CN1670625A - Formation of projections and spacers and radiation sensitive resin composition for the same - Google Patents

Formation of projections and spacers and radiation sensitive resin composition for the same Download PDF

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Publication number
CN1670625A
CN1670625A CNA200510054242XA CN200510054242A CN1670625A CN 1670625 A CN1670625 A CN 1670625A CN A200510054242X A CNA200510054242X A CN A200510054242XA CN 200510054242 A CN200510054242 A CN 200510054242A CN 1670625 A CN1670625 A CN 1670625A
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methyl
liquid crystal
protrusion
resin composition
radiation
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花村美里
阿部慈
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JSR Corp
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JSR Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
    • B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
    • B02C18/16—Details
    • B02C18/18—Knives; Mountings thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
    • B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
    • B02C18/16—Details
    • B02C18/24—Drives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27L—REMOVING BARK OR VESTIGES OF BRANCHES; SPLITTING WOOD; MANUFACTURE OF VENEER, WOODEN STICKS, WOOD SHAVINGS, WOOD FIBRES OR WOOD POWDER
    • B27L11/00—Manufacture of wood shavings, chips, powder, or the like; Tools therefor
    • B27L11/06—Manufacture of wood shavings, chips, powder, or the like; Tools therefor of wood powder or sawdust

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  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

A radiation sensitive resin composition contains at least one alkali-soluble resin selected from the linear phenolic resinPolystyrene with the molecular weight of 2,000-20,000 which is measured by the gel permeation chromatography by taking the polystyrene as a standard sample, and the hydroxyl styrene resin with the molecular weight of 10,000-100,000 which is measured by the gel permeation chromatography by taking the polystyrene as a standard sample; a polyfunctional monomer; and a photopolymerization initiator. The radiation sensitive resin composition is used in formation of protrusions and/or spacers for a vertical alignment type liquid crystal display device having a residual image erasing time of 100 s or shorter.

Description

The formation of protrusion and sept and be used to form their radiation-sensitive resin composition
Technical field
Protrusion that is used for vertical orientated liquid crystal display and the sept that the present invention relates to the radiation-sensitive resin composition of a kind of protrusion (projections) that is used to form vertical orientated liquid crystal display and/or sept (spacers), makes by radiation-sensitive resin composition, comprise the vertical orientated liquid crystal display of protrusion and/or sept and form protrusion and/or the method for sept.
Background technology
Liquid crystal display is widely used in flat-panel monitor.In recent years along with for example popularization of personal computer and word processor and liquid crystal TV of OA equipment, the requirement of the display quality of TFT (thin film transistor (TFT)) LCD (TFT-LCD ' s) is just being become more and more stricter.
Among TFT-LCD ' s, TN (twisted-nematic) LCD is most popular now.This LCD makes by following method: form the inclined to one side film that rises that two directions of orientation differ 90 ° each other having on two substrates of transparency electrode outside of (hereinafter being called " transparency electrode substrate "), and form alignment films on the inboard of two transparency electrode substrates; Between alignment films, insert nematic liquid crystal, and the direction of orientation of liquid crystal is reversed to another electrode side from an electrode side with 90 ° angle.
When nonpolarized light incided on the TN LCD, the linearly polarized photon that has passed a polarizer passed liquid crystal, its change of polarized direction, so it can pass another polarizer, the formation bright state.When making liquid crystal molecule upright when all applying voltage to two transparency electrodes, the linearly polarized photon of arrival liquid crystal can not change its polarization direction when passing liquid crystal, so it just can not pass another polarizer, the formation dark state.After this, when stopping to apply voltage, LCD just is returned to bright state.
Though, because in recent years technical progress, aspect the contrast and color reprodubility in front, above-mentioned TN LCD become with cathode ray tube (CRT) quite or more superior, it still has a big problem to need to solve, that is exactly narrow visual angle.
As a solution of this problem, developed MVA (multizone is vertical orientated) LCD.
This vertical orientated liquid crystal display uses birefringent mode, wherein having negative anisotropic negative type liquid crystal and vertical alignment layer on specific inductive capacity combines, and be unlike in " Liquid Crystals ", the 3rd volume, the 2nd phase, the optically-active pattern among the disclosed TN LCD of 117 pages (1999) and JP-A 11-258605 (term " JP-A " that is used for herein means " uncensored disclosed Japanese patent application ").Even when not applying voltage, because the direction of orientation of liquid crystal roughly keeps vertically near alignment films, MVALCD has excellent contrast and visual angle, and does not need just energy aligned liquid-crystal of friction.Therefore, MVA LCD also is remarkable aspect production technology.
In vertical orientated liquid crystal display, has slit in a pixel region in the transparency electrode of display side, and at the band of position sloping protrusion different with the slit of transparency electrode, for example shape forms in the suprabasil same pixel of the transparency electrode of light incident side zone as the protrusion of triangular pyramidal or semi-convex lens, makes the liquid crystal in same pixel region obtain a plurality of directions of orientation as the region limits device.
Usually, in the liquid crystal display of prior art, in order to keep two intervals between the transparency electrode substrate, promptly box gap constant uses the spherical or shaft-like sept of being made by resin or pottery.When two basalises stacked, sept was dispersed in one of substrate, and the diameter of sept is depended in the box gap.
Owing to can't eliminate the certain measurement difference on the diameter of protrusion and sept, as the method for avoiding such as the heterogeneity problem in the box gap that is caused by above-mentioned difference, JP-A 2001-201750 has proposed a kind of by making the method that forms protrusion and sept with photoresist.Though this method has the advantage that possibility obtains accurate pattern and is easy to control shape, above-mentioned publication does not have to disclose the performance of composition and the formed protrusion and the sept of this photoresist.
Enumerate requirement below for the photoresist of protrusion that is used to form vertical orientated liquid crystal display and sept.
That is, photoresist should have high film hardness, and protrusion and sept with outstanding surface flatness are provided, and produces development residue or stain hardly in the part substrate that is not exposed to radiation.The vertical orientated liquid crystal display of gained should not have fluorescent screen images to keep and shows unevenness.
Applicant of the present invention has proposed a kind of radiation-sensitive resin composition that is used for forming simultaneously protrusion and sept, it comprises [A] (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) contain the unsaturated compound of epoxy radicals and the multipolymer that (a3) is different from these unsaturated compound, [B] undersaturated polymerizable compound and [C] radiosensitive polymerization initiator, protrusion and the sept made by radiation-sensitive resin composition, and the liquid crystal display (JP-A 2003-29405) that comprises protrusion and sept.
Yet the exploitation that is used to form the radiation-sensitive resin composition of the protrusion of vertical orientated liquid crystal display and sept just just begins.For the quick popularization of tackling TFT-LCD and the more and more stricter requirement of TFT-LCD, the exploitation that can form the novel radiation-sensitive resin composition of protrusion with excellent performance and sept is very important technically.
Summary of the invention
Based on above-mentioned situation, an object of the present invention is to provide a kind of protrusion of vertical orientated liquid crystal display and/or radiation-sensitive resin composition of sept of being used to form, more specifically, a kind of radiation-sensitive resin composition is provided, it can provide protrusion and the sept with excellent surface flatness, in the substrate of unexposed portion, produce the development residue hardly, be provided separating and can provide and having excellent liquid crystal vertical-tropism of protrusion and sept hardly, but high voltage retentivity and short afterimage are eliminated the time and are not almost had fluorescent screen images and keep and show heteropical vertical orientated liquid crystal display; With a kind of method that forms protrusion and/or sept is provided.
By following description, other purpose of the present invention and advantage will become apparent.
First, according to the present invention, above-mentioned purpose of the present invention and advantage realize by radiation-sensitive resin composition, it is that the weight-average molecular weight that standard specimen is measured by gel permeation chromatography is 2 that said composition comprises (A) at least a being selected from the polystyrene, 000-20,000 linear phenol-aldehyde resin and be that the weight-average molecular weight that standard specimen is measured by gel permeation chromatography is 10 with the polystyrene, 006-100, the alkali soluble resins of 000 hydroxy styrenes resin, (B) polyfunctional monomer or polyfunctional monomer and simple function group monomer combination, (C) Photoepolymerizationinitiater initiater, and said composition is used for having 100 seconds or shorter afterimage is eliminated the vertical orientated liquid crystal display of time and formed protrusion and/or sept.
The second, according to the present invention, above-mentioned purpose of the present invention and advantage realize that by the protrusion that is used for vertical orientated liquid crystal display wherein this protrusion is prepared by above-mentioned radiation-sensitive resin composition.
The 3rd, according to the present invention, above-mentioned purpose of the present invention and advantage realize that by the sept that is used for vertical orientated liquid crystal display wherein this sept is prepared by above-mentioned radiation-sensitive resin composition.
The 4th, according to the present invention, above-mentioned purpose of the present invention and advantage by being formed for vertical orientated liquid crystal display protrusion and/or the method for sept realize that wherein this method may further comprise the steps:
(a) coating of the above-mentioned radiation-sensitive resin composition of formation in substrate;
(b) partial coating is exposed in the radiation;
(c) behind the irradiation coating is developed to form pattern; And
(d) development back heating coating.
The 5th, according to the present invention, above-mentioned purpose of the present invention and advantage realize that by vertical orientated liquid crystal display this equipment comprises above-mentioned protrusion and/or above-mentioned sept, and have 100 seconds or the shorter afterimage elimination time.
To describe the present invention in detail below.
Radiation-sensitive resin composition
Use description to form the radiation-sensitive resin composition component (hereafter is " radiation-sensitive resin composition ") of the protrusion and/or the sept of vertical orientated liquid crystal display of the present invention hereinafter.
(A) alkali soluble resins
The alkali soluble resins that uses among the present invention is a kind of linear phenol-aldehyde resin and/or hydroxy styrenes resin.
Above-mentioned linear phenol-aldehyde resin is to obtain by polycondensation phenol and aldehyde in the presence of acid catalyst.
The example that is used to prepare the phenol of linear phenol-aldehyde resin comprises: phenol, orthoresol, metacresol, paracresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-pseudocuminol, 3,4,5-pseudocuminol, resorcinol, 2-methylresorcinol, 4-ethyl resorcinol, p-dihydroxy-benzene, methyl hydroquinone, catechol, 4-methyl pyrocatechol, pyrogallol, phloroglucin, thymol and isothymol.
Among these phenol, preferred phenol, metacresol, paracresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-pseudocuminol.
Above-mentioned phenol can use separately or two or more are used in combination.When above-mentioned two or more phenol are used in combination, preferred combination comprises: the combination of metacresol and paracresol, metacresol and 2, the combination of 3-xylenol, metacresol and 2, the combination of 4-xylenol, metacresol and 2, the combination of 5-xylenol, metacresol and 2,3, the combination of 5-pseudocuminol, phenol, 2,3-xylenol and 3, the combination of 4-xylenol, metacresol, 2,3-xylenol and 2, the combination of 4-xylenol, metacresol, 2,3-xylenol and 3, the combination of 4-xylenol, metacresol, 2,4-xylenol and 2, the combination of 5-xylenol, metacresol, 2,5-xylenol and 3, the combination of 4-xylenol, metacresol, 2,3-xylenol and 2,3, the combination of 5-pseudocuminol, metacresol, paracresol and 2, the combination of 3-xylenol, metacresol, paracresol and 2, the combination of 4-xylenol, metacresol, paracresol and 2, the combination of 5-xylenol, and metacresol, paracresol and 2,3, the combination of 5-pseudocuminol.
And the example of the aldehyde of phenol polycondensation comprise formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, phenylacetaldehyde, α-benzenpropanal, β-Ben Bingquan, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde, p-tolyl aldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde and m-terephthal aldehyde.Among these aldehyde, formaldehyde and salicylaldhyde are preferred.
Above-mentioned aldehyde can use separately or two or more are used in combination.
The amount of aldehyde is preferably 0.4-2.0mol, and more preferably 0.6-1.5mol is based on 1mol phenol meter.
Condensed polymer, the metacresol, 2 of condensed polymer, metacresol, paracresol and the formaldehyde of preferred especially metacresol of linear phenol-aldehyde resin of the present invention and formaldehyde, the condensed polymer of 3-xylenols and formaldehyde, metacresol, 2, the condensed polymer of 4-xylenols and formaldehyde or metacresol, 2, the condensed polymer of 5-xylenols and formaldehyde.
The example that is used for the acid catalyst of phenol and aldehyde polycondensation comprises: hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetate, methane-sulforic acid and p-toluenesulfonic acid.
These acid catalysts can use separately or two or more are used in combination.
The amount of acid catalyst is generally 1 * 10 -5-5 * 10 -1Mol is based on 1mol phenol meter.
The polycondensation reaction between phenol and the aldehyde can not or have solvent in the presence of carry out.
The example of solvent comprises: alcohol is methyl alcohol, ethanol, n-propanol, isopropyl alcohol and normal butyl alcohol for example; Ether is tetrahydrofuran, diox and propylene glycol monomethyl ether for example; With ketone for example MEK, methyl isobutyl ketone and 2-heptanone.
These solvents can use separately or two or more are used in combination.
When polycondensation reaction was carried out in solvent, the amount of solvent was generally 20-1,000 weight portion, and preferred 50-800 weight portion is based on the total reaction raw materials meter of 100 weight portions.
The temperature of polycondensation reaction can be done suitably to regulate according to the reactivity of reaction raw materials, is generally 10-200 ℃.
In order to carry out polycondensation reaction, (i) simultaneously phenol, aldehyde and acid catalyst are added reactor, or (ii) acid catalyst is added reactor, then in the presence of acid catalyst, add phenol and aldehyde along with reaction.
Collect linear phenol-aldehyde resin in order to finish the back in polycondensation reaction, (iii) the internal temperature with reaction system is elevated to 130-230 ℃, and under reduced pressure remove volatile matter, so that collection linear phenol-aldehyde resin, or (iv) will be dissolved in the good solvent by the linear phenol-aldehyde resin of solvent-free polycondensation acquisition or by the linear phenol-aldehyde resin that said method is (iii) collected, for example normal hexane or normal heptane mix with the precipitation resin with gained solution and water or poor solvent, and the resin of precipitation separation, so that collect the polymer moieties of linear phenol-aldehyde resin, wherein good solvent for example is an ethylene glycol monomethyl ether acetate, the diglycol ethyl methyl ether, 3-methoxypropionic acid methyl esters, ethyl lactate, propylene glycol monomethyl ether, methyl isobutyl ketone, 2-heptanone diox, methyl alcohol or ethyl acetate.
Be that the weight-average molecular weight (hereinafter being called " Mw ") that standard specimen passes through the linear phenol-aldehyde resin that gel permeation chromatography (GPC) records is 2 with the polystyrene, 000-20,000, preferred 3,000-15,000.Having outstanding coating, development, susceptibility and stable on heating radiation-sensitive resin composition can obtain by the linear phenol-aldehyde resin that use has an above-mentioned Mw.
In the present invention, above-mentioned linear phenol-aldehyde resin can use separately or two or more are used in combination.
Above-mentioned hydroxy styrenes resin is single polymkeric substance or the combination of polymers of two or more hydroxy styrenes or the multipolymer of at least a hydroxy styrenes and at least a other polymerisable monomer, and wherein hydroxy styrenes for example is o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene, adjacent hydroxyl-α-Jia Jibenyixi, hydroxyl-α-Jia Jibenyixi and to hydroxyl-α-Jia Jibenyixi.
The example of other polymerisable monomer comprises: styrene, alpha-alkyl phenylethylene (alkyl is the straight or branched alkyl with 1-10 carbon atom, and is hereinafter suitable equally) and by by at least one substituting group styrene derivative that phenyl ring obtained of alkyl, haloalkyl, the straight or branched alkoxy with 1-10 carbon atom, halogen atom, nitro, cyano group, amino or ester group substituted phenylethylene for example; Diolefin, for example 1,3-butadiene, isoprene and chlorbutadiene; (methyl) acrylate, (methyl) methyl acrylate for example, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid peopentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 4-isopentyl cyclohexyl, (methyl) allyl acrylate, (methyl) acrylic acid alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid benzene methyl, (methyl) phenylethyl, (methyl) acrylic acid 1-naphthalene ester, (methyl) acrylic acid 9-anthracene ester, (methyl) acrylic acid isopropyl benzene ester, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid three ring [5.2.1.02.6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid anthraquinone ester, (methyl) acrylic acid piperonyl ester, (methyl) acrylic acid salicyl ester, (methyl) CA, (methyl) glycidyl acrylate, (methyl) acrylic acid 1,1, the 1-trifluoro ethyl ester, (methyl) acrylic acid five fluorine ethyl esters, (methyl) acrylic acid seven fluorine n-propyls, (methyl) acrylic acid seven fluorine isopropyl esters, (methyl) acrylic acid triphenyl methyl esters, (methyl) acrylic acid 2-(N, the N-dimethylamino) ethyl ester, (methyl) acrylic acid 3-(N, N-dimethylamino) propyl ester, (methyl) acrylic acid furyl ester and (methyl) acrylic acid furfuryl group ester; (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N; N-diethyl (methyl) acrylamide; N; N-di (methyl) acrylamide; N, N-diisopropyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-anthryl (methyl) acrylamide; (methyl) vinyl cyanide; acryl aldehyde; fluorothene; vinylidene fluoride; vinyl chloride; vinylidene chloride; the N-vinyl pyrrolidone; the 2-vinylpyridine; the 3-vinylpyridine; 4-vinylpridine; vinyl acetate; N-phenylmaleimide; N-(4-hydroxyphenyl) maleimide; N-cyclohexyl maleimide and N-(methyl) acryloyl group phthalimide.
In the multipolymer of hydroxy styrenes and other copolymerisable monomer, the content of other copolymerisable monomer is preferably 30wt% or lower, and more preferably 20wt% or lower is based on the total amount meter of monomer.When the content of other copolymerisable monomer was higher than 30wt%, the alkali solubility of the multipolymer that is obtained may be unsatisfactory.
Particularly preferred in the present invention hydroxy styrenes resin is multipolymer or the para hydroxybenzene ethene and the cinnamic multipolymer of for example poly(4-hydroxystyrene), para hydroxybenzene ethene and adjacent methyl para hydroxybenzene ethene.
In the presence of solvent, can prepare the hydroxy styrenes resin by utilizing polymerization initiator polymerization hydroxy styrenes and other optional copolymerisable monomer.
The example that is used to prepare the solvent of hydroxy styrenes resin comprises: alcohol is methyl alcohol, ethanol and diacetone alcohol for example; Ether is tetrahydrofuran, oxinane He diox for example; Glycol ether is glycol monoethyl ether and ethylene glycol monoethyl ether for example; Ethylene glycol alkyl ether acetic acid esters is ethylene glycol monomethyl ether acetate and ethyl cellosolve acetate for example; Diglycol ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol and diglycol ethyl methyl ether for example; Propylene glycol is propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether and propylene glycol mono-n-butyl ether for example; Propylene glycol alkyl ether acetic acid ester is propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol positive propyl ether acetic acid esters and propylene glycol n-butyl ether acetic acid esters for example; Propylene glycol alkyl ether propionic ester is propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol positive propyl ether propionic ester and propylene glycol n-butyl ether propionic ester for example; Aromatic hydrocarbons is toluene and dimethylbenzene for example; Ketone is MEK, cyclohexanone and 4-hydroxyl 4-methyl-2 pentanone for example; With other ester class methyl acetate for example, ethyl acetate, n-propyl acetate, n-butyl acetate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the positive butyl ester of glycolic acid, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, the positive propoxy methyl acetate, positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, the n-butoxy n-butyl acetate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxypropionic acid n-propyl, the positive butyl ester of 2-methoxypropionic acid, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-propionic acid n-propyl, the positive butyl ester of 2-ethoxy-propionic acid, 2-n-butoxy methyl propionate, 2-n-butoxy ethyl propionate, 2-n-butoxy propionic acid n-propyl, 2-n-butoxy n-butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxypropionic acid n-propyl, the positive butyl ester of 3-methoxypropionic acid, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid n-propyl, the positive butyl ester of 3-ethoxy-propionic acid, 3-positive propoxy methyl propionate, 3-positive propoxy ethyl propionate, 3-positive propoxy propionic acid n-propyl, 3-positive propoxy n-butyl propionate, 3-n-butoxy methyl propionate, 3-n-butoxy ethyl propionate, 3-n-butoxy propionic acid n-propyl and 3-n-butoxy n-butyl propionate.
These solvents can use separately or two or more are used in combination.
The preferred 20-1 of the amount of the solvent in polyreaction, 000 weight portion, more preferably 100-500 weight portion is based on 100 weight portion overall reaction raw material meters.
The polymerization initiator that is used to prepare the hydroxy styrenes resin generally is known radical polymerization initiator.The example of known radical polymerization initiator comprises: azo-compound for example 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile) and 2,2 '-azo two-(4-methoxyl-2,4-methyl pentane nitrile); Organic peroxide is benzoyl peroxide, lauroyl peroxide, the peroxidating neopentanoic acid tert-butyl ester and 1 for example, 1 '-two-(t-butyl peroxyization) cyclohexane; And hydrogen peroxide.When superoxide was used as radical polymerization initiator, reductive agent can use as redox initiator with radical polymerization initiator.
As the interchangeable method for preparing the hydroxy styrenes resin; with the monomer of one or more phenolic hydroxyl group preparations by protecting above-mentioned hydroxy styrenes with blocking group such as alkyl, acetyl group or benzoyl group and optional above-mentioned other copolymerisable monomer polymerization and hydrolysis, to remove blocking group.
In the present invention, the transparency of hydroxy styrenes resin and softening point can be improved by methods such as hydrogenation before use.
The Mw of hydroxy styrenes resin is 10,000-100, and 000, preferred 15,000-50,000.Have the hydroxy styrenes resin of above-mentioned Mw by use, can obtain to have pattern form, resolution, development and thermotolerance and the good radiation-sensitive resin composition of balance between development and susceptibility.
The commercially available prod of hydroxy styrenes resin comprises: Malkarincar M and Malkarincar PHM-C (Maruzen Petrochemical Co., Ltd. make) and VP-15000 (Nippon Soda Co., Ltd. make), it is hydroxy styrenes homopolymer and multipolymer, and partially hydrogenated product.
In the present invention, above-mentioned hydroxy styrenes resin can use separately or two or more are used in combination, and can mix with above-mentioned linear phenol-aldehyde resin.
(B) polyfunctional monomer or polyfunctional monomer and simple function group monomer combination
In the present invention, the example of polyfunctional monomer comprises: aklylene glycol is two (methyl) acrylate of ethylene glycol or propylene glycol for example; Poly alkylene glycol is two (methyl) acrylate of polyglycol or polypropylene glycol for example; Poly-(methyl) acrylate with polyvalent alcohol of 3 or more a plurality of hydroxyls, wherein polyvalent alcohol is for example glycerine, trimethylolpropane, pentaerythrite or dipentaerythritol and their dicarboxylic acid modified product; Oligomeric (methyl) acrylate is polyester, epoxy resin, urethane resin, alkyd resin, silicones and spirane resin for example; Two (methyl) acrylate that has the polymkeric substance of hydroxyl at two ends, this polymkeric substance be the polycaprolactone for having the poly-1,3-butadiene of hydroxyl at two ends, having the polyisoprene of hydroxyl or have hydroxyl at two ends at two ends for example; With three [2-(methyl) acryloxy ethyl] phosphate.
Among these polyfunctional monomers, poly-(methyl) acrylate and dicarboxylic acid modified product thereof with polyvalent alcohol of 3 or more a plurality of hydroxyls are preferred.Particularly, three acrylic acid trihydroxy methyl propyl ester, trimethyl acrylic acid trihydroxy methyl propyl ester, pentaerythritol triacrylate, trimethyl acrylic acid pentaerythritol ester, the succinic acid modified product of pentaerythritol triacrylate, the succinic acid modified product of trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, dipentaerythritoltetraacrylate, tetramethyl acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester and hexamethyl acrylic acid dipentaerythritol ester are preferred, and three acrylic acid trihydroxy methyl propyl ester, pentaerythritol triacrylate and six acrylic acid dipentaerythritol ester are particularly preferred, can produce stain and film residue hardly because protrusion that is obtained and sept have in high intensity and excellent surface flatness and the zone outside the part that forms protrusion and/or sept.
Above-mentioned polyfunctional monomer can use separately or two or more are used in combination.
In the present invention, the amount of polyfunctional monomer is preferably 5-1,000 weight portion, and more preferably the 20-500 weight portion is counted based on 100 weight portion alkali soluble resinss (A).
When the amount of polyfunctional monomer was less than 5 weight portions, the protrusion that is obtained and the intensity of sept and surface flatness can become unsatisfactory.When this measures greater than 1,000 weight portion, alkali development meeting variation, or can produce stain and film residue in the zone outside the part that forms protrusion and/or sept.
In the present invention, the part polyfunctional monomer can substitute with the simple function group monomer.
The example of above-mentioned simple function group monomer comprises: with hydroxy styrenes and cited those identical monomers of those compounds of other polymerisable monomer of above-mentioned hydroxy styrenes resin; Unsaturated monocarboxylic acid, for example (methyl) acrylic acid, butenoic acid, α-Lv Daibingxisuan and cinnamic acid; Unsaturated dicarboxylic acid and acid anhydrides thereof, for example maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Unsaturated polybasic carboxylic acid and acid anhydrides thereof with three or more carboxyls; List [(methyl) acryloxyalkyl] ester with polybasic carboxylic acid of two or more carboxyls, for example succinic acid list [2-(methyl) acryloxy ethyl] ester and phthalic acid list [2-(methyl) acryloxy ethyl] ester; Esters of unsaturated carboxylic acids for example has list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl at two ends, for example single (methyl) acrylic acid ω-carboxyl polycaprolactone ester; With other esters of unsaturated carboxylic acids, for example (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester and (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester.
Among these simple function group monomers, preferred succinic acid list (2-acryloxy ethyl) ester (trade name: M-5300, by Toagosei Chemical Industry Co., Ltd. makes), succinic acid list (2-methacryloxyethyl) ester, single acrylic acid ω-carboxyl polycaprolactone ester, monomethyl acrylic acid ω-carboxyl polycaprolactone ester, acrylic acid methoxyl triethyleneglycol ester, methacrylic acid methoxy base triethyleneglycol ester, acrylic acid methoxyl dipropylene glycol ester, methacrylic acid methoxy base dipropylene glycol ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester and methacrylic acid 2-hydroxyl-3-phenoxy group propyl ester.
Above-mentioned simple function group monomer can use separately or two or more are used in combination.
The preferred 90wt% of the amount of simple function group monomer or lower, more preferably 50wt% or lower is based on the total amount meter of polyfunctional monomer and simple function group monomer.
(C) Photoepolymerizationinitiater initiater
Employed term " Photoepolymerizationinitiater initiater " means a kind of compound among the present invention, it is by being exposed to the fracture that radiation (hereinafter being called " irradiation ") causes decomposition or key, thereby form the active specy that can cause said components (B) polymerization, for example free radical, negative ion or kation.
Photoepolymerizationinitiater initiater is for example diimidazole compound, acetophenone compound, other optical free radical propellant or have the compound of trihalomethyl group.
The example of diimidazole compound comprises: 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 ' diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 ' diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole and 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Above-mentioned diimidazole based compound has excellent solvent soluble, can not produce impurity for example insolubles and precipitation, have high susceptibility and contrast, just can promote curing reaction fully with the irradiation of less energy, and can not cause curing reaction in the unexposed portion.Therefore, can clearly be divided into cured portion that is insoluble to alkaline developer and the uncured portion that in alkaline developer, has high dissolubility filming behind the irradiation, thus may not form can lack, the protrusion and the sept of loss or undercut.
The example of above-mentioned acetophenone compound comprises: 1-phenyl-2-hydroxy-2-methyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxy-cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-dimethoxy-1,2-diphenyl second-1-ketone, 1-[4-(methyl mercapto) phenyl]-2-methyl-2-morpholino third-1-ketone and 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino fourth-1-ketone.
The example of above-mentioned other optical free radical propellant comprises: benzophenone, 3; 3 '-dimethyl-4-methoxyl benzophenone, 2; 4-diethyl thioxanthone, 4-phenylazide formaldehyde, 4-phenylazide ethyl ketone, 4-nitrine benzylidene acetophenone, azido pyrene, 4-nitrine diphenylamine, 4-nitrine-4 '-methoxy diphenylamine, 4-nitrine-3-methoxy diphenylamine, two (2; 6-dimethoxy benzoyl)-2; 4,4-trimethylphenyl phosphine oxide, dibenzoyl, benzoin isobutyl butyl ether, N-phenyl sulfo-acridone and triphenyl pyrans perchlorate.
Above-mentioned example with compound of trihalomethyl group comprises: 1,3,5-three (trichloromethyl)-s-triazine, 1, two (the trichloromethyl)-5-(2-chlorphenyl) of 3--s-triazine, 1, two (the trichloromethyl)-5-(4-chlorphenyl) of 3--s-triazine, 1, two (the trichloromethyl)-5-(2-methoxyphenyl) of 3--s-triazine and 1, two (the trichloromethyl)-5-(4-methoxyphenyl) of 3--s-triazine.
At above-mentioned acetophenone compound, other optical free radical propellant with have among the compound of trihalomethyl group, 1-phenyl-2-hydroxy-2-methyl third-1-ketone, 1-[4-(methyl mercapto) phenyl]-2-methyl-2-morpholino third-1-ketone and 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino fourth-1-ketone are preferred, because they have high susceptibility, and the protrusion that forms during developing and sept can come off and have high intensity hardly from substrate.
In the present invention, above-mentioned Photoepolymerizationinitiater initiater can use separately or two or more are used in combination.
In the present invention, if desired, at least a photocrosslinking agent that is selected from sensitizer, curing accelerator and is made up of polymer compound or the material of photosensitizer (hereinafter being called " polymkeric substance photo-crosslinking/sensitizer ") can use with above-mentioned Photoepolymerizationinitiater initiater.
The example of above-mentioned sensitizer comprises: 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid ethyl ester, 1; 4-dimethylaminobenzoic acid 2-ethylhexyl, 2, two (the 4-diethylamino benzylidene) cyclohexanone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin and 4-(diethylamino) chalcone.
The example of above-mentioned curing accelerator comprises: chain-transferring agent is 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 for example, 5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-4,6-dimethyl aminopyridine, 1-phenyl-5-sulfydryl-1H-tetrazolium and 3-sulfydryl-4-methyl-4H-1,2, the 4-triazole.
In addition, above-mentioned polymkeric substance photo-crosslinking/sensitizer is for having the polymer compound of the functional group that can be used as photocrosslinking agent and/or sensitizer in main chain and/or side chain.The example of polymer compound comprises: the homopolymer of the condensation product of the condensation product of 4-phenylazide formaldehyde and polyvinyl alcohol (PVA), 4-phenylazide formaldehyde and linear phenol-aldehyde resin, 4-acryloyl group phenyl cinnamoyl ester and multipolymer, poly--1; 4-butadiene and poly--1, the 2-butadiene.
Among these sensitizers, curing accelerator and polymkeric substance photo-crosslinking/sensitizer, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone and 2-mercaptobenzothiazole are preferred, because they have high susceptibility and the protrusion that forms during developing and sept can come off and have high strength hardly from substrate.
In the present invention, Photoepolymerizationinitiater initiater is preferably diimidazole compound and at least a combination of compounds that is selected from acetophenone compound, benzophenone sensitizer and thiazolyl curing accelerator.
The preferred example of combinations thereof comprises: 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole and 4, the combination of 4 '-two (diethylamino) benzophenone, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 4, the combination of 4 '-two (diethylamino) benzophenone and 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino fourth-1-ketone, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 4,4 '-two (diethylamino) benzophenone and 1-[4-(methyl mercapto) phenyl]-combination of 2-methyl-2-morpholino third-1-ketone, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 4,4 '-two (dimethylamino) benzophenone, 1-[4-(methyl mercapto) phenyl]-combination of 2-methyl-2-morpholino third-1-ketone and 2-mercaptobenzothiazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole and 4, the combination of 4 '-two (diethylamino) benzophenone, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, the combination of 4,4 '-two (diethylamino) benzophenone and 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino fourth-1-ketone, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 4,4 '-two (diethylamino) benzophenone and 1-[4-(methyl mercapto) phenyl]-combination of 2-methyl-2-morpholino third-1-ketone, with 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 4,4 '-two (dimethylamino) benzophenone, 1-[4-(methyl mercapto) phenyl]-combination of 2-methyl-2-morpholino third-1-ketone and 2-mercaptobenzothiazole.
In the present invention, acetophenone compound, other optical free radical propellant and the total amount with compound of trihalomethyl group are preferably the 80wt% of Photoepolymerizationinitiater initiater total amount or lower, the total amount of sensitizer and curing accelerator is preferably the 80wt% of Photoepolymerizationinitiater initiater total amount or lower, and further the amount of polymkeric substance photo-crosslinking/sensitizer is preferably 200 weight portions or still less, more preferably 180 weight portions or still less are based on 100 weight portion diimidazole compound meters.
The amount of Photoepolymerizationinitiater initiater is preferably the 0.01-500 weight portion in the present invention, more preferably 1-300 weight portion, and preferred especially 10-200 weight portion is based on component (B) meter of 100 weight portions.When the amount of Photoepolymerizationinitiater initiater is less than 0.01 weight portion, because the incomplete curing of irradiation, the protrusion of some formation and sept can lack, loss or undercut, and when it measures greater than 500 weight portions, the protrusion and the sept that form during developing can come off from substrate, and can produce stain and film residue on the zone outside the part that forms protrusion and/or sept.
(D) melamine compound
Preferably, radiation-sensitive resin composition of the present invention further comprises the melamine compound (hereinafter being called " melamine compound (D) ") by following formula (1) expression:
Figure A20051005424200161
R wherein 1, R 2, R 3, R 4, R 5And R 6Be independently of one another hydrogen atom or-CH 2OR, R are hydrogen atom or the straight or branched alkyl with 1-6 carbon atom.
The example of melamine compound (D) comprising: melamine; The hydroxyalkyl melamine is N for example, N-dihydroxymethyl melamine, N, N, N ', N '-tetra methylol melamine, hexamethylolmelamine and six positive hydroxyl melamine-butyls; With alkoxy methyl melamine N for example, N-two (methoxy) melamine, N, N, N ', N '-four (methoxy) melamine, six (methoxy) melamines and six (n-butoxy methyl) melamine.
The commercially available prod of melamine compound (D) comprising: Simel 202,238, and 266,267,272,300,301,303,325,327,370,701,1141,1156 and 1158 (Mitsui Cyanamid Co., Ltd. makes), Nicalak Mx-31,-40 ,-45 ,-032,-706 ,-708 and-750, Nicalak Ms-11 and-001 and Nicalak Mw-22 and-30 (Sanwa Chemical Co., Ltd. make).
In the present invention, above-mentioned melamine compound (D) can use separately or two or more are used in combination.
The amount of melamine compound (D) is preferably the 1-500 weight portion in the present invention, and more preferably the 5-250 weight portion is counted based on 100 weight portion alkali soluble resinss (A).By in this scope, using melamine compound (D), can obtain in alkaline developer, to demonstrate the composition of suitable solubleness, and can form protrusion and sept with excellent in shape.
(E) phenolic compound
Preferably, radiation-sensitive resin composition of the present invention can further comprise the phenolic compound (hereinafter being called " phenolic compound (E) ") that has less than 10,000 Mw.
The example of phenolic compound (E) comprising: poly-(vinylphenol), for example poly-(adjacent vinylphenol), poly-(vinylphenol), poly-(to vinylphenol), poly-(to isopropenyl phenol) and poly-(3-methyl-4-vinylphenol); With the low-molecular-weight phenolic compound by following formula (2)-(8) expressions:
Figure A20051005424200181
R wherein 7Be hydrogen atom or methyl independently of one another, and a, b, c, d, p, q, r and s respectively do for oneself 0-3 integer and satisfy (a+b+c+d) 〉=2.
Among these phenolic compounds (E), poly-(vinylphenol) is preferred.It is synthetic that poly-(vinylphenol) can carry out cationic polymerization by vinylphenol in the presence of as the boron trifluoride of polymerization initiator or hydrogen iodide, perhaps in the presence of as the azoisobutyronitrile of polymerization initiator or benzoyl peroxide vinylphenol to carry out free radical polymerization synthetic.
The example of the commercially available prod of poly-(vinylphenol) comprises MARUKALYNCUR-M (MaruzenPetrochemical Co., Ltd. makes).
The Mw of poly-(vinylphenol) is preferably less than 10,000, and more preferably 1,000 or bigger and less than 10,000.When the Mw of poly-(vinylphenol) is 10,000 or when bigger, on the zone outside the part that forms protrusion and/or sept, can form the development residue.
The Mw of low-molecular-weight phenolic compound is preferably 1,000 or lower.When the Mw of low-molecular-weight phenolic compound is higher than at 1,000 o'clock, resolution can variation.
In the present invention, above-mentioned phenolic compound (E) can use separately or two or more are used in combination.
The amount of phenolic compound (E) is preferably the 0.1-300 weight portion in the present invention, and more preferably the 1-150 weight portion is counted based on 100 weight portion alkali soluble resinss (A).By use phenolic compound (E) in this scope, susceptibility and resolution can improve.
-other adjuvant-
If need, radiation-sensitive resin composition of the present invention can further comprise other adjuvant.
Other adjuvant comprises dispersing aid, for example is enumerated as the blue pigment derivant or the yellow uitramarine derivant of copper phthalocyanine derivative thing; Polymer compound, for example polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether or poly-(fluoroalkyl acrylate); Nonionic, kation or anionic surfactant; Adhesion promoter, vinyltrimethoxy silane for example, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane or 3-sulfydryl propyl trimethoxy silicane; Antioxidant, for example 2,2-thiobis (4-methyl-6-tert butyl phenol) or 2,6 di t butyl phenol; UV absorbers, for example 2-(the 3-tert-butyl group-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxy benzophenone; And anti-coagulants, for example sodium polyacrylate.
-solvent-
Radiation-sensitive resin composition of the present invention is dissolved in the suitable solvent before use usually to be prepared into composition solution.
Only otherwise with component (A)-(E) and other additive reaction and have suitable volatility, suitable solvent can be selected and as the solvent of preparation above-mentioned composition solution.
The example of solvent comprises: (gathering) alkylene glycol monoalkyl ethers, for example glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary positive propyl ether, diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, 3 third glycol monomethyl ethers and 3 third glycol list ether; (gathering) aklylene glycol alkyl ether acetic acid esters, for example ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, diethylene glycol methyl ether acetic acid esters, DGDE acetic acid esters, propylene glycol methyl ether acetate and propylene-glycol ethyl ether acetic acid esters; Other ether, for example diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol and tetrahydrofuran; Ketone, for example methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl ester, for example methyl lactate and ethyl lactate; Other ester, for example 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetate 3-methyl-3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate and 2-ketobutyric acid ethyl ester; Aromatic hydrocarbons, for example toluene and dimethylbenzene; And carboxylic acid amide, for example N-Methyl pyrrolidone, N, dinethylformamide and N,N-dimethylacetamide.
These solvents can use separately or two or more are used in combination.
In addition, high boiling solvent is benzyl ether, two n-hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, phenmethylol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate or ethylene glycol phenyl ether acetic acid esters for example, can use with solvent.
These high boiling solvents can use separately or two or more are used in combination.
In above-mentioned solvent, for the viewpoint of dissolubility and coating performance, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, the propylene-glycol ethyl ether acetic acid esters, diethylene glycol dimethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, ethyl lactate, propionic acid 3-methyl-3-methoxyl butyl ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, positive butyl ester of butyric acid and ethyl pyruvate are preferred.Gamma-butyrolacton is preferred as high boiling solvent.
The amount of solvent is preferably 100-10,000 weight portion, and more preferably 500-5,000 weight portion is counted based on 100 weight portion alkali soluble resinss (A).
The available before use millipore filter with about 0.5 μ m aperture of composition solution filters.
Form the method for protrusion and sept
The method of the protrusion and/or the sept that are formed for vertical orientated liquid crystal display of the present invention is described subsequently.
In the present invention, protrusion and the sept that only is used for the protrusion of vertical orientated liquid crystal display or is used for vertical orientated liquid crystal display is preferably formed in substrate.
Being formed for the protrusion of vertical orientated liquid crystal display of the present invention and/or the method for sept may further comprise the steps:
(a) coating of formation radiation-sensitive resin composition of the present invention in substrate;
(b) partial coating is exposed in the radiation;
(c) behind the irradiation coating is developed to form pattern; And
(d) development back heating coating.
Above-mentioned each step will be described below.
In step (a), with in the substrate of composition solution paint and preroast desolvate to remove so that form the coating of radiation-sensitive resin composition.
Above-mentioned substrate is that perhaps by transparent plastic, for example polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate are made by glass for example float glass or soda-lime glass.Appropriate pretreatment can be randomly carried out in substrate, for example carries out chemical treatment, Cement Composite Treated by Plasma, ion plating, spraying plating, gas vapour-phase reaction or vacuum moulding machine with silane coupling agent.
Can adopt for example spraying of suitable coating technique, roller coat or spin coating, in the substrate of composition solution paint.
The thickness of coating is preferably 0.1-10 μ m after prebake, and more preferably 0.2-5.0 μ m is preferably 1.0-4.0 μ m especially.
As for the prebake condition, and different, coating was at 70-120 ℃ of following prebake 1-15 minute according to the type of each component and amount for it.
In step (b), partial coating is exposed under the UV radiation.
The preferred photomask that uses is with the expose portion coating.For making protrusion and sept all be formed in the substrate, (a) use single photomask with protrusion and spacer patterns, with coating irradiation once, perhaps (b) uses photomask with protrusion pattern and the photomask with spacer patterns, with twice of coating irradiation.The photomask with protrusion and spacer patterns that transmissivity each other is different can be used as the photomask that uses in method (a).
In order in substrate, to form protrusion or sept, (c) have the photomask of protrusion pattern or have the photomask of spacer patterns, once coating irradiation by use.In this case, other protrusions of formation that vertical orientated liquid crystal display is required or the method for sept are not particularly limited, and can use known method.
The radiation that is used for irradiation is visible radiation, UV radiation, far ultraviolet radiation, electron beam or X-ray, but preferred UV radiation.
The dosage of radiation is preferably about 10-10,000J/m 2
In step (c), with the alkaline developer coating of developing, remove unwanted part, so that form predetermined pattern.
The aqueous solution of the preferred inorganic base of above-mentioned alkaline developer, for example NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammonia; Primary amine, for example ethamine or n-propylamine; Secondary amine, for example diethylamine or di-n-propylamine; Tertiary amine, for example trimethylamine, methyl diethylamide, dimethylethyl amine or triethylamine; Alkanolamine, for example dimethylethanolamine, methyldiethanolamine or triethanolamine; Alicyclic tertiary amine, for example pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diaza-bicyclo [5.4.0]-7-undecylene or 1,5-diaza-bicyclo [4.3.0]-5-nonene; Aromatic uncle amine, for example pyridine, collidine, lutidines or quinoline; Or quaternary ammonium salt, for example Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
In above-mentioned alkaline developer, can add an amount of water-miscible organic solvent such as methyl alcohol or ethanol and/or surfactant.
Can adopt and stir development method, immersion development method, shower development method or its similar approach, and development time is preferably about 5-300 second.
After alkaline development, for example coating is with running water flushing 30-90 second, and with pressurized air or compressed nitrogen drying.
In following step (d), with the coating after developing with well heater for example hot plate or baking box (hereinafter being called " back roasting ") heat, to form predetermined protrusion and/or sept.
As for the back roasting condition, temperature is preferably 150-250 ℃, and the time on hot plate be about 5-30 minute, the time in baking box is about 30-90 minute.
The height of the protrusion of Xing Chenging is preferably 0.1-3.0 μ m like this, more preferably 0.5-2.0 μ m, especially preferably 1.0-1.5 μ m.Their bottom size is preferably 1-50 μ m, more preferably 2-30 μ m, especially preferably 3-10 μ m.
The height of sept is preferably 1-10 μ m, more preferably 2-8 μ m, especially preferably 3-5 μ m.Their bottom size is preferably 5-150 μ m, more preferably 5-100 μ m, especially preferably 10-50 μ m.
Vertical orientated liquid crystal display
Vertical orientated liquid crystal display of the present invention comprises by the protrusion of radiation-sensitive resin composition preparation of the present invention and/or the sept that is prepared by radiation-sensitive resin composition of the present invention, and had preferred 50 seconds or shorter residual image elimination time 100 seconds or shorter.
Vertical orientated liquid crystal display can be by following method (e) or (f) is prepared.
(e) on a side of substrate, form transparent conductive film with predetermined pattern, by said method protrusion is formed on the conductive film, and the mode by roller coat, spin coating or printing is in the substrate of liquid crystal orientating agent paint, and heating is to form liquid crystal orientation film.
Above-mentioned substrate is to be used in glass described in the method that forms protrusion and/or sept or transparent plastic preparation.
Tin oxide (SnO 2) film or by indium oxide-tin oxide (In 2O 3-SnO 2) preparation ito thin film can be used as transparent conductive film.
In order to form the transparent conductive film pattern, can use the method for photo-engraving process or use photomask.
Before adopting liquid crystal orientating agent, in order further to improve substrate or the surface of transparent conductive film and the bounding force between the liquid crystal orientation film, functionalized silane compound or functionalized titanium compound paint can be had on the substrate surface of transparent conductive film.
After adopting liquid crystal orientating agent, heating-up temperature is preferably 80-300 ℃, more preferably 120-250 ℃.
The thickness of liquid crystal orientation film is preferably 0.001-1 μ m, more preferably 0.005-0.5 μ m.
(f) two of preparations have the substrate of the liquid crystal orientation film that forms with said method (e), will be toward each other by the film formed substrate surface of liquid crystal aligning, between it, keep the box gap, use bonding agent that the outer boundary of substrate is linked together, liquid crystal is inserted the box gap that surface and adhesive phase by substrate are limited, and filler opening is sealed up to constitute liquid crystal cell.Thereafter, with the outside surface of liquid crystal cell, the another one surface that promptly constitutes the substrate of liquid crystal cell is connected on separately the polarizer, to obtain liquid crystal display.
Above-mentioned bonding agent is the epoxy resin that for example contains hardening agent, and as the alumina balls of sept.
The example of above-mentioned liquid crystal comprises: nematic crystal, smectic crystal and ferroelectric liquid crystal, for example cinnamic acid is to the n-decyloxy benzylidene-to the amino-2-methyl butyl ester, among these liquid crystal, nematic crystal is preferred.
The object lesson of above-mentioned nematic crystal comprises: schiff bases liquid crystal, azoxy liquid crystal, xenyl liquid crystal, cyclohexylbenzene base fluid crystalline substance, ester group liquid crystal, terphenyl liquid crystal, cyclohexyl biphenyl hexyl liquid crystal, pyrimidine radicals liquid crystal, alkyl dioxin liquid crystal, bicyclooctane base fluid crystalline substance and cubane base fluid crystalline substance.
Before use, in above-mentioned liquid crystal, can add for example chiral reagent of cholest chlorine, cholesteryl nonanoate or cholesteryl carbonate and the commercial trade mark that can buy C-15 by name and CB-15 (Merk Co., Ltd. makes) of cholesteryl liquid crystal.
Be connected to the polarizer on the liquid crystal cell outside surface, stretch and absorbed during orientation the polarizer that the H film of iodine is formed by polyvinyl alcohol (PVA), or the polarizer of making by the polarized film that interlayer between the cellulose acetate diaphragm is made up of the H film.
Radiation-sensitive resin composition of the present invention, it is used for vertical orientated the liquid crystal display for example protrusion of color display apparatus and/or the formation of sept, protrusion and sept with excellent surface flatness can be provided, in the substrate of unexposed portion, produce the development residue hardly, cause peeling off of protrusion and sept hardly, disappearance or loss, but and can provide the liquid crystal with excellence vertical orientation, but high voltage retentivity and short afterimage are eliminated the time and are not almost had fluorescent screen images to keep and show the vertical orientated liquid crystal display of unevenness.
Form the method for the protrusion and/or the sept of vertical orientated chromatic liquid crystal display equipment of the present invention, can access fine pattern, be convenient to control shape and size (height and bottom size), and can form meticulous protrusion and sept in high and stable yields ground with above-mentioned excellent properties.
Embodiment
Embodiment
To limit the present invention absolutely not in order further setting forth, following embodiment to be provided.
Synthetic embodiment 1
Formalin, 0.63g oxalic anhydride and the 264g methyl isobutyl ketone of 57g metacresol, 38g paracresol, 75.5g37wt% are joined in the flask that cooling tube, stirrer and thermometer are housed, and flask immersed in the oil bath, reflux at solution and carried out polycondensation reaction 4 hours under the condition of stirring simultaneously.Subsequently, the temperature of oil bath is elevated to 150 ℃, and in 3 hours that the internal drop of flask is low to 30-50mmHg, to remove volatile matter, then the resin cool to room temperature of fusion is collected.Then the concentration of this resin with 30wt% is dissolved in the ethyl acetate, and adds respectively first alcohol and water, stir and leave standstill in 1.3 times of solution weights and 0.9 times.Subsequently, solution is divided into two-layer, takes out lower floor, concentrates and dry, thereby obtain to have the linear phenol-aldehyde resin of 8,000 Mw.This linear phenol-aldehyde resin note is made resin (A-1).
Synthetic embodiment 2
176g is being joined in the flask that cooling tube, stirrer and thermometer are housed tert-butoxy styrene and 5.8g azo dibutyronitrile, and further adding the 250ml propylene glycol monomethyl ether, under 75 ℃, carrying out polymerization 4 hours with after dissolving these components.Subsequently, the aqueous sulfuric acid of 50g5wt% is mixed with the gained resin solution, reaction 3 hours is hydrolyzed under 100 ℃.Add the 500ml propylene glycol methyl ether acetate then in reaction solution, 1, washing is three times in the 000ml deionized water with reaction solution, separate organic layer, under reduced pressure remove and desolvate, and under vacuum the reaction solution of dry gained, thereby obtain to have 24, poly-(the para hydroxybenzene ethene) of 000Mw.This poly-(para hydroxybenzene ethene) note is made resin (A-2).
Synthetic embodiment 3
3g azoisobutyronitrile and 300g dihydroxypropane single-ether are joined in the flask that cooling tube, stirrer and thermometer are housed, and further add 25g methacrylic acid, 15g styrene and 60g benzyl methacrylate, the flask interior nitrogen replacement, and in gentle agitation, solution temperature is elevated to 70 ℃, and kept this temperature 5 hours so that carry out polyreaction.Under reduced pressure from reaction solution, remove desolvate after, the gained reaction solution is dry under vacuum, to obtain having 8, the multipolymer of the methacrylic acid of 000Mw, styrene and benzyl methacrylate (weight ratio 25/15/60).This multipolymer note is made resin (a-1).
Embodiment 1
Will be as 100 parts by weight resin (A-1) of component (A), 40 weight portions, six acrylic acid dipentaerythritol ester as component (B), 10 weight portions 2 as component (C), 2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 10 weight portions 4,4 '-two (diethylamino) benzophenone and 20 weight portion 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 20 weight portion Cymel, 300 (trade (brand) names as component (D), Mitsui Cyanamid Co., Ltd. make), mix and be dissolved in together as poly-(to vinylphenol) (Mw=8,000) of 10 weight portions of component (E) with as 1,500 weight portion 3-ethoxyl ethyl propionate of solvent, and the solution of gained is filtered with the film filter with 0.2 μ m aperture, with the solution (hereinafter being called " composition solution (S1) ") of preparation radiation-sensitive resin composition.
The formation of-protrusion-
On the surface of spin coater with the substrate of composition solution (S1) paint soda-lime glass, this substrate of glass has silicon dioxide (SiO 2) film is with the wash-out of the sodion that prevents to form from the teeth outwards, and 90 ℃ of following prebakes 4 minutes, so that form the thick coating of 1.3 μ m.
Subsequently, with the substrate cool to room temperature, and adopt high-pressure sodium lamp, it is 365nm's and pass 2 of photomask, 000J/m that coating is exposed to wavelength 2In the UV radiation, be cured.Subsequently, under 23 ℃, substrate is immersed in the potassium hydroxide aqueous solution of 0.04wt% and made it to develop in 1 minute, in ultrapure water flushing and with air drying with the formation pattern.Then, coating 250 ℃ of following back roastings 30 minutes, had the protrusion of reservation shape with formation in substrate.
In the substrate of gained unexposed portion, do not observe the development residue, do not see separation, disappearance or the loss of protrusion yet.When by observation by light microscope protrusion surface, do not see coarse surface, protrusion has excellent surface flatness.
The manufacturing of-vertical orientated the liquid crystal display that is used to estimate-
With spin coater with composition solution (S1) paint on the transparent conductive film of forming by the ITO film that forms on the side of the thick substrate of glass of 1mm, and 90 ℃ of following prebakes 4 minutes, so that form the thick coating of 1.3 μ m.Subsequently,, and adopt high-pressure sodium lamp, the whole surface of coating is exposed to has 2 of 365nm wavelength, 000J/m the substrate cool to room temperature 2UV radiation in, be cured.Then, under 23 ℃, substrate is immersed in the potassium hydroxide aqueous solution of 0.04wt% and made it to develop in 1 minute, flushing and use air drying in ultrapure water.Then, substrate is descended back roastings 30 minutes at 250 ℃, in substrate, to form the coating of radiation-sensitive resin composition.
Subsequently, with liquid crystal orientating agent (trade (brand) name JALS2095-S2, JSR Corporation manufacturing) on the side with having of spinner paint substrate radiation-sensitive resin composition coating formed thereon, on the side that does not have coating of substrate, and under 80 ℃, heated 1 minute, heated 1 hour down at 180 ℃ then, so that in substrate, form liquid crystal orientation film with 600 thickness.The epoxy adhesive that will contain alumina balls by serigraphy is applied on the outward flange of substrate, with the lip-deep liquid crystal orientation film that is formed on two substrates toward each other, between it, keep the box gap, the outward flange of substrate is contacted with each other so that its pressure sticks together cure adhesive.Then, to bear nematic crystal (Ltd. makes for trade (brand) name MLC6608, Merk Co.) inserts in the box gap that adhesive phase limited by the surface of substrate and outer edge part, and filler opening is sealed up the vertical orientated liquid crystal display that is used to estimate with manufacturing with epoxy adhesive.
The evaluation of the vertical orientated liquid crystal display of gained is as follows.Evaluation result is shown in Table 1.
The evaluation of-vertical orientated performance-
When voltage take-off and when adopting the direct current of 12V (peak-peak), under crossed nicols, observe vertical orientated liquid crystal display.When not observing the orientation failure in liquid crystal, vertical orientated assessment of performance is excellent.
But the evaluation of-voltage retentivity-
After applying 5V voltage 60 microseconds to vertical orientated liquid crystal display with 167 milliseconds of septs, the voltage after 167 milliseconds of moment that finally stops to apply voltage keeps performance with Toyo Technica Co., and the VHR-1 of Ltd. measures.
The evaluation of-afterimage elimination time-
By under 70 ℃ the square wave with 30Hz frequency and 3.0V voltage of the alternating current stack gained of the direct current of 6.0V (peak value) and 6.0V (peak value) being applied to vertical orientated liquid crystal display after last 167 hour, stop to apply, and measure afterimage and visually eliminate the time before.
Embodiment 2
With with embodiment 1 in identical method prepare radiation-sensitive resin composition solution (hereinafter being called " composition solution (S2) "), except replacing the resin (A-1) of 100 weight portions as component (A) with resin (A-2).
Then, use with embodiment 1 in identical method carry out the formation of protrusion and the manufacturing of liquid crystal display, except replacing composition solution (S1), make an appraisal with composition solution (S2).Evaluation result is shown in Table 1.
Comparative Examples 1
Will be as 100 parts by weight resin (a-1) of alkali soluble resins (A), 80 weight portions, six acrylic acid dipentaerythritol ester as component (B), 20 weight portions 2 as component (C), 2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 20 weight portions 4,4 '-two (diethylamino) benzophenone and 40 weight portion 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone and as 1 of solvent, 500 weight portion 3-ethoxyl ethyl propionates mix and are dissolved in together, and the solution of gained is filtered with the film filter with 0.2 μ m aperture, with the solution (hereinafter being called " composition solution (s1) ") of preparation radiation-sensitive resin composition.
Then, use with embodiment 1 in identical method carry out the formation of protrusion and the manufacturing of liquid crystal display, except replacing composition solution (S1), make an appraisal with composition solution (s1).Evaluation result is shown in Table 1.
Table 1
The development residue Separate, lack and loss Surface flatness Vertical orientated performance But voltage retentivity (%) Afterimage is eliminated the time (second)
??Ex.1 Do not have Do not have Excellent Excellent ????99.0 ??10
??Ex.2 Do not have Do not have Excellent Excellent ????98.8 ??15
??C.Ex.1 Do not have Do not have Excellent Excellent ????98.5 200 or longer
Ex.: embodiment
C.Ex.: the comparative example

Claims (7)

1. radiation-sensitive resin composition, it comprises (A) at least a being selected from the polystyrene is that the weight-average molecular weight that standard specimen is measured by gel permeation chromatography is 2,000-20,000 linear phenol-aldehyde resin and be that the weight-average molecular weight that standard specimen is measured by gel permeation chromatography is 10 with the polystyrene, 000-100, the alkali soluble resins of 000 hydroxy styrenes resin, (B) polyfunctional monomer or polyfunctional monomer and simple function group monomer combination, (C) Photoepolymerizationinitiater initiater, and said composition is used for having 100 seconds or shorter afterimage is eliminated the vertical orientated liquid crystal display of time and formed protrusion and/or sept.
2. according to the radiation-sensitive resin composition of claim 1, it further comprises the melamine compound by following formula (1) expression:
R wherein 1, R 2, R 3, R 4, R 5And R 6Be independently of one another hydrogen atom or-CH 2OR, R are hydrogen atom or the straight or branched alkyl with 1-6 carbon atom.
3. according to the radiation-sensitive resin composition of claim 1, weight-average molecular weight that to be standard specimen with the polystyrene measure by gel permeation chromatography that it further comprises (E) is less than 10,000 phenolic compound.
4. the protrusion of vertical orientated liquid crystal display, it is made by each described radiation-sensitive resin composition of claim 1-3.
5. the sept of vertical orientated liquid crystal display, it is made by each described radiation-sensitive resin composition of claim 1-3.
6. one kind forms the protrusion of vertical orientated liquid crystal display and/or the method for sept, and it may further comprise the steps:
(a) coating of each described radiation-sensitive resin composition of formation claim 1-3 in substrate;
(b) partial coating is exposed in the radiation;
(c) behind the irradiation coating is developed to form pattern; And
(d) development back heating coating.
7. vertical orientated liquid crystal display, it comprises described protrusion of claim 4 and/or the described sept of claim 5, and has 100 seconds or shorter afterimage is eliminated the time.
CNA200510054242XA 2004-02-09 2005-02-08 Formation of projections and spacers and radiation sensitive resin composition for the same Pending CN1670625A (en)

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