thermoplastic resin, with the distance setting between the surface of the side that contacts with the middle layer of mask face and photosensitive polymer combination layer is 100 μ m, is 90mJ/cm by mask with the exposure from the thermoplastic resin side
2Carry out proximi-ty printing.
Then, with triethanolamine class developer solution (contain triethanolamine 30%, with T-PD2 (trade name, the Off イ of Fuji Le system (strain) is made) with pure water dilution (ratio with 11 parts of 1 part of T-PD2 and pure water is mixed) to 12 times liquid) under 30 ℃, with tack nozzle pressure 0.04MPa, spray and developed 50 seconds, remove thermoplastic resin and middle layer.Continuation is carried out utilizing the spray mode that pure water was sprayed 10 seconds after liquid cuts to the top injection air of this glass substrate, carries out the pure water spray washing, injection air and reduce liquid holdup on the substrate.
Continue to use sodium carbonate class developer solution (to contain the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 5% nekal, anionic surfactant, defoamer and stabilizing agent; T-CD1 (trade name, the Off イ of Fuji Le system (strain) is made) is diluted to 10 times liquid with pure water) under 29 ℃, with conical nozzle pressure 0.15MPa, spray and developed 30 seconds, obtain the pattern image of chock insulator matter.
Continue to use washing agent (is contained phosphate silicate non-ionic surfactant defoamer stabilizing agent; T-SD3 (trade name, the Off イ of Fuji Le system (strain) is made)) is diluted to 10 times liquid with pure water, under 33 ℃, with conical nozzle pressure 0.02MPa,, the residue around the pattern image that forms removed, obtain desirable chock insulator matter pattern by the spray injection.
Then, the color filter substrate that is provided with the chock insulator matter pattern is carried out 30 minutes heat treated (heat treatment step) under 230 ℃, make the photonasty spacer.
The chock insulator matter pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.In addition, the assay method of average height is as follows: use three-dimensional surface structure analysis microscope (manufacturing plant: ZYGO Corporation, model: New View 5022), to 1000 of the chock insulator matters that obtain, measure the extreme higher position of the highest chock insulator matter (20) from ito transparent electrode formation face.
The making of＜liquid crystal indicator 〉
In addition, prepare glass substrate as opposed substrate, on by the transparency electrode of the above-mentioned color filter substrate that obtains and carry out the pattern that the PVA pattern uses on the opposed substrate respectively and forms, the further oriented film that constitutes by polyimide of setting thereon.
Then, the position that is equivalent to housing on the black matrix around being arranged in the mode of surrounding the color filter pixel group, utilize and divide leakage device (dispenser) mode to apply the ultraviolet curable resin sealant, instillation PVA pattern liquid crystal, after the opposed substrate stickup, the substrate that pastes is carried out the UV irradiation, heat-treat then, make sealant cures.The polaroid HLC2-2518 that is made by (strain) サ Application リ Star Star is pasted on two sides at the liquid crystal cell that obtains like this.
Then, use the DB1112H (the chip type LED of ス Application レ one Electricity mood (strain) manufacturing) of DG1112H (the chip type LED that ス Application レ one Electricity mood (strain) is made), blue (B) LED of conduct of FR1112H (the chip type LED that ス Application レ one Electricity mood (strain) is made), green (G) LED of conduct as redness (R) LED, construct the backlight of sidelight mode, with its rear side that is configured in the liquid crystal cell that is provided with aforementioned polaroid, make liquid crystal indicator.
(embodiment 2～21,30～37, comparative example 1,2)
Change the resin (A) among the embodiment 1, compound structure P-1～P-15, the P-21, the P-29～P-35 that obtain with table 2 or the described synthesis example 2～17,25～32 of table 3 replace the compound structure P-1 that is obtained by synthesis example 1, the photosensitive polymer combination layer is changed to the described prescription 1～7 of table 1 with the prescription 1 that applies liquid, in addition, make photonasty spacer and liquid crystal indicator with method similarly to Example 1.The chock insulator matter pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
The described carbon black dispersion liquid 1 of table 1 composed as follows.
Carbon black
(trade name: Nipex35, デ グ サ ジ ヤ パ Application (strain) are made)
13.1 part
0.65 part of spreading agent 1 (following compound 1)
6.72 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand)
79.53 parts of propylene glycol monomethyl ether acetic acid esters
Compound 1
Use the Na ノ ト ラ Star Network UPA-EX150 of Ri Machine dress society manufacturing, measure the particle diameter of this carbon black dispersion liquid 1, number average bead diameter is 20nm.
(embodiment 22): coating process
The making of-photonasty spacer (liquid method against corrosion)-
Be formed with on the ITO film of color filter substrate of ITO film the photosensitive polymer combination layer usefulness coating liquid that constitutes by the prescription shown in the following table 1 with coating machine MH-1600 (manufacturings of エ Off エ one エ ス ア ジ ア society) coating with glass substrate with slit-shaped nozzle in the sputter of above-mentioned making.Continue to use vacuum drier VCD (East capital ying society to make) make dry 30 seconds of the part of solvent, make the coated film lost flowability after, 120 ℃ of following prebake conditions 3 minutes, form the photosensitive polymer combination layer (layer forms operation) of thickness 4.0 μ m.
Next, utilize pattern similarly to Example 1 to form operation and heat treatment step, on the color filter substrate, make the photonasty spacer.Wherein, exposure is set at 300mJ/cm
2, utilize the development conditions of KOH class developer solution to be set at 23 ℃, 60 seconds.The chock insulator matter pattern that obtains is the cylindric of diameter 24 μ m, average height 3.6 μ m.
After making the photonasty spacer, use this color filter substrate, the liquid crystal indicator of PVA pattern of the present invention is made in operation similarly to Example 1.
[table 1]
| The photosensitive polymer combination layer is with applying liquid | Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 | Prescription 5 | Prescription 6 | Prescription 7 |
| Embodiment 1～17,22,30～37 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 | Comparative example 1 | Comparative example 2 | |
| 1-methoxyl-2-propyl-acetic acid ester | 26 | 24 | 28 | 28 | 10 | 35 | 28 |
| Butanone | 28 | 27 | 29 | 29 | 30 | 30 | 28 |
| Cataloid disperses thing (cataloid: 30 parts; Methylisobutylketone: 70 parts; The MIBKst that daily output chemical industry is made) | 14.1 | 14.1 | 14.1 | 14.1 | 0 | 14 | 14.1 |
| ソ Le ス パ one ス 20000 (pigment dispersing agent) | 0.42 | 0.42 | 0.42 | 0.42 | 0 | 0.42 | 0.42 |
| Carbon black dispersion liquid 1 | 0 | 0 | 0 | 0 | 32.1 | 0 | 0 |
| DPHA liquid (dipentaerythritol acrylate: 76 parts: 1-methoxyl-2-propyl-acetic acid ester: 24 parts) | 9.1 | 7.2 | 12.7 | 14.1 | 9.2 | 9 | 9.1 |
| The solution of resin (A) (wherein, resin (A) is the compound that utilizes the described synthesis example of table 2 synthetic) | 20.5 | 24.2 | 14.3 | 11.9 | 15.8 | 0 | 0 |
| Methacrylic acid/allyl methacrylate copolymer (mol ratio)=20/80 (weight-average molecular weight=3.6 ten thousand) | 0 | 0 | 0 | 0 | 0 | 9.17 | 0 |
| Alkali soluble resin (20) (solid constituent 50%) | 0 | 0 | 0 | 0 | 0 | 0 | 18.4 |
| 2,4-two (trichloromethyl)-6-[4 '-(N, N-two (ethoxy carbonyl methyl) amino)-3 '-bromophenyl]-the s-triazine | 0.227 | 0.152 | 0.316 | 0.35 | 0.23 | 0.23 | 0.227 |
| Monomethyl ether of hydroquinone | 0.0036 | 0.0024 | 0.005 | 0.0055 | 0.0036 | 0.0036 | 0.0036 |
| Surfactant 1 (メ ガ Off ア Star Network F-780-F, big Japanese イ Application キ chemical industry Co., Ltd. makes) | 0.032 | 0.032 | 0.032 | 0.032 | 0.032 | 0.03 | 0.032 |
| 5% methanol solution of Victoria blue-NAPS (protect native ケ paddy chemical industry Co., Ltd. make) | 2.05 | 2.05 | 2.05 | 2.05 | 2.04 | 2.04 | 2.05 |
Unit: mass parts
[table 2]
Record is the material suitable with x in 0 parantheses.
*Allyl methacrylate/methacrylic acid=80mol%/20mol% molecular weight is 36000 polymkeric substance.
[table 3]
| Resin (A) | B/A | Particulate (D) | The formation method | Estimate | ||||||||||||||
| Synthesis example | Compound structure | Glass transition temperature (℃) | Weight-average molecular weight | Acid number (mgKOH/g) | X: monomer | x | y | z | Kind | Mean grain size (nm) | Distortion recovery rate (%) | Development | Stacked adaptability | Wrinkle | Show inhomogeneous | |||
| Embodiment 30 | 25 | P-29 | 100 | 15000 | 74 | D-4 | 40 | 25 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 31 | 26 | P-30 | 91 | 15000 | 73.1 | D-3 | 41 | 24 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 32 | 27 | P-31 | 40 | 15000 | 73.3 | D-1 | 39 | 26 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 33 | 28 | P-32 | 111 | 11000 | 82.1 | T-2 | 35 | 30 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 34 | 29 | P-33 | 122 | 11000 | 73.9 | T-6 | 42 | 28 | 30 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 35 | 30 | P-34 | 74 | 11000 | 71.6 | T-4 | 37 | 28 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 36 | 31 | P-35 | 73 | 11000 | 64.9 | T-8 | 39 | 26 | 35 | 0.75 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
| Embodiment 37 | 32 | P-21 | 108 | 13000 | 57 | ADMA | 45 | 20 | 35 | 0.90 | Cataloid | 15 | Transfer printing | 5 | 3 | 3 | 3 | A |
X: what monomeric compound used is that Hitachi changes into the product (ADMA: methacrylic acid 2-diamantane ester) that industry (strain) is made.
(embodiment 23～28): the example of the chock insulator matter that diameter is little, average height is high
In small-sized liquid crystal indicators such as portable telephone equipment, generally use the liquid crystal mode of the little and TN type of pixel.Therefore, require the diameter of chock insulator matter little and highly higher mostly.But part can take place and come off in chock insulator matter that diameter is little, highly high sometimes in operation.
As adapting to example this requirement, that be more suitable for, in the present embodiment, (A) changes to resin, compound structure P-24～the P-28 that obtains with synthesis example 18～22 replaces the compound structure P-1 that is obtained by synthesis example 1, the photosensitive polymer combination layer is changed to the described prescription 8～12 of table 4 with the prescription 1 that applies liquid, in addition, make the photonasty spacer with method similarly to Example 1.Wherein, T-CD1 is diluted to 5 times of uses with pure water.The chock insulator matter pattern that obtains is the cylindric of diameter 15 μ m, average height 4.7 μ m.Coming off of chock insulator matter do not taken place in operation.In addition, in the present embodiment, increase the ratio of cataloid, improve the thickness and precision of chock insulator matter.
(embodiment 29)
Adjust the photosensitive polymer combination layer coating amount that applies liquid among the embodiment 28, making the chock insulator matter pattern that obtains is the cylindric of diameter 15 μ m, average height 4.7 μ m, in addition, makes the photonasty spacer according to method similarly to Example 28.
[table 4]
| The photosensitive polymer combination layer is with applying liquid | Prescription 8 | Prescription 9 | Prescription 10 | Prescription 11 | Prescription 12 | Prescription 13 |
| Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28,29 | |
| 1-methoxyl-2-propyl-acetic acid ester | 22 | 22 | 22 | 22 | 22 | 22 |
| Butanone | 16 | 16 | 16 | 16 | 16 | 16 |
| Cataloid disperses thing (with listed identical in the table 1) | 26 | 26 | 26 | 26 | 26 | 26 |
| ソ Le ス パ one ス 20000 | 0.22 | 0.22 | 0.22 | 0.22 | 0.22 | 0.22 |
| DPHA liquid (with listed identical in the table 1) | 11 | 11 | 11 | 11 | 11 | 11 |
| The solution of resin (A) (synthesis example 18) | 20 | 0 | 0 | 0 | 0 | 0 |
| The solution of resin (A) (synthesis example 19) | 0 | 20 | 0 | 0 | 0 | 0 |
| The solution of resin (A) (synthesis example 20) | 0 | 0 | 20 | 0 | 0 | 0 |
| The solution of resin (A) (synthesis example 21) | 0 | 0 | 0 | 20 | 0 | 0 |
| The solution of resin (A) (synthesis example 22) | 0 | 0 | 0 | 0 | 20 | 0 |
| The solution of resin (A) (synthesis example 24) | 0 | 0 | 0 | 0 | 0 | 20 |
| 2,4-two (trichloromethyl)-6-[4 '-(N, N-two (ethoxy carbonyl methyl) amino)-3 '-bromophenyl]-the s-triazine | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 |
| Surfactant 1 (with listed identical in the table 1) | 0.042 | 0.042 | 0.042 | 0.042 | 0.042 | 0.042 |
| 5% methanol solution of Victoria blue NAPS (protect native ケ paddy chemical industry Co., Ltd. make) | 5.8 | 5.8 | 5.8 | 5.8 | 5.8 | 5.8 |
Unit: mass parts
[evaluation]
-distortion recovery rate-
To each photonasty spacer, (DUH-W201, (strain) Island Jin System does manufacturing) following mensuration are estimated to utilize micro-hardness tester.Adopt the top fuller platform pressure head of 50 μ m , when the diameter of photonasty spacer is 24 μ m, maximum loading is 50mN, retention time is 5 seconds, utilize load-unloading test method(s) to measure, when the diameter of photonasty spacer was 15 μ m, maximum loading was 21mN, retention time is 5 seconds, according to measuring with quadrat method.Utilize following formula to obtain distortion recovery rate [%] according to this measured value, estimate according to following standard.Under 22 ± 1 ℃, the environment of 50%RH, measure.
Distortion recovery rate (%)=(amount of recovery [μ m] after deflection [μ the m]/removal loading that causes by loading) * 100
＜evaluation criterion 〉
5: the distortion recovery rate is more than 90%.
4: the distortion recovery rate is more than 87% and is lower than 90%.
3: the distortion recovery rate is more than 85% and is lower than 87%.
2: the distortion recovery rate is more than 80% and is lower than 85%.
1: the distortion recovery rate is more than 75% and is lower than 80%.
0: the distortion recovery rate is lower than 75%.
-development-
In above-mentioned " making of photonasty spacer-", carry out proximi-ty printing after, use with the same method of the development conditions of each embodiment and develop, the photonasty spacer periphery that forms is carried out SEM observes, confirm whether residual residue of periphery.
＜evaluation criterion 〉
5: can't see residue fully.
4: see a little residue in the pattern periphery.
3: see residue in the pattern periphery.
2: near the substrate pattern periphery and the pattern, see residue.
1: on substrate, can see residue everywhere.
-stacked adaptability＜stacked bubble〉estimate-
To transfer printing on the color filter substrate state of photosensitive resin transfer film, after peeling off interim stilt,, observe having or not of stacked bubble (being involved in the bubble that air produces when stacked) with observation by light microscope stacked state.
＜evaluation criterion 〉
3: do not have stacked bubble fully.
2: stacked bubble produces outside pattern formation is sentenced.
1: stacked bubble forms part at pattern and produces.
-wrinkle-
With the surface of the photosensitive resin transfer film of microscopic examination after placing 24 hours under the 45 ℃/75%RH environment, estimate by range estimation according to following standard.
＜evaluation criterion 〉
4: can't see the generation of thin " gauffer " etc. fully.
3: see the generation of a little thin " gauffer " etc., but be in fact operable degree.
2: see the generation of less thin " gauffer " etc.
1: obviously see the generation of thin " gauffer " etc.
-show inhomogeneous-
To each liquid crystal indicator, the grey when observing the test signal of importing grey with range estimation and magnifier shows, has or not according to following evaluation criterion evaluation to show uneven generation.
＜evaluation criterion 〉
A: it is inhomogeneous to can't see demonstration fully.
B: the demonstration of seeing a little is inhomogeneous.
C: see that tangible demonstration is inhomogeneous.
Claims (12)
1. photosensitive composite, it is characterized in that, at least comprise resin (A), polymerizable compound (B), Photoepolymerizationinitiater initiater (C), described resin (A) contains the group that has the olefinic unsaturated group on the group that has acidic groups on the group that has side chain and/or alicyclic structure on the side chain, the side chain and the side chain.
2. photosensitive composite as claimed in claim 1 is characterized in that, the glass transition temperature (Tg) of described resin (A) is that 40～180 ℃ and weight-average molecular weight are 10,000～100,000.
3. photosensitive composite as claimed in claim 1 is characterized in that, described polymerizable compound (B) is 0.5～2 with respect to the quality ratio ((B)/(A)) of resin (A).
4. photosensitive composite as claimed in claim 1 is characterized in that, it also comprises particulate (D).
5. photosensitive composite as claimed in claim 4, it is characterized in that the mean grain size of described particulate (D) is 5～50nm and this particulate (D) with respect to the quality ratio of the total solid composition in the described photosensitive composite of claim 4 is 5～50 quality %.
6. photosensitive composite as claimed in claim 4 is characterized in that, described particulate (D) is a cataloid.
7. photosensitive resin transfer film, it has photo-sensitive resin at least on interim stilt, it is characterized in that, and this photo-sensitive resin uses each described photosensitive composite in claim 1～6 and forms.
8. photosensitive resin transfer film as claimed in claim 7 is characterized in that, is provided with oxygen barrier layers and/or thermoplastic resin between described photo-sensitive resin and described interim stilt.
9. the manufacture method of a photonasty spacer is characterized in that, it has following operation: use the described photosensitive composite of claim 1 to apply, form photo-sensitive resin thus on stilt.
10. the manufacture method of a photonasty spacer, it is characterized in that, it has following operation: use the described photosensitive resin transfer film of claim 7, come the transfer printing photo-sensitive resin by heating and/or pressurization, form photo-sensitive resin thus on stilt.
11. a liquid crystal indicator substrate is characterized in that, it has the photonasty spacer that the manufacture method manufacturing that utilizes the described photonasty spacer of claim 9 forms.
12. a liquid crystal indicator is characterized in that, it has the described liquid crystal indicator substrate of claim 11.
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| JP2006-203926 | 2006-07-26 | ||
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| JP2006-309042 | 2006-11-15 |
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| JP (1) | JP4994136B2 (en) |
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- 2007-07-17 JP JP2007185797A patent/JP4994136B2/en active Active
- 2007-07-24 TW TW096126854A patent/TW200813630A/en unknown
- 2007-07-26 KR KR1020070075221A patent/KR20080010354A/en not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2008146018A (en) | 2008-06-26 |
| JP4994136B2 (en) | 2012-08-08 |
| TW200813630A (en) | 2008-03-16 |
| CN101114124B (en) | 2013-05-01 |
| KR20080010354A (en) | 2008-01-30 |
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