CN101689022A - Negative photosensitive resin composition, spacer and liquid crystal display - Google Patents

Negative photosensitive resin composition, spacer and liquid crystal display Download PDF

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Publication number
CN101689022A
CN101689022A CN200880017670A CN200880017670A CN101689022A CN 101689022 A CN101689022 A CN 101689022A CN 200880017670 A CN200880017670 A CN 200880017670A CN 200880017670 A CN200880017670 A CN 200880017670A CN 101689022 A CN101689022 A CN 101689022A
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China
Prior art keywords
methyl
alkali soluble
soluble resin
resin
acid
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保坂幸宏
前沢典明
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Fujifilm Wako Pure Chemical Corp
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Wako Pure Chemical Industries Ltd
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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
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • 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
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Disclosed is a negative photosensitive resin composition suitable as a photosensitive material for spacers. Specifically disclosed is a negative photosensitive resin composition having excellent developability, which enables to produce a spacer having high shrinkage ratio and high elasticity recovery ratio. Also disclosed are a spacer produced by using such a negative photosensitive resin composition, and a liquid crystal display. The negative photosensitive resin composition is characterized by containing [A] an alkali-soluble resin (a) composed of a monomer unit derived from an unsaturated carboxylic acid and a monomer unit derived from a radically polymerizable unsaturated compound, and an alkali-soluble resin (b) composed of a monomer unit derived from an unsaturated carboxylic acid and a monomer unit derived from an epoxy group-containing radically polymerizable unsaturated compound, [B] a polyfunctional (meth)acrylate and [C] a photopolymerization initiator. Also specifically disclosed are a spacer made of such a negative photosensitive resin composition, and a liquid crystal display comprising such a spacer.

Description

Negative light-sensitive resin combination, interval body and liquid crystal indicator
Technical field
The present invention relates to negative light-sensitive resin combination.More particularly, relate to and be suitable as interval body with the negative light-sensitive resin combination of photosensitive material, the interval body and the liquid crystal indicator that use this negative light-sensitive resin combination to make.
Background technology
Usually, liquid crystal indicator is to form by dispose liquid crystal orientating membrane, liquid crystal etc. between the substrate that stacked transparency electrode forms on thin film transistor (TFT) (being designated hereinafter simply as " TFT ") substrate and the opposed with it filter substrate.In order to obtain high-quality liquid crystal indicator, must accurately and equably control two gaps (gap) between the substrate, in order to control this gap, adopted silica bead or plastic bead even-granular interval body with regulation particle diameter in the past always.Yet, because the isolation of these granular interval bodies is shaped as sphere, therefore, be difficult to it is dispersed on the ad-hoc location of substrate, cause variety of problems thus.Promptly, these granular interval bodies might be dispersed on the black matrix (Black Matrix), on any one member on the pixel electrode of TFT or on the TFT, when being dispersed on the black matrix, granular interval body can not cause any problem, but when granular interval body is dispersed on the pixel electrode of TFT, because granular interval body exists the pixel of part what contribution demonstration is not had, therefore, if normality black mode (normally blackmode) liquid crystal, the light that then produces backlight sees through in the granular interval body, so-called hickie phenomenon (white spot phenomenon) exists the problem that contrast reduces.In addition, when being dispersed on the TFT,, when applying TFT substrate and filter substrate, the worry that mechanically destroys TFT is arranged, exist the problem that reduces the liquid crystal indicator yield rate because granular interval body is the high particle of hardness as if granular interval body.
On the other hand, as solving because of using the method for the variety of issue that these granular interval bodies produce, propose the usability photosensitive resin composition, and made the method (for example, patent documentation 1 etc.) of interval body by photolithography (photolithography) in the position of regulation.The interval body of Ti Chuing in the method, both can on the TFT substrate, make, also can on filter substrate, make, but because it is made by the technology identical with the manufacture craft of look filter, therefore on filter substrate, make specially, wherein, the color filter manufacture craft is meant the technology that is coloured to the photonasty resist layer of red, green, blue by photolithography processing.Specifically; for example; on glass substrate, form color filter and be coated with diaphragm; perhaps, be not coated with as required, but sputter becomes the indium-tin-oxide (ITO) of transparency electrode; after directly making interval body by photolithography; then, implement friction treatment, thereby produce filter substrate with print process coating oriented film and after calcining.The oriented film that uses in the manufacturing of this filter substrate, in most cases adopt polyimide film or polyamide acid film, owing to only in the high polar solvent of gamma-butyrolacton or N-Methyl pyrrolidone etc., just have dissolubility, therefore, when being coated on oriented film on the transparency electrode by print process, if even the development residue when making interval body is present on the minimum part, this residue part can be stained with (promptly, repel) contain the high polar solvent of oriented film material, cause not having oriented film in this part, finally cause the reduction of liquid crystal indicator yield rate.Development when therefore, being necessary fully to improve the making interval body in advance.As the nearest interval body that proposes resin combination, for example, disclose and contained the alkali-soluble multipolymer, compound with ethene unsaturated double-bond, the content that the radiation-sensitive resin composition of epoxy compound and radioactive ray radical polymerization initiator is suitable as spacer material (for example, patent documentation 2 etc.), but nowadays, in the manufacturing of the filter substrate of the large-size glass substrate about using a length of side as 2m, do not allow to exist the development residue of a wee bit, in this case, because the alkali-soluble of the epoxy compound in the above-mentioned resin combination is low, therefore, exist the problem that can't solve the development residue.
On the other hand, though make liquid crystal indicator usually at normal temperatures, the liquid crystal indicator of manufacturing might transport under the extremely low temperature condition, maybe might be exposed under the extremely low temperature of cold district.So, if liquid crystal indicator is placed on the environment of extremely low temperature for a long time, then the liquid crystal that exists between TFT substrate and filter substrate shrinks, under the situation of granular interval body that is the plastic bead that in the past always uses etc., along with the contraction of liquid crystal, granular interval body is deformed into ellipse and shrinks from positive circle, when liquid crystal indicator comes back to normal temperature environment, granular interval body recovers original positive circle, and therefore existing problem is less.But, when by common photosensitive polymer combination, promptly by containing alkali soluble resin, at least have the polymerizable compound of an ethene unsaturated double-bond and the photosensitive polymer combination of Photoepolymerizationinitiater initiater (for example patent documentation 3 etc.) when making interval body, it is abundant that in most cases the shrinkage factor of interval body does not have the contraction of liquid crystal, contact portion at substrate and interval body produces the space that is known as " low-temp foaming " thus, even and if liquid crystal indicator is got back under the environment of normal temperature, also can't eliminate this space, its result exists the problem that causes that demonstration is bad.And then, the resin combination that contains multipolymer is also disclosed, described multipolymer be in the alkali-soluble multipolymer, contain ormal weight for example from the multipolymer (for example, patent documentation 4,5 etc.) of the monomeric unit of 1,3-butadiene or isoprene equiconjugate dienes unsaturated compound.But, in patent documentation 4 disclosed resin combinations, since little from the content of the monomeric unit of conjugated diolefine unsaturated compounds shared ratio in the multipolymer total amount, therefore, be difficult to the interval body that obtains having desired shrinkage factor from this resin combination; In patent documentation 5 disclosed resin combinations, but contain from 1 though put down in writing with respect to multipolymer total amount height ratio ground, the content of the monomeric unit of 3-butadiene or isoprene, but in fact, contain from 1 even want to produce with height ratio according to patent documentation 5 disclosed methods, the multipolymer of the monomeric unit of 3-butadiene or isoprene, because 1,3-butadiene or isoprene equiconjugate dienes unsaturated compound reactive low, be difficult to produce the target multipolymer, its result exists the problem that is difficult to obtain having from this resin combination the interval body of required shrinkage factor as can be known.On the contrary, if just the interval body raw material itself is softened, when liquid crystal indicator is positioned over the environment of utmost point low temperature, even height step-down according to the contraction interval body of liquid crystal, can not return to when getting back to normal temperature environment and be placed on utmost point low-temperature condition height before, cause interval body from strippable substrate thus, can't play the gap that makes between the substrate and remain on constant original effect.Recently, in order to solve the problem that produces low-temp foaming in this utmost point low temperature environment, the scheme that has proposed to form on the surface of interval body small jog (for example, patent documentation 6 etc.), but because it is small jog, when being placed for a long time under the state that occurs being out of shape when this small jog pressurized, also be difficult to reproduce original concavo-convex problem under the normal temperature even exist to get back to.
In this case, wish to develop and to make the problem that does not produce aforesaid development residue, and then with granular interval body in the same manner, contraction along with liquid crystal under the state that is positioned over utmost point low temperature is shunk, when the negative light-sensitive resin combination that comes back to the interval body that can recover original height under the normal temperature state.
Patent documentation 1:JP spy opens clear 62-90622 communique
Patent documentation 2:JP spy opens flat 10-319592 communique
Patent documentation 3:JP spy opens flat 6-43643 communique
Patent documentation 4:JP spy opens flat 6-157716 communique
Patent documentation 5:JP spy opens flat 11-133600 communique
Patent documentation 6:JP spy opens the 2005-99278 communique
Summary of the invention
The problem that invention will solve
Problem of the present invention is, a kind of negative light-sensitive resin combination is provided, this negative light-sensitive resin combination is for example in the manufacturing of liquid crystal indicator, can suppress to make the development residue that produces when adopting photolithography in the operation of interval body etc., can not produce the problem that the quality of the liquid crystal indicator that causes because of the development residue reduces.And then, problem of the present invention is, a kind of negative light-sensitive resin combination is provided, according to this negative light-sensitive resin combination, can produce and to suppress problems such as the demonstration that causes because of low-temp foaming is bad and interval body with high shrinkage and high resiliency response rate.
In addition, another problem that the present invention will solve is that interval body and the liquid crystal indicator made by this resin combination are provided.
Solve the method for problem
Negative light-sensitive resin combination of the present invention, it is characterized in that, contain: [A] is (a) by the alkali soluble resin that constitutes from the monomeric unit of unsaturated carboxylic acid and monomeric unit from free-radical polymerised unsaturated compound and multi-functional (methyl) acrylate of alkali soluble resin, [B] and [C] Photoepolymerizationinitiater initiater of (b) being made of the monomeric unit from the monomeric unit of unsaturated carboxylic acid and the free-radical polymerised unsaturated compound that comes self-contained epoxy radicals.
In addition, the present invention is the interval body of being made by above-mentioned negative light-sensitive resin combination.
And then the present invention is a kind of liquid crystal indicator, it is characterized in that having above-mentioned interval body.
The effect of invention
Because alkali-soluble (development) excellence of negative light-sensitive resin combination of the present invention, therefore, when using resin combination Production Example of the present invention such as liquid crystal indicator to use interval body, can not produce because of the development residue cause, because to repel the coating that high polar solvent etc. that (は じ I) contain oriented film material causes bad, and then the quality that can suppress liquid crystal indicator reduces.
In addition, because the interval body by negative light-sensitive resin combination manufacturing of the present invention has high shrinkage and high resiliency response rate, therefore, even will have under the situation that the liquid crystal indicator of this interval body is positioned over utmost point low temperature, than compared the generation that can suppress low-temp foaming in the past, and then it is bad to suppress the demonstration that causes because of low-temp foaming.
Embodiment
Among the present invention, as the alkali soluble resin a kind of composition in two kinds of alkali soluble resins, that use [A] (a) to represent, can be by in The suitable solvent, use suitable radical initiator, make unsaturated carboxylic acid and free-radical polymerised unsaturated polymerizable compound and make, alkaline developer described later is had the dissolubility of appropriateness.In addition, each monomeric unit that constitutes alkali soluble resin is not a composition independently, but forms multipolymer jointly with other monomeric unit, but for convenience of explanation following, sometimes with original monomer record.
These unsaturated carboxylic acids both can be used alone, and also several suitably the combination can be used.
Above-mentioned [A] free-radical polymerised unsaturated compound in (a) is meant it mainly is, above-mentioned unsaturated carboxylic acid that the alkali soluble resin (a) represent with [A] uses the dissolubility of alkaline developer or mechanical property etc. in order to regulate aptly and the free-radical polymerised unsaturated compound free-radical polymerised unsaturated compound in addition that contains epoxy radicals described later.Concrete example as this free-radical polymerised unsaturated compound, for example, can enumerate (methyl) methyl acrylate { (methyl) acrylic acid is meant acrylic or methacrylic acid, as follows Specifications }, (methyl) ethyl acrylate, (methyl) acrylic acid n-pro-pyl ester, (methyl) acrylic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) acrylic acid isobutyl, (methyl) acrylic acid sec-butyl ester, (methyl) acrylic acid tertiary butyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid n-hexyl ester, (methyl) acrylic acid-2-ethyl hexyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid two cyclopentyl esters, (methyl) alkyl acrylate of (methyl) acryloxy two cyclopentyloxy ethyl esters etc.; (methyl) acrylic acid aryl ester of (methyl) phenyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid phenoxy ethyl etc.; (methyl) acrylic acid hydroxyalkyl acrylate of (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-3-hydroxyl n-pro-pyl ester etc.; The α of dimethyl maleate, diethyl maleate, maleic acid di ester, maleic acid diisopropyl ester, maleic acid di-n-butyl ester, dimethyl fumarate, DEF, fumaric acid di ester, fumaric acid diisopropyl ester, fumaric acid di-n-butyl ester etc., β-unsaturated dicarboxylic dialkyl; The N-substituted maleimide amine of N-phenylmaleimide, N-cyclohexyl maleimide etc.; The phenylethylene of styrene, α-Jia Jibenyixi, o-methyl styrene, m-methyl styrene, p-methyl styrene etc.; 1,3-butadiene, isoprene, chlorbutadiene, 2,3-dimethyl-1, the conjugated diolefine unsaturated compounds of 3-butadiene, 1,3-pentadiene etc. etc., wherein, preferred conjugated diolefine unsaturated compounds, conjugated diolefine unsaturated compounds be the combination of yoke dienes unsaturated compound free-radical polymerised unsaturated compound in addition together, as the conjugated diolefine unsaturated compounds, more preferably 1,3-butadiene, isoprene.These other free-radical polymerised unsaturated compound both can be used alone, and also several suitably the combination can be used.
In monomeric unit from above-mentioned free-radical polymerised unsaturated compound, particularly import in the alkali soluble resin, can access the high shrinkage with one of effect of the present invention and the resin of high resiliency response rate by the monomeric unit of self-conjugate dienes unsaturated compound in the future.In addition,, can regulate the polymerization speed when making resin by the free-radical polymerised unsaturated compound beyond conjugated diolefine unsaturated compounds and the conjugated diolefine unsaturated compounds is made up, and then, the control of molecular weight is also become easy.
The content of monomeric unit in the alkali soluble resin of (a) representing with [A] from unsaturated carboxylic acid, usually employing can make the acid value of resin reach the content of the scope of 30～250mgKOH/g, and preferred employing can make the acid value of resin reach the content of the scope of 40～150mgKOH/g.If acid value is lower than 30mgKOH/g,, when for example with the alkali development treatment in the resin combination enforcement photolithography that contains this resin,, therefore exist the problem that produces the development residue because developing performance is poor because the quantity of carboxyl is few in the resin.On the other hand, if acid value surpasses 250mgKOH/g, for example, when with the alkali development treatment in the resin combination enforcement photolithography that contains this resin, because alkali affinity is very high, therefore, existing the side etching amount increases, and can not get fully and the problem of the tack of transparent electrode substrate.In addition, acid value be by in and the needed potassium hydroxide of 1g alkali soluble resin the milligram number represent, can carry out titration by mixed solution usually and obtain with alcohols such as potassium hydroxide aqueous solution or potassium hydroxide aqueous solution and ethanol.
In addition, the monomeric unit that comprises in the alkali soluble resin of (a) representing with [A] from unsaturated carboxylic acid, it not only can be monomeric unit from monocarboxylic acid, it also can be monomeric unit from dicarboxylic acid, in addition, because molecular weight is different respectively, very difficult regulation can reach the weight % of the acid value scope of above-mentioned resin, but the content of this monomeric unit is generally 10～40 weight %, is preferably 15～30 weight %.
The content of shared monomeric unit from free-radical polymerised unsaturated compound is generally 60～90 weight % in the alkali soluble resin of (a) representing with [A], is preferably 70～85 weight %.
Particularly, in order to obtain having the high shrinkage of one of effect of the present invention and the resin of high resiliency response rate, preferably the monomeric unit from the conjugated diolefine unsaturated compounds is generally 5～80 weight % at the content of (a) representing with [A] from the monomeric unit of free-radical polymerised unsaturated compound that alkali soluble resin comprised, be preferably 10～70 weight %, have the alkali soluble resin of usefulness (a) expression of this composition by use, can more effectively reach above-mentioned effect.
Consider the negative light-sensitive resin combination of the present invention that contains the alkali soluble resin that [A] (a) represent thermotolerance, coating, in the dissolubility of solvent, the alkali development treatment to dissolubility of alkaline developer etc., the weight average molecular weight of the alkali soluble resin of (a) representing with [A] is preferably 8000～50000, and more preferably 10000～30000.In addition, weight average molecular weight is by gel permeation chromatography, and the numerical value that converts with polystyrene standard.
The alkali soluble resin of (b) representing as the usefulness [A] of another composition in two kinds of alkali soluble resins that constitute the present composition, can by with unsaturated carboxylic acid with contain the free-radical polymerised unsaturated compound of epoxy radicals in The suitable solvent, and use the in addition polymerization and making of suitable radical initiator, alkaline developer described later is had favorable dissolution properties.
As above-mentioned [A] unsaturated carboxylic acid in (b), can enumerate the identical compound of unsaturated carboxylic acid in (a) with above-mentioned [A], and, as preferred carboxylic acid can enumerate with above-mentioned [A] (a) in the preferred identical compound of unsaturated carboxylic acid, and then, as carboxylic acid more preferably also can enumerate with above-mentioned [A] the identical compound of preferred unsaturated carboxylic acid in (a).These unsaturated carboxylic acids both can use wherein a kind of separately, also can be and use with wherein several the combination, and these unsaturated carboxylic acids both can use the identical compound of unsaturated carboxylic acid in (a) with above-mentioned [A], also can use other compound.
These free-radical polymerised unsaturated compounds that contain epoxy radicals both can be used alone, and also several the combination can be used.
Monomeric unit content in the alkali soluble resin of (b) representing with [A] from unsaturated carboxylic acid, usually employing can make the acid value of resin reach the content of 30～250mgKOH/g scope, wherein, preferred employing can make the acid value of resin reach the content of 40～150mgKOH/g scope.If acid value is lower than 30mgKOH/g,, therefore, for example when with the alkali development treatment in the resin combination enforcement photolithography that contains this resin, there is the problem that produces the development residue owing to the developing performance difference because the carboxyl quantity in the resin is few.On the other hand, if acid value surpasses 250mgKOH/g, for example can reduce the storage stability when preserving this resin, perhaps, when with the alkali development treatment in the resin combination enforcement photolithography that contains this resin, be difficult to control the alkali developing powder, produce the problem be difficult to guarantee that the fidelity to the tack of substrate or pattern reduces.
In addition, the monomeric unit that comprises in the alkali soluble resin of (b) representing with [A] from unsaturated carboxylic acid, it not only can be monomeric unit from monocarboxylic acid, it also can be monomer list from dicarboxylic acid, and, because molecular weight is respectively different, therefore be difficult to stipulate to reach the weight % of the acid value scope of above-mentioned resin, but the content of this monomeric unit is generally 5～40 weight %, is preferably 10～30 weight %.
The monomeric unit content of the free-radical polymerised unsaturated compound of the next self-contained epoxy radicals in the alkali soluble resin of (b) representing with [A] is generally 60～95 weight %, is preferably 70～90 weight %.
Consider the negative light-sensitive resin combination that contains the alkali soluble resin that [A] (b) represent thermotolerance, coating, in the dissolubility of solvent, the alkali development treatment to dissolubility of developer solution etc., the weight average molecular weight of the alkali soluble resin of (b) representing with [A] is preferably 8000～50000, and more preferably 10000～30000.
The alkali soluble resin of (b) representing with [A], it is the alkali soluble resin that the monomeric unit from the monomeric unit of unsaturated carboxylic acid and the free-radical polymerised unsaturated compound that comes self-contained epoxy radicals by said possibility with gelation in the past constitutes, but known condition during by selective polymerization, can under the situation that does not cause gelation, carry out polymerization, thus, by common use [A] (a) and [A] resin of (b) representing, can realize the resin that alkali-soluble is high, and then, can realize the resin combination of development property excellence.And, because the necessary all rerum naturas of monomeric unit of coming the free-radical polymerised unsaturated compound of self-contained epoxy radicals in the alkali soluble resin of using [A] (b) to represent, for example, even the monomeric unit of the free-radical polymerised unsaturated compound that contains epoxy radicals low from alkali-soluble, that molecular weight is high, because resin itself contains the monomeric unit from unsaturated carboxylic acid, therefore, can make it have high-alkali developing performance.
The ratio that cooperates with [A] alkali soluble resin of (a) representing and alkali soluble resin of (b) representing with [A] is generally (a)/(b)=20/80～80/20 weight %, more preferably (a)/(b)=40/60～60/40 weight %.If use the ratio of the alkali soluble resin of (a) expression to surpass 80 weight %, then use the alkali soluble resin ratio of (b) expression relatively to reduce, have the reaction that can not get with existing in the carboxyl that exists in the alkali soluble resin of (a) expression and the alkali soluble resin of representing with (b) between the epoxy radicals.On the other hand, ratio with the alkali soluble resin of (b) expression surpasses 80 weight %, then use the ratio of alkali soluble resin of (a) expression relatively to reduce, therefore, exist and for example be difficult to obtain having the high shrinkage of one of effect of the present invention and the problems such as resin of high resiliency response rate.
Owing to have carboxyl in the alkali soluble resin that above-mentioned usefulness [A] (a) is represented, and there is epoxy radicals in the alkali soluble resin of using [A] (b) to represent on the other hand, therefore, for example when (a) reached the solution coat of alkali soluble resin (b) at glass substrate, heat after forming film, then carboxyl and epoxy radicals are carried out crosslinkedly easily, can form the high thermotolerance cured film of hardness thus.In addition, owing to (a) and in the alkali soluble resin (b) have carboxyl, the resin of (a) and (b) all has high-alkali developing performance, therefore, to the favorable solubility of alkaline developer, can not produce the development residue.And then, by as [A] the monomeric unit in (a), use monomeric unit from the conjugated diolefine unsaturated compounds from free-radical polymerised unsaturated compound, make the resin after crosslinked have high shrinkage and high resiliency response rate.
As carrying in the above, with [A] (a) and [A] alkali soluble resin of (b) representing, can be by the conventional method manufacturing, for example, the monomer that will constitute each resin as required is dissolved in the suitable organic solvent, then behind the radical initiator that the interpolation solution polymerization is used in this solution, be heated to the above temperature of temperature of this radical initiator generation free radical, then, under the situation of considering heat of polymerization, control temperature limit, limit makes its reaction (solution polymerization) and makes.In addition, also can be according to following method manufacturing: radical initiator is dissolved in the suitable organic solvent in advance, this solution is heated to after radical initiator produces temperature more than the temperature of free radical, speed in accordance with regulations to wherein slowly interpolation will constitute the potpourri that the monomer of resin is mixed, make it react (solution polymerization), produce alkali soluble resin thus, and then, also can radical initiator be dissolved in the suitable organic solvent in advance, this solution is heated to after radical initiator produces temperature more than the temperature of free radical, under the situation of the free radical reaction of considering each monomer, change interpolation speed and slowly add the monomer that constitutes resin respectively to this solution, thereby make its reaction (solution polymerization), make alkali soluble resin thus.
As above-mentioned organic solvent, specifically, for example can enumerate the ethylene glycol monoalkyl ether of glycol monoethyl ether, ethylene glycol monoethyl ether, glycol monomethyl n-propyl ether, glycol monomethyl n-butyl ether etc.; The ethylene glycol bisthioglycolate alkyl ether of glycol dimethyl ether, ethylene glycol ethyl ethers ylmethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate n-propyl ether, ethylene glycol bisthioglycolate n-butyl ether etc.; The propylene-glycol monoalky lether of propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether etc.; The propylene glycol dialkyl ether of Propylene Glycol Dimethyl Ether, propylene glycol ethyl-methyl ether, propylene glycol Anaesthetie Ether, propylene glycol di ether, propylene glycol di-n-butyl ether etc.; The diethylene glycol monoalky lether of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether etc.; The diethylene glycol dialkyl ether of diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether etc.; The dipropylene glycol monoalky lether of dipropylene glycol monomethyl ether, the single ether of dipropylene glycol etc.; The dipropylene glycol dialkyl ether of dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol Anaesthetie Ether etc.; The ethylene glycol monoalkyl ether acetate of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl n-propyl ether acetic acid esters, glycol monomethyl n-butyl ether acetic acid esters etc.; The propylene-glycol monoalky lether acetic acid esters of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list n-propyl ether acetic acid esters, propylene glycol list n-butyl ether acetic acid esters etc.; The diethylene glycol monoalky lether acetic acid esters of diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters etc.; Methoxy Methyl Acetate, the ethoxy methyl acetate, the positive propoxy methyl acetate, the n-butoxy methyl acetate, the Methoxy acetic acid ethyl ester, the ethoxy ethyl acetate, the positive propoxy ethyl acetate, the n-butoxy ethyl acetate, Methoxy acetic acid n-pro-pyl ester, ethoxy acetic acid n-pro-pyl ester, positive propoxy acetic acid n-pro-pyl ester, n-butoxy acetic acid n-pro-pyl ester, the Methoxy acetic acid n-butyl, ethoxy acetic acid n-butyl, positive propoxy acetic acid n-butyl, the alkoxy acetic acid Arrcostab of n-butoxy acetic acid n-butyl etc.; The 3-alkoxypropan acid alkyl ester of 3-methoxypropionic acid methyl esters, 3-ethoxy-propionic acid methyl esters, 3-positive propoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-positive propoxy ethyl propionate, 3-methoxypropionic acid n-pro-pyl ester, 3-ethoxy-propionic acid n-pro-pyl ester, 3-positive propoxy propionic acid n-pro-pyl ester etc.; The hydroxacetic acid Arrcostab of hydroxacetic acid methyl esters, hydroxacetic acid ethyl ester, hydroxacetic acid n-pro-pyl ester etc.; The 3-hydracrylic acid Arrcostab of 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-pro-pyl ester etc.; The lactic acid alkyl ester of methyl lactate, ethyl lactate, lactic acid n-pro-pyl ester, lactic acid n-butyl etc.; The 2-hydroxy-iso-butyric acid Arrcostab of 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, 2-hydroxy-iso-butyric acid n-pro-pyl ester etc.; The aklylene glycol diacetate esters of ethylene acetate, propylene-glycol diacetate etc.; The 3-alkoxy propyl alcohol of 3-methoxypropanol, 3-ethoxy propyl alcohol, 3-positive propoxy propyl alcohol etc.; The dialkyl malonate of dimethyl malenate, diethyl malonate, malonic acid di ester etc.; The succinic acid dialkyl ester of dimethyl succinate, diethyl succinate, succinic acid di-n-propyl ester etc. etc., wherein, the propylene-glycol monoalky lether acetic acid esters of preferred propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list n-propyl ether acetic acid esters, propylene glycol list n-butyl ether acetic acid esters etc.; The diethylene glycol dialkyl ether of diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether etc.; The dipropylene glycol dialkyl ether of dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol Anaesthetie Ether etc., wherein, more preferably propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, dipropylene glycol dimethyl ether.To the chain transfer coefficient of this solvent, long preservation stability etc., these organic solvents both can be used alone, and also several suitably the mixing can be used when considering the gained alkali soluble resin to the dissolubility of this solvent, polymerization.In addition, the use amount of these organic solvents is not done special qualification, but usually with respect to [A] (a) and [A] alkali soluble resin 100 weight portions of (b) representing, the use amount of organic solvent is 100～400 weight portions.
The radical initiator of using as above-mentioned solution polymerization, specifically, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2, the 4-methyl pentane nitrile), 1,1 '-azo two (cyclohexane-1-formonitrile HCN), 2,2 '-azo two (isobutyric acid) dimethyl ester, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionamide], 2,2 '-azo two 2-methyl-N-[1, two (the hydroxymethyl)-2-hydroxyethyls of 1-] propionamide }, 2, the azo-compound of 2 '-azo two { 2-methyl-N-[2-(1-hydroxybutyl)] propionamide } etc.; 1; 1-two (t-butylperoxy) cyclohexane; 1; 1-two (t-butylperoxy)-2-methylcyclohexane; 1; 1-two (t-butylperoxy)-3; 3; the 5-trimethyl-cyclohexane; hydrogen phosphide cumene; 2; 2-two (t-butylperoxy) butane; two lauroyl peroxides; benzoyl peroxide; benzoyl-m-methylbenzoyl peroxide; t-butylperoxy-2 ethyl hexanoic acid; uncle's hexyl peroxy-2 ethyl hexanoic acid; 1; 1; 3; the organic peroxide of 3-tetramethyl butyl peroxy-2 ethyl hexanoic acid etc. etc.; wherein; preferred 2; 2 '-azoisobutyronitrile; 2; 2 '-azo two (2-methylbutyronitrile); 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (4-methoxyl-2; the 4-methyl pentane nitrile); 1; 1 '-azo two (cyclohexane-1-formonitrile HCN); 2; 2 '-azo-bis-iso-dimethyl; 4; 4 '-azo two (4-cyanopentanoic acid); 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionamide]; 2,2 '-azo two { 2-methyl-N-[1; two (the hydroxymethyl)-2-hydroxyethyls of 1-] propionamide }; 2; the azo-compound of 2 '-azo two { 2-methyl-N-[2-(1-hydroxybutyl)] propionamide } etc., wherein, more preferably 2; 2 '-azo two (2, the 4-methyl pentane nitrile).These radical initiators both can be used alone, and also several suitably the combination can be used, and the temperature when beginning according to polymerization or the weight average molecular weight of alkali soluble resin control its kind or addition gets final product.In addition, these radical initiators also can suitably use commercially available radical initiator.
Make with [A] (a) and [A] (b) represent alkali soluble resin the time, except above-mentioned organic solvent and radical initiator,, can also add molecular weight regulator in order to control the weight average molecular weight of alkali soluble resin.As molecular weight regulator, particularly, for example can enumerate the thio-alcohol of n-hexyl mercaptan, n-octyl mercaptan, n-dodecane mercaptan, uncle's dodecyl mercaptans etc.; The xanthate class of two sulfo-dimethyl yellow ortho esters, isopropyl xanthogen disulfide etc.; The terpenes hydrocarbon of terpinolene (Terpinolene) etc.; α-Jia Jibenyixi dimer etc., wherein, the thio-alcohol of preferred n-hexyl mercaptan, n-octyl mercaptan, n-dodecane mercaptan, uncle's dodecyl mercaptans etc.; The α-Jia Jibenyixi dimer, wherein, more preferably uncle's dodecyl mercaptans, α-Jia Jibenyixi dimer.These molecular weight regulators both can be used alone, and also several suitably the combination can be used.There is no particular limitation to the use amount of these molecular weight regulators.In addition, these molecular weight regulators also can suitably use commercially available molecular weight regulator.
For above-mentioned solution polymerization, since make with [A] (a) and [A] (b) represent alkali soluble resin the time reaction (solution polymerization) temperature be according to the weight average molecular weight of desired alkali soluble resin, employed radical initiator kind or addition, have or not molecular weight regulator or its addition etc. to change, therefore cannot treat different things as the same, but get final product suitably selecting desirable temperature usually from 0～100 ℃ of temperature range.
In the alkali soluble resin of [A], also can make by known emulsion polymerization with the alkali soluble resin that [A] (a) represents.Specifically, after for example in water, adding emulsifying agent, emulsion polymerization radical initiator, molecular weight regulator as required, perhaps in this solution, add the potpourri that mixing unsaturated carboxylic acid and free-radical polymerised unsaturated compound form quickly, perhaps slowly add the potpourri that mixing unsaturated carboxylic acid and free-radical polymerised unsaturated compound form, and make it under suitable temperature, to react (emulsion polymerization), thereby the alkali soluble resin that the usefulness of producing [A] (a) is represented.
As mentioned emulsifier, particularly, for example can enumerate the alkyl carboxylate of sodium laurate, potassium laurate, sodium oleate, potassium oleate, odium stearate, potassium stearate etc.; The alkyl sulfate of NaLS, lauryl potassium sulfate, Texapon Special etc.; The alkyl benzene sulphonate hydrochlorate of neopelex etc.; Disproportionated rosin acid potassium etc.These emulsifying agents both can be used alone, and also several suitably the mixing can be used, and the use amount of these emulsifying agents is not done special qualification.In addition, these molecular weight regulators can also use commercially available material.
The radical initiator that polymerization is used as above-mentioned emulsion particularly, for example can be enumerated the persulfate of sodium peroxydisulfate, potassium persulfate, ammonium persulfate etc.; 2,2 '-azoisobutyronitrile, 2, the azo-compound of 2 '-azo two (2-methyl-propyl amidine) dihydrochloride etc.; The organic peroxide of benzoyl peroxide, acetyl peroxide, lauroyl peroxide, hydrogen phosphide cumene etc.; Hydrogen peroxide etc.These radical initiators both can be used alone, and also several suitably the combination can be used, and the temperature in the time of can beginning according to polymerization or the weight average molecular weight of alkali soluble resin are controlled its kind or addition.In addition, these radical initiators can use commercially available radical initiator.
In addition, temperature of reaction when reducing emulsion polymerization, for example, the redox class polymerization initiator that also can use the reductive agent with the oxygenant of the persulfate of sodium peroxydisulfate, potassium persulfate, ammonium persulfate etc. and hydrogen phosphide cumene, iron sulfate etc. and acid sodium sulphite etc. to be made up.In addition, these redox class polymerization initiators can suitably use commercially available redox class polymerization initiator.
As above-mentioned molecular weight regulator, the identical compound of molecular weight regulator that can use in the time of can enumerating with above-mentioned solution polymerization.These molecular weight regulators both can be used alone class, also several suitably the mixing can be used, and the use amount of these molecular weight regulators is not done special qualification.
For the above-mentioned emulsion polymerization, reaction (emulsion polymerization) temperature when making the alkali soluble resin of (a) representing with [A] be according to the weight average molecular weight of desired alkali soluble resin, employed radical initiator kind or addition, have or not variations such as molecular weight regulator or its addition, therefore, cannot treat different things as the same, suitably select temperature desired to get final product from 0～100 ℃ temperature range usually.
In addition, because emulsion polymerization is in aqueous solvent, monomer separately participates in reaction in the formed micella of emulsifying agent (micelle), therefore, we can say and used aqueous solvent, but come down to block polymerization.Therefore, aggregate rate is high more, and is easy more crosslinked and produce gelation between the resin that is generated, and aggregate rate is more near 100%, exists the resin that forms with little bulk (Network ラ system shape) and is dissolved in problem in the organic solvent hardly.For this reason,, be necessary to measure repeatedly aggregate rate, before gelation occurs, make reaction terminating in order to obtain to be dissolved in the resin in the organic solvent.
Obtain the method for alkali soluble resin as the reactant liquor after solution polymerization or emulsion polymerization, can separate by known method, specifically, for example, by reactant liquor is carried out steam distillation, after unreacted monomer or solvent etc. are removed in distillation, and then pass through as methyl alcohol, the alcohols solvent of ethanol etc., n-pentane, the non-polar solvent of normal hexane etc., water etc. wash gained bottoms (resin), then, carry out drying under reduced pressure or reactant liquor is dropped to as methyl alcohol, the alcohols solvent of ethanol etc., n-pentane, in the solvent of the non-polar solvent of normal hexane etc. etc., after obtaining the resin of separating out by filtration because of the drippage crystallization, further pass through as methyl alcohol, the alcohols solvent of ethanol etc., n-pentane, the non-polar solvent of normal hexane etc., washing such as water gained resin, then, by carrying out drying under reduced pressure, can isolate alkali soluble resin.
Constitute multi-functional (methyl) acrylate present composition, that use [B] expression, it is (methyl) acrylate with two above ethene unsaturated double-bonds that can polymerization by rayed, specifically, for example can enumerate many ethylene glycol bisthioglycolates (methyl) acrylate of ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate etc.; Many propylene glycol two (methyl) acrylate of propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc.; 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1, alkyl diol two (methyl) acrylate of 9-nonanediol two (methyl) acrylate etc.; Neopentyl glycol two (methyl) esters of acrylic acid of neopentyl glycol two (methyl) acrylate, ethylene oxide modification neopentyl glycol two (methyl) acrylate, propylene oxide modification neopentyl glycol two (methyl) acrylate etc.; Bisphenol-A two (methyl) esters of acrylic acid of bisphenol-A two (methyl) acrylate { 2, two [4-(methyl) acryloxy phenyl] propane of 2-}, ethylene oxide modified bisphenol A two (methyl) acrylate, propylene oxide modified bisphenol A two (methyl) acrylate etc.; Three (methyl) acrylic acid glyceride type of three (methyl) acrylic acid glyceride, ethylene oxide modification three (methyl) acrylic acid glyceride, propylene oxide modification three (methyl) acrylic acid glyceride etc.; Trimethylolpropane tris (methyl) esters of acrylic acid of trimethylolpropane tris (methyl) acrylate, ethylene oxide modification trimethylolpropane tris (methyl) acrylate, propylene oxide modification trimethylolpropane tris (methyl) acrylate, 6-caprolactone modification trimethylolpropane tris (methyl) acrylate etc.; Three [(methyl) acryloxyalkyl] isocyanuric acid ester of three [2-(methyl) acryloxy ethyl] isocyanuric acid ester, three [3-(methyl) acryloxy propyl group] isocyanuric acid ester etc.; Two-trimethylolpropane four (methyl) esters of acrylic acid of two-trimethylolpropane four (methyl) acrylate, 6-caprolactone modification two-trimethylolpropane four (methyl) acrylate etc.; Pentaerythrite four (methyl) esters of acrylic acid of pentaerythrite four (methyl) acrylate, 6-caprolactone modification pentaerythrite four (methyl) acrylate etc.; Dipentaerythritol six (methyl) esters of acrylic acid of dipentaerythritol six (methyl) acrylate, 6-caprolactone modification dipentaerythritol six (methyl) acrylate etc. etc.The performance of resin combination according to the present invention, these multi-functional (methyl) acrylate can be used alone, and also can suitably make up several and use.
The effect of multi-functional (methyl) acrylate with [B] expression; film speed when mainly being control use resin combination enforcement of the present invention photolithography; and by the distance (length) between two above acryloyl group chains that exist in multi-functional (methyl) acrylate, control has the characteristics such as physical strength, shrinkage factor of the resin of IPN (Interpenetrating) structure.Promptly, sense of control ray velocity as first effect, be meant that when carrying out photolithography the free radical that Photoepolymerizationinitiater initiater produced that control is represented by the usefulness [C] that constitutes the present composition with multi-functional (methyl) acrylate of [B] expression carries out free radical chain reactions and polymerization speed during polymerization; Be meant as characteristics such as the second control physical strength that acts on, shrinkage factors, by described later make cause between the alkali soluble resin hot high molecular weight reactive after cure, carry out three-dimensional cross-linked between the alkali soluble resin, thereby formation interpenetrating structure, characteristics such as control physical strength, shrinkage factor are meant characteristics such as the physical strength, shrinkage factor of this structure of control.
Total total amount with respect to the usefulness [A] of 100 weight portions alkali soluble resin of (a) representing and the alkali soluble resin of (b) representing with [A], the addition of multi-functional (methyl) acrylate with [B] expression is generally 30～120 weight portions, is preferably 50～120 weight portions.If be lower than 30 weight portions; because the concentration of the acryloyl group that exists in multi-functional (methyl) acrylate of usefulness [B] expression of the formation present composition relatively reduces; therefore; the speed of above-mentioned free radical chain reactions is slack-off; can not improve sensitivity; and the dissolution velocity between exposure portion, the unexposed portion is poor can not give sufficient alkali development treatment the time, therefore, exists the problem that is difficult to obtain the target interval body.On the other hand, if surpass 120 weight portions, though sensitivity improves, but compare with alkali soluble resin, too promoted the polymerization (curing) of multi-functional (methyl) acrylate that molecular weight is little, therefore, exist the problem of the interval body that is difficult to obtain one of the object of the invention with high shrinkage and high resiliency response rate.In addition, these multi-functional (methyl) acrylate with [B] expression can suitably use commercially available material.
Photoepolymerizationinitiater initiater as usefulness [C] expression that constitutes the present composition, be by rayed generation free radical, and can cause the optical free radical polymerization initiator of the polyreaction of the ethene unsaturated double-bond in multi-functional (methyl) acrylate of usefulness [B] expression, specifically, for example can enumerate benzophenone, 2,2 '-dichloro benzophenone, 4, the benzophenone of 4 '-dichloro benzophenone, 2-benzoyl benzoic acid, 4-benzoyl benzoic acid, 2-benzoyl benzoic acid methyl esters, 4-benzoyl benzoic acid methyl esters etc.; The benzoin class of benzoin, benzoin methylether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether etc.; 2,2-diethoxy acetophenone, 2,2-two n-butoxy acetophenones, 2, the acetophenones of 2-dimethoxy-2-phenyl acetophenone etc.; 1-hydroxyl hexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl-propane]-1-ketone, 2-hydroxy-2-methyl-1-{4-[4-(2-hydroxy-2-methyl propiono) benzyl] phenyl-propane }-Alpha-hydroxy ketones such as 1-ketone; 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-(N, the N-dimethylamino)-the alkyl benzene ketone of 1-(4-morpholinyl phenyl) butane-1-ketone, 2-(N, N-dimethylamino)-2-(4-methyl-benzyl)-1-(4-morpholinyl phenyl) butane-1-ketone etc.; 2,4,6-three (trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-[2-(furyl-2-yl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-[2-(5-methylfuran base-2-yl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(3, the 4-dimethoxy styrene)-4, the triazines of two (the trichloromethyl)-1,3,5-triazines of 6-etc.; 2,4, the acylphosphine oxide class of 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide etc.; 1,2-octadione-1-[4-(phenyl sulfo-)-2-(2-benzoyloxy oxime)], 2,2 '-two (2-chlorophenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., wherein, preferred 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-(N, N-dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone, 2,4,6-three (trichloromethyl)-1,3,5-triazines.These Photoepolymerizationinitiater initiaters can be selected according to the luminescent spectrum of the exposer exposure lamp that uses in the photolithography, both can be used alone, and also several suitably the combination can be used.In addition, when having the peak value of several exposure lamp luminescent spectrums,, then can improve film speed if a plurality of Photoepolymerizationinitiater initiaters are used in combination according to this peak value.
With respect to multi-functional (methyl) acrylate that the usefulness [B] of 100 weight portions is represented, use the addition of the Photoepolymerizationinitiater initiater of [C] expression to be generally 0.5～50 weight portion, be preferably 1～30 weight portion.If be lower than 0.5 weight portion, can't produce the free radical of abundant amount when in photolithography, exposing, can't fully constitute the polymerization (curing) of multi-functional (methyl) acrylate of usefulness [B] expression of the present composition, its result exists the problem that is difficult to obtain the target interval body.On the other hand, if surpass 50 weight portions, the free radical that produces during exposure carries out combination again or causes that disproportionation stops reaction, not only can't carry out polymerization (curing) effectively, and this Photoepolymerizationinitiater initiater is separated out to developer solution when carrying out the alkali development treatment sometimes, the polymerization initiator that this is separated out or attached on the substrate, perhaps after distillation and in well heater when curing attached to wall, exist that this attachment becomes impurity and the problem of polluting substrate.In addition, these Photoepolymerizationinitiater initiaters with [C] expression can suitably use commercially available material.
In addition, as required, also further make up, thereby obtain highly sensitive resin combination with sensitizer by Photoepolymerizationinitiater initiater with above-mentioned usefulness [C] expression.As sensitizer, for example can enumerate 4,4 '-two (N, N-dimethylamino) benzophenone, 4, the alkyl of 4 '-two (N, N-diethylamino) benzophenone etc. replaces diaminobenzophenone; The N of 4-(N, N-dimethylamino) benzoic acid methyl esters, 4-(N, N-dimethylamino) ethyl benzoate, 4-(N, N-dimethylamino) benzoic acid isopentyl ester etc., N-dialkyl amido benzoic acid Arrcostab etc.These sensitizers both can be used alone, and also several suitably the combination can be used.In addition, these sensitizers also can suitably use commercially available sensitizer.
Resin combination of the present invention can prepare by above-mentioned [A], [B] and [C] composition are mixed equably, it is dissolved in the The suitable solvent, thereby provides use with the form of solution.
As the solvent that in the preparation of above-mentioned resin combination, uses, so long as each composition of above-mentioned [A], [B] and [C] is dissolved equably, and do not get final product with each composition reaction, specifically, can enumerate and make above-mentioned usefulness [A] (a) and the identical solvent of organic solvent that uses during the alkali soluble resin of (b) representing with [A].And these solvents both can be used alone, and also several suitably the combination can be used.
In the scope of not damaging the object of the invention, as required, resin combination of the present invention can also contain other compositions except above-mentioned [A], [B] and [C] composition.
As other compositions, can enumerate bonding auxiliary agent, this bonding auxiliary agent is used for strengthening resin combination of the present invention is coated on glass substrate or transparent electrode substrate, and by photolithography form that predetermined pattern produces have predetermined pattern film and substrate between cementability.As this bonding auxiliary agent, can preferably enumerate silane coupling agent, particularly, can enumerate 3-glycidoxy propyl group methyl dimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-aminopropyl methyl dimethoxysilane, the 3-TSL 8330,3-aminopropyl methyldiethoxysilane, the 3-aminopropyltriethoxywerene werene, vinyltrimethoxy silane, vinyltriethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy radicals cyclohexyl) ethyl triethoxysilane, p-styrene trimethoxy silane, p-styrene triethoxysilane, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, the hexyl trimethoxy silane, the hexyl triethoxysilane, the trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane etc.These bonding auxiliary agents both can be used alone, also several suitably the combination can be used, the addition of bonding auxiliary agent is generally below 20 weight portions with respect to (a) reaching alkali soluble resin 100 weight portions that [A] (b) represents with [A], is preferably below 10 weight portions.If surpass 20 weight portions, then exist as being easy to generate the problem of development residue.
In addition, as other compositions, can enumerate the surfactant that is used to improve coating.Promptly, when coating resin combination of the present invention, for example, when the generation because of striped in the coating of being undertaken by spin-coating method causes when surface formation striated is concavo-convex, perhaps produce when being known as pears skin shape or orange peel shape surperficial delicate concavo-convex, perhaps, because the high composition solution of use surface tension, because of coating residue or substrate periphery portion return the liquid phenomenon when the substrate end periphery can not form film, add surfactant for the surface tension that reduces composition.In addition, the purpose of above-mentioned interpolation surfactant is an example wherein after all, also can add surfactant for other purposes.This surfactant can directly use commercially available surfactant, as this commercially available product, for example can enumerate MegafacF-173, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-475, Megafac F-479, Megafac F-483 (big Japanese ink chemical industry (strain) is made); Fluorad F-430, Fluorad F-431, Fluorad F-4430 (manufacturing of Sumitomo 3M company), EFTOP EF-351, EFTOP EF-352, EFTOP EF-801, EFTOP EF-802, EFTOP EF-601 (JEMCO Corporation manufacturing); Ftergent 250, ftergent251, ftergent 222F2, FTX-218 (NEOS CO., LTD. makes); The fluorine class surfactant of Surflon S-381, Surflon S-383, Surflon S-393, Surflon S-101, Surflon KH-40 (SeimiChemical Co., Ltd. makes) etc.; The silicon class surfactant of SH-28PA, SH-190, SH-193 (Toray Silicone Co., Ltd. makes) etc. etc.These surfactants both can be used alone, and also several suitably the combination can be used.In addition, the addition of surfactant is generally below 10 weight portions with respect to (a) reaching alkali soluble resin 100 weight portions that [A] (b) represents with [A], is preferably below 5 weight portions.If surpass 10 weight portions, be easy to generate when then existing coating as film problem such as chap.
So the solution of the resin combination of the present invention of preparation is to A], the concentration of [B] and [C] composition adjusts, be adjusted into can produce the solid component concentration of aimed thin film by the method for regulation after, be coated on the substrate surface.In addition, be adjusted into the resin combination solution of this concentration, after also can further filtering usually, supply with and use by filtrator with 0.1～0.45 μ m aperture.In addition, when using the alkali soluble resin of [A] expression by above-mentioned solution polymerization manufacturing, can not separate resin the solution after polymerization yet, but further add multi-functional (methyl) acrylate of usefulness [B] expression and the Photoepolymerizationinitiater initiater of representing with [C] to this solution, and same as described above adjust concentration after, be coated on the substrate surface.In addition, can certainly add other compositions such as bonding auxiliary agent, surfactant to this solution, perhaps, re-use after similarly filtering this solution by filtrator with above-mentioned.
Interval body of the present invention can be made by the following method: with the above-mentioned resin combination solution coat of the present invention of having adjusted concentration on the substrate of regulation and form film, then, carry out prebake and after removing solvent, by having the photomask irradiates light (radioactive ray) of predetermined pattern, and then develop and form pattern with alkaline developer, after clean (flushings) such as flowing water, make by curing after carrying out.
Above-mentioned coating can be adopted known method, particularly, can enumerate spin-coating method, rolling method, scraper rubbing method, dip coating etc.In addition, the prebake after the coating can be undertaken by blow heat drying wind to filming in the well heater of cleaning oven etc., perhaps, is undertaken by substrate is placed on the heating plate.Because the heat drying temperature of being undertaken by well heaters such as cleaning ovens during prebake or the heating-up temperature of heating plate, be monomeric unit or the kind of compound or the cooperation ratio difference of each composition because of each composition that constitutes [A], [B] and [C], therefore cannot treat different things as the same, but be generally 70～100 ℃, be preferably 80～90 ℃ temperature range, and be to be 10～30 minutes when for cleaning oven heat time heating time, be 3～5 minutes when for heating plate, can be from above-mentioned, select and get final product desirable temperature range and heat time heating time.In addition, heating-up temperature can remain on constant, also can heat up interimly.
As the alkaline developer that uses when the above-mentioned development, can enumerate the electrodeless bases of NaOH, potassium hydroxide, sodium carbonate, sal tartari, sal tartari etc.; The aqueous solution of organic bases of Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethyl ethanolamine etc. etc.In addition,, be generally 0.01～5 weight %, be preferably 0.05～2.5 weight % as the concentration of above-mentioned aqueous alkali.In addition, also can in above-mentioned aqueous alkali, add the surfactant of nonionic surfactant with the removal effect that promotes the development residue etc. or the water-miscible organic solvent of methyl alcohol, ethanol etc. in right amount, thereby use as alkaline developer.And then, as developing method, can use any means in dip coating, spray process, the spraying process etc., be generally 30～60 seconds as development time.On the other hand, the washing of carrying out after the development (flushing) has in the unwanted part that flushing do not remove in development fully, removes the effect attached to the alkaline developer on filming, and its wash time is generally 30～150 seconds.
Cure after above-mentioned, usually can be by in well heaters such as cleaning oven, blowing heat drying wind and carry out to forming figuratum filming.After heating-up temperature when curing be generally 150～230 ℃, and heated usually 30～60 minutes.Also carried to some extent in the superincumbent narration, the purpose of curing after this is, by in the high temperature heating, when removing solvent and moisture, make hot high molecular weight reactive takes place between the alkali soluble resin shown in [A], that is, make between carboxyl in the alkali soluble resin and the epoxy radicals to react, simultaneously, the non-reacted parts of multi-functional (methyl) acrylate is crosslinked shown in the initiation [B], thereby further promoted three-dimensional cross-linked filming, that is, and so-called interval body.Thus, characteristics such as the physical strength of raising gained interval body, shrinkage factor, thermotolerance, solvent resistance.
Liquid crystal indicator of the present invention is characterised in that, has the interval body of being made by the resin combination of the invention described above, below, the manufacture method of this liquid crystal indicator is described.At first, for example on the transparency electrode surface of the glass substrate that the transparency electrode of stacked indium-tin-oxide (ITO) on the color filter etc. forms, according to the manufacture method of above-mentioned interval body, be coated with resin combination solution of the present invention, have the film of purpose thickness with formation.Then, by have as the quadrilateral transmittance section of 5 μ m * 5 μ m～15 μ m * 15 μ m, form figuratum photomask irradiates light (radioactive ray), develop with alkaline developer in the same manner with the manufacture method of above-mentioned interval body, after the washing, after carrying out, cure, produce interval body.On the surface of the aforesaid substrate that so obtains, be coated with oriented film, and after calcining, implement friction treatment, obtain being laminated with the substrate of oriented film thus.And then, be laminated with the substrate periphery of oriented film at this, the coating of liquid crystalline encapsulant, behind the promptly so-called sealant, with this substrate be laminated with other substrates of oriented film, fitted and carried out crimping in the mutual opposed mode in oriented film surface.At last, between substrate, inject liquid crystal,, produce liquid crystal indicator by the sealing inlet from liquid crystal injecting port.So, can access and assembled that can not to produce coating that high polar solvent of containing oriented film material because of repulsion etc. causes bad and have a liquid crystal indicator of the interval body of high shrinkage and high resiliency response rate.
The oriented film that uses in the manufacturing of above-mentioned liquid crystal indicator, liquid crystal sealing material (sealant) and liquid crystal, so long as compound or the composition that uses in this field gets final product usually, do special the qualification, in addition, also there is no particular limitation to its coating process and method for implanting.In addition, in above-mentioned manufacture method, also can be on the surface that stacks gradually the glass substrate that transparency electrode and oriented film form on the color filter, to make interval body.In addition, also can be by being laminated with the substrate periphery coating sealant of oriented film, and in advance to behind the dispersed LCD on this substrate, between applying TFT substrate and the substrate and the method that seals is made liquid crystal indicator.
Spacer height during above-mentioned liquid crystal indicator is made is that the pattern because of liquid crystal indicator changes, but considers answer speed, is generally 3～5 μ m.In addition, the shape of this interval body, so long as the interval body shape of using in this field gets final product usually, do special the qualification, but preferably from directly over be square, rectangle, circle, ellipse when observing, when being rectangle, ellipse, preferred its long axis direction is parallel with frictional direction or vertical mutually, during preferably from the observation of positive side is square, rectangle, trapezoidal, wherein, more preferably trapezoidal.In addition, trapezoidal last base angle can be a fillet, and the bottom can also be with in trapezoidal bottom.Trapezoidal shape is to implement behind the stacked oriented film on this interval body in the friction treatment, and is effective especially when stacked uniform oriented film or when implementing uniform friction treatment.
In the above description, the concrete example when resin combination of the present invention is used with photosensitive material as the interval body manufacturing has been described in detail, but resin combination of the present invention also can be used as dielectric film or outer jacket (overcoat) film uses with material.
Embodiment
Below, specifically describe the present invention according to embodiment and comparative example, but the present invention is not limited to these embodiment.In addition, the weight average molecular weight of gained resin is the solution after a small amount of polymerization of extraction, and passes through the polystyrene conversion molecular weight that GPC (gel permeation chromatography) measures.
Synthesizing of synthesis example 1 alkali soluble resin (a)-1
To the flask that has cooling tube, thermometer and stirrer, add 110g propylene glycol methyl ether acetate (PGMEA), 5g styrene, 34g methacrylic acid two cyclopentyl esters, 8g methacrylic acid and 5g butadiene.Then, when beginning is slowly stirred, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) is 3g (ADMVN).And then, solution temperature is warming up to 70 ℃, under this temperature, kept 3 hours and make it to carry out polymerization, thereby obtain the solution that contains alkali soluble resin (a)-1 that solid component concentration is 33.3 weight %.The acid value of gained alkali soluble resin (a)-1 is 94.8mgKOH/g, and its weight average molecular weight is 8500.
Synthesizing of synthesis example 2～13 alkali soluble resins (a)-2～(a)-13
In synthesis example 2～13, except each composition shown in the table 1 and solvent were added with the amount shown in the table 1, other and synthesis example 1 were operated in the same manner, obtain containing the solution of resin (a)-2～(a)-13.The result of its result and resin (a)-1 is shown in Table 1 in the lump.In addition, unless dated especially, the numerical value in the table 1 is all represented weight portion.
Synthesizing of synthesis example 14 alkali soluble resins (b)-1
To the flask that has cooling tube, thermometer and stirrer, add propylene glycol methyl ether acetate (PGMEA) 110g, glycidyl methacrylate 40g and methacrylic acid 8g.Then, when beginning is slowly stirred, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) is 3g (ADMVN).And then, this solution temperature is warming up to 70 ℃, under this temperature, kept 3 hours and make to carrying out polymerization, thereby obtain the solution that contains alkali soluble resin (b)-1 that solid component concentration is 34.1 weight %.The acid value of gained alkali soluble resin (b)-1 is 91.5mgKOH/g, and its weight average molecular weight is 11300.
Synthesizing of synthesis example 15～26 alkali soluble resins (b)-2～(b)-13
In synthesis example 15～26, except each composition shown in the table 2 and solvent are added with the amount shown in the table 2, and kept 5 hours down and beyond the polymerization, other and synthesis example 14 are operated in the same manner at 70 ℃, obtain containing the solution of resin (b)-2～(b)-13.The result of its result and resin (b)-1 is shown in Table 2 in the lump.In addition, unless dated especially, the numerical value in the table 2 is all represented weight portion.
Figure A20088001767000361
Synthesizing of synthesis example 27 alkali soluble resins (a)-14
Flow into drying nitrogen to the flask that has reflux cooler, stirrer, thermometer, with the air in the nitrogen replacement flask.In this flask, add propylene glycol methyl ether acetate (PGMEA) 526 weight portions.And adding 2 successively, 2 '-azo two (2, the 4-methyl pentane nitrile) is 11 weight portions, methacrylic acid benzyl ester 79 weight portions, methacrylic acid 53 weight portions, methacrylic acid two cyclopentyl esters 105 weight portions, 1,3-butadiene 26 weight portions (ADMVN).Then, begin to stir, flask is immersed in the oil bath, the control oil bath temperature remains on 70 ℃ condition with interior temperature, carries out 4 hours polyreaction.After 4 hours interior temperature is increased to 80 ℃, and then continues polyreaction after 1 hour, flask is taken out from oil bath, be cooled to room temperature, thereby obtain the solution that contains alkali soluble resin (a)-14 that solid component concentration is 31.5 weight %.The acid value of gained alkali soluble resin (a)-14 is 130mgKOH/g, and its weight average molecular weight is 15000.
Synthesizing of synthesis example 28 alkali soluble resins (a)-15
Flow into drying nitrogen to the flask that has reflux cooler, stirrer, thermometer, with the air in the nitrogen replacement flask.In this flask, add dipropylene glycol dimethyl ether 526 weight portions.And add 2 successively, 2 '-azo two (2, the 4-methyl pentane nitrile) (ADMVN) 11 weight portions, methacrylic acid benzyl 52 weight portions, methacrylic acid 13 weight portions, methacryloxyethyl malonic acid monoester 78 weight portions, methacrylic acid two cyclopentyl esters 91 weight portions, 1,3-butadiene 26 weight portions.Then, begin to stir, flask is immersed in the oil bath, the control oil bath temperature remains on 70 ℃ condition with interior temperature, carries out 4 hours polyreaction.After 4 hours interior temperature is increased to 80 ℃, and then continues polyreaction after 1 hour, flask is taken out from oil bath, be cooled to room temperature, thereby obtain the solution that contains alkali soluble resin (a)-15 that solid component concentration is 32.5 weight %.The acid value of gained alkali soluble resin (a)-15 is 110mgKOH/g, and its weight average molecular weight is 13000.
Synthesizing of synthesis example 29 alkali soluble resins (a)-16
Flow into drying nitrogen to the autoclave that has stirrer, thermometer (autoclave), with the air in the nitrogen replacement autoclave.Add pure water 524 weight portions from the soup input port, and add neopelex 2 weight portions, α-Jia Jibenyixi dimer 8 weight portions, methacrylic acid 66 weight portions, methacrylic acid two cyclopentyl esters 79 weight portions, 1,3-butadiene 79 weight portions successively.Then, beginning is slowly stirred, and autoclave is immersed in the oil bath, and the control oil bath temperature is so that interior temperature remains on 60 ℃ and carry out polyreaction.Along with the solid component concentration of measuring interior solution of polyreaction, when being about 50%, the aggregate rate that is converted by this numerical value removes oil bath, be cooled to room temperature.Then, to the container that 2 weight % sodium bicarbonate aqueous solutions are housed, the limit is slowly stirred the limit and is slowly added content in the autoclave, obtain alkali soluble resin (a)-16, (a)-16 is dissolved in the propylene glycol methyl ether acetate with this alkali soluble resin, and the mixture ratio of putting into water/methyl alcohol is to make with extra care in 50/50 the precipitation agent.Then, gained alkali soluble resin (a)-16 is added in the vacuum dryer, under 60 ℃, to carry out 24 hours vacuum drying.The acid value of gained alkali soluble resin (a)-16 is that 110mgKOH/g, its weight average molecular weight are 45000.To be dissolved in propylene glycol methyl ether acetate through the alkali soluble resin (a)-16 of super-dry, thereby the preparation solid component concentration is the solution of 30 weight %.
Synthesizing of synthesis example 30 alkali soluble resins (b)-14
Flow into drying nitrogen to the flask that has reflux cooler, stirrer, thermometer, with the air in the nitrogen replacement flask.In this flask, add dipropylene glycol dimethyl ether 521 weight portions.Add 2 successively, 2 '-azo two (2, the 4-methyl pentane nitrile) is 18 weight portions, methacryloxyethyl malonic acid monoester 78 weight portions, glycidyl methacrylate 182 weight portions (ADMVN).Then, begin to stir, flask is immersed in the oil bath, and the control oil bath temperature is so that interior temperature remains on 70 ℃ and carry out 4 hours polyreaction.After 4 hours interior temperature is increased to 80 ℃, and then proceeds polyreaction after 1 hour, flask is taken out from oil bath, be cooled to room temperature, obtaining solid component concentration is the solution that contains alkali soluble resin (b)-14 of 32.0 weight %.The acid value of gained alkali soluble resin (b)-14 is 77.0mgKOH/g, and its weight average molecular weight is 18000.
Synthesizing of synthesis example 31～38 alkali soluble resins (b)-15～(b)-22
In synthesis example 31～38, except each composition and solvent shown in the table 3 are added with the amount shown in the table 3, operate in the same manner with synthesis example 30, obtain containing the solution of resin (b)-15～(b)-22.The result of its result and resin (b)-14 is shown in Table 3 in the lump.In addition, unless dated especially, the numerical value in the table 3 is all represented weight portion.
Figure A20088001767000391
Synthesizing of synthesis example 39 poly (glycidyl methacrylate)s
Do not use the methacryloxyethyl malonic acid monoester in the synthesis example 30, but by with only polymerization glycidyl methacrylate of synthesis example 30 identical operations 182 weight portions, synthetic thus poly (glycidyl methacrylate).The solid component concentration that contains the solution of poly (glycidyl methacrylate) is 25.9 weight %, and the weight average molecular weight of poly (glycidyl methacrylate) is 13000.
The preparation of synthesis example 40 oriented film solution
Flow into drying nitrogen to flask, with the air in the nitrogen replacement flask with stirrer, thermometer.In this flask, add N-Methyl pyrrolidone 225 weight portions and 4,4 '-diaminodiphenyl-methane, 12.3 weight portions.Then, beginning is slowly stirred, flask is immersed in the water-bath that temperature is controlled at 40 ℃, temperature reaches 40 ℃ in confirming, and added 4, after the dissolving of 4 '-diaminodiphenyl-methane, add pyromellitic acid anhydride 6.7 weight portions, cyclo-butane tetracarboxylic dianhydride 6 weight portions, begin to carry out polyreaction.React after 4 hours, remove water-bath, be cooled to room temperature after, further add N-Methyl pyrrolidone 750 weight portions, preparing solid component concentration thus is the oriented film solution of 2.5 weight %.
Embodiment 1
(i) preparation of compositions
The complete soln that contains resin (a)-1 that will obtain as the synthesis example 1 of the alkali soluble resin of representing with (a) mixes with the complete soln that contains resin (b)-1 that the synthesis example 14 as the alkali soluble resin of representing with (b) obtains, and then dilute this mixed liquor with diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) 120g, 2-benzyl-2-(N of Photoepolymerizationinitiater initiater shown in dipentaerythritol acrylate 100g of multi-functional (methyl) acrylate shown in the interpolation conduct [B] and the conduct [C], the N-dimethylamino)-mixed behind 1-(4-morpholinyl phenyl) butane-1-ketone (Ciba SpecialtyChemicals Inc. make the IRGCURE369) 25g, and the millipore filter by aperture 0.2 μ m filters, thereby prepares composition solution of the present invention.
The (ii) making of interval body
Use spinner, with the rotating speed of 1000rpm, the composition solution for preparing in (i) is coated on the glass substrate of band ITO, the coating time is 10 seconds.Should be coated with metacoxal plate and place on the heating plate, under 80 ℃, carry out 3 minutes prebake.Utilize the pattern mask of regulation, and by the ultraviolet ray (200mj/cm) of extra-high-pressure mercury vapour lamp gained is filmed and to expose.Then, at room temperature impregnated in the tetramethylammonium hydroxide aqueous solution of 0.15 weight %, carry out 60 seconds immersion development.From developer solution, take out substrate,, put into the cleaning oven that temperature is controlled at 220 ℃ with pure water rinsing after 60 seconds, carry out 60 minutes after cure.Gained photonasty interval body is the interval body of 15 μ m * 15 μ m, high 4.5 μ m.
The (iii) mensuration of elastic recovery rate
Utilize dynamic submicroscopic sclerometer DUH-W201S (manufacturing of (strain) Shimadzu Seisakusho Ltd.), measure the (ii) elastic recovery rate of middle gained interval body.At room temperature,, interval body is applied load, when load reaches 5gf, under this load, kept for 5 seconds, then, discharge with same speed with the constant speed of 0.22gf/ second by the plane pressure head of diameter 50 μ m.Obtain total displacement amount (μ m) and elastic displacement (μ m) from this measurement result, and obtain elastic recovery rate by following mathematical expression.
Elastic recovery rate (%)=(elastic displacement (μ m) * 100)/total displacement amount (μ m)
The (iv) coating of oriented film solution
By spin-coating method, on the ito glass substrate with the interband spacer in (ii), made of oriented film solution coat of preparation in the synthesis example 40.Place temperature to be controlled on 90 ℃ the heating plate this substrate, carry out 3 minutes prebake.Visualization prebake metacoxal plate confirms to have formed uniform oriented film.Therefore, as can be known on the ito glass substrate of the interband spacer of in (ii), making, there is not residue when developing in the interval body manufacture craft (below, be recited as " no residue " sometimes) fully.Hence one can see that, and resin combination of the present invention can easily be peeled off with respect to alkaline developer, can eliminate the residual residue when developing.
Embodiment 2～13
In embodiment 2～13, except the alkali soluble resin that uses usefulness (a) expression shown in the table 4, alkali soluble resin and diluting solvent that usefulness (b) is represented, operate in the same manner with embodiment 1, prepare each composition solution, and by with after the (ii) identical method of embodiment 1 is made interval body, the elastic recovery rate of implementing is (iii) measured the coating that reaches oriented film solution (iv), carries out the evaluation of elastic recovery rate and development.The acid value and the solid component concentration of each composition solution are shown in Table 4 in the lump.
Table 4
Embodiment Resin (a) Resin (b) Diluting solvent Solid component concentration (weight %) Acid value (mgKOH/g) Elastic recovery rate (%) Residue
??1 ??(a)-1 ??(b)-1 Propylene glycol methyl ether acetate ??30.5 ??96.7 ??60 Do not have
??2 ??(a)-2 ??(b)-2 Diethylene glycol dimethyl ether ??21.8 ??96.8 ??75 Do not have
??3 ??(a)-3 ??(b)-3 Diethylene glycol dimethyl ether ??26.0 ??96.5 ??77 Do not have
??4 ??(a)-4 ??(b)-4 Diethylene glycol dimethyl ether ??26.0 ??96.5 ??75 Do not have
??5 ??(a)-5 ??(b)-5 Diethylene glycol dimethyl ether ??20.0 ??96.5 ??72 Do not have
??6 ??(a)-6 ??(b)-6 Propylene glycol methyl ether acetate ??30.5 ??96.7 ??82 Do not have
??7 ??(a)-7 ??(b)-7 Propylene glycol methyl ether acetate ??25.0 ??96.8 ??80 Do not have
??8 ??(a)-8 ??(b)-8 Propylene glycol methyl ether acetate ??25.0 ??97.6 ??78 Do not have
??9 ??(a)-9 ??(b)-9 Propylene glycol methyl ether acetate ??30.5 ??96.7 ??80 Do not have
??10 ??(a)-10 ??(b)-10 The dipropylene glycol dimethyl ether ??30.5 ??96.7 ??75 Do not have
??11 ??(a)-11 ??(b)-11 The dipropylene glycol dimethyl ether ??27.2 ??94.9 ??81 Do not have
??12 ??(a)-12 ??(b)-12 The dipropylene glycol dimethyl ether ??27.8 ??92.4 ??81 Do not have
??13 ??(a)-13 ??(b)-13 Diethylene glycol dimethyl ether ??26.7 ??96.6 ??83 Do not have
Embodiment 14
(i) preparation of compositions
Solution 156 weight portions that contain alkali soluble resin (b)-14 synthetic in solution 159 weight portions that contain alkali soluble resin (a)-14 synthetic in the synthesis example 27 and the synthesis example 30 are mixed, and are the solution of (a)/(b)=50/50 with the solid constituent ratio for preparing alkali soluble resin (a)-14 and alkali soluble resin (b)-14.The dipentaerythritol acrylate that adds 100 weight portions to this solution, 5 weight portions are as 2-methyl isophthalic acid-[4-(methyl sulfo-) the phenyl]-2-morpholinyl propane-1-ketone of Photoepolymerizationinitiater initiater, 2-benzyl-2-dimethylamino-the 1-of 10 weight portions (4-morpholinyl phenyl)-butanone-1,2 weight portions are as 4 of sensitizer, 4 '-two (N, the N-diethylamino) benzophenone further adds the 3-glycidoxypropyltrime,hoxysilane of 3 weight portions as bonding auxiliary agent, 0.1 weight portion is as the Megafac F475 (big Japanese ink chemical industry (strain) is made) of surfactant.For the total solid constituent concentration being adjusted into 35 weight %, add propylene glycol methyl ether acetate 55 weight portions, dipropylene glycol dimethyl ether 139 weight and fully stirring, millipore filter by aperture 0.2 μ m filters, thereby prepares composition solution of the present invention.
The (ii) making of interval body, the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate
In (ii)～(iv), after adopting the (ii) identical method making interval body with embodiment 1, implement the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate by the method identical, thereby carry out the evaluation of elastic recovery rate and development with embodiment 1.
Embodiment 15～43
In embodiment 15～43, as shown in table 5, except the combination that changes alkali soluble resin of representing with (a) and the alkali soluble resin of using (b) expression, operate in the same manner with embodiment 14, prepare each composition solution, and, implement the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate by with after the (ii) identical method of embodiment 1 is made interval body, carry out the evaluation of elastic recovery rate and development.With the result of its result and embodiment 14-and be shown in Table 5.In addition, the ratio of the solid constituent of expression alkali soluble resin of " resin (a)/resin (b)=mixing ratio (weight) " in the table 5 (a) and alkali soluble resin (b).
Table 5
Embodiment Resin (a)/resin (b)=mixing ratio (weight) Elastic recovery rate (%) Residue
??14 ??(a)-14/(b)-14＝50/50 ??78 Do not have
??15 ??(a)-14/(b)-15＝50/50 ??82 Do not have
??16 ??(a)-14/(b)-16＝50/50 ??70 Do not have
??17 ??(a)-14/(b)-17＝50/50 ??80 Do not have
??18 ??(a)-14/(b)-18＝50/50 ??79 Do not have
??19 ??(a)-14/(b)-19＝50/50 ??68 Do not have
??20 ??(a)-14/(b)-20＝50/50 ??80 Do not have
??21 ??(a)-14/(b)-21＝50/50 ??78 Do not have
??22 ??(a)-14/(b)-22＝50/50 ??80 Do not have
??23 ??(a)-15/(b)-14＝50/50 ??80 Do not have
??24 ??(a)-15/(b)-15＝50/50 ??88 Do not have
??25 ??(a)-15/(b)-16＝50/50 ??73 Do not have
??26 ??(a)-15/(b)-17＝50/50 ??81 Do not have
??27 ??(a)-15/(b)-18＝50/50 ??80 Do not have
??28 ??(a)-15/(b)-19＝50/50 ??71 Do not have
??29 ??(a)-15/(b)-20＝50/50 ??82 Do not have
??30 ??(a)-15/(b)-21＝50/50 ??80 Do not have
??31 ??(a)-15/(b)-22＝50/50 ??83 Do not have
??32 ??(a)-16/(b)-14＝50/50 ??85 Do not have
??33 ??(a)-16/(b)-15＝50/50 ??90 Do not have
??34 ??(a)-16/(b)-16＝50/50 ??75 Do not have
??35 ??(a)-16/(b)-17＝50/50 ??85 Do not have
??36 ??(a)-16/(b)-18＝50/50 ??83 Do not have
??37 ??(a)-16/(b)-19＝50/50 ??74 Do not have
??38 ??(a)-16/(b)-20＝50/50 ??85 Do not have
??39 ??(a)-16/(b)-21＝50/50 ??82 Do not have
??40 ??(a)-16/(b)-22＝50/50 ??87 Do not have
??41 ??(a)-14/(b)-22＝20/80 ??73 Do not have
??42 ??(a)-14/(b)-22＝40/60 ??75 Do not have
??43 ??(a)-14/(b)-22＝60/40 ??75 Do not have
Comparative example 1
(i) preparation of compositions
Do not use the solution that contains alkali soluble resin (b)-14 in embodiment 14 (i) preparation of compositions, only use solution 318 weight portions that contain alkali soluble resin (a)-14, in order to make the total solid constituent concentration be adjusted into 35 weight %, propylene glycol methyl ether acetate 191 weight portions have been added, in addition, operate the preparation composition solution in the same manner with embodiment 14.
The (ii) making of interval body, the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate
In (ii)～(iv), after adopting the (ii) identical method making interval body with embodiment 1, implement the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate by the method identical, carry out the evaluation of elastic recovery rate and development with embodiment 1.Its result owing to formed uniform oriented film in the coating of (iv) oriented film solution, residue do not occur when therefore developing in the interval body production process, but in the mensuration of (iii) elastic recovery rate, the elastic recovery rate that obtains is 55% low value.
Comparative example 2
(i) preparation of compositions
Replace the solution that contains alkali soluble resin (b)-14 in embodiment 14 (i) preparation of compositions with the synthetic solution that contains poly (glycidyl methacrylate) 159 weight portions of synthesis example 39, mixed with solution 159 weight portions that contain alkali soluble resin (a)-14, add propylene glycol methyl ether acetate 96 weight portions in order to make the total solid constituent concentration be adjusted into 35 weight %, in addition, operate the preparation composition solution in the same manner with embodiment 14.
The (ii) making of interval body, the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate
In (ii)～(iv), adopt with after the (ii) identical legal system of embodiment 1 is made interval body, implement the (iii) mensuration and the (iv) coating of oriented film solution of elastic recovery rate by the method identical, carry out the evaluation of elastic recovery rate and development with embodiment 1.Its result, though the elastic recovery rate in the mensuration of (iii) elastic recovery rate is 65%, but in the coating of (iv) oriented film solution, owing to confirm to exist on the substrate coating residue of oriented film, this means when developing in the interval body production process to have residue, it is insufficient to judge development.
Result from table 4 and table 5 and comparative example 1 and 2 compares with resin combination in the past as can be known, the development excellence of resin combination of the present invention, and the interval body of being made by this resin combination has the high resiliency response rate.Hence one can see that, and for example by making liquid crystal indicator have the interval body of being made by resin combination of the present invention, the demonstration that can suppress the liquid crystal panel that causes because of low-temp foaming is bad.
Industrial applicibility
Because the development of negative light-sensitive resin combination of the present invention is excellent, therefore the development residue that produces in the time of can suppressing to adopt photolithography in the production process such as the interval body in the manufacturing of liquid crystal indicator etc., and then, liquid crystal indicator with excellent effect can be provided, this excellent effect shows, the bad liquid crystal panel that brings of coating that does not produce high polar solvent that the repulsion that causes because of the development residue contains oriented film material etc. shows the liquid crystal indicator of bad beneficial effect.
In addition, can produce the interval body with high shrinkage and high resiliency response rate by negative light-sensitive resin combination of the present invention, and then, have the liquid crystal indicator that the liquid crystal panel that can suppress to cause because of low-temp foaming shows bad beneficial effect by having this interval body, can providing.

Claims (7)

1. a negative light-sensitive resin combination is characterized in that, contains:
[A] is (a) by alkali soluble resin that constitutes from the monomeric unit of unsaturated carboxylic acid and monomeric unit from free-radical polymerised unsaturated compound and the alkali soluble resin that (b) is made of the monomeric unit from the monomeric unit of unsaturated carboxylic acid and the free-radical polymerised unsaturated compound that comes self-contained epoxy radicals;
[B] multi-functional (methyl) acrylate; And
[C] Photoepolymerizationinitiater initiater.
2. composition according to claim 1, wherein, described [A] free-radical polymerised unsaturated compound in (a) is the conjugated diolefine unsaturated compounds.
3. composition according to claim 1, wherein, described [A] free-radical polymerised unsaturated compound in (a) is the combination of the free-radical polymerised unsaturated compound beyond the yoke dienes unsaturated compound together of conjugated diolefine unsaturated compounds.
4. according to claim 2 or 3 described compositions, wherein, described conjugated diolefine unsaturated compounds is 1,3 one butadiene and/or isoprene.
5. according to each described composition in the claim 1～4, wherein, described negative light-sensitive resin combination is the composition of interval body manufacturing usefulness.
6. interval body, it is by the described composition manufacturing of claim 5.
7. a liquid crystal indicator is characterized in that, has the described interval body of claim 6.
CN200880017670A 2007-08-10 2008-08-08 Negative photosensitive resin composition, spacer and liquid crystal display Pending CN101689022A (en)

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