CN101131511B - Polymer having unsaturated side chain, radiation-sensitive resin composition and spacer for liquid crystal display element - Google Patents

Polymer having unsaturated side chain, radiation-sensitive resin composition and spacer for liquid crystal display element Download PDF

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CN101131511B
CN101131511B CN2006100647360A CN200610064736A CN101131511B CN 101131511 B CN101131511 B CN 101131511B CN 2006100647360 A CN2006100647360 A CN 2006100647360A CN 200610064736 A CN200610064736 A CN 200610064736A CN 101131511 B CN101131511 B CN 101131511B
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ester
acrylic acid
acid
methyl
methacrylic acid
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CN101131511A (en
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一户大吾
米仓勇
西尾寿浩
志保浩司
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JSR Corp
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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
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a polymer having unsaturated side chain, a radiation-sensitive resin composition and a spacer for a liquid crystal display element, and relates to the radiation-sensitive resin composition which includes a polymer obtained by reacting a copolymer comprising: (a1) unsaturated carboxylic acid and carboxylic anhydride; (a2) an unsaturated compound containing hydroxyl group; and (a3) the polymer obtained by reacting copolymer of another unsaturated compound except the compounds (a1) and (a2) with isocyanate compound. The invention also provides the radiation-sensitive resin composition having high sensitivity, forming a sufficient spacer form even by the exposure rate of <=1,200 J/m<2> and giving a spacer for a liquid crystal display element having excellent softness, high recovery rate, rubbing resistance, adhesiveness to a transparent substrate, heat resistance, etc.

Description

Side chain unsaturated polymer, radiation sensitive resin composition and used for liquid crystal display element sept
Technical field
The present invention be more particularly directed to be very suitable for forming the side chain unsaturated polymer of the middle parting of liquid crystal display cells, the radiation sensitive resin composition that contains this side chain unsaturated polymer, sept and forming method thereof and liquid crystal display cells.
Background technology
All the time, in liquid crystal display cells, in order to make the certain interval (cel-gap) of maintenance between 2 substrates; Use the sept of beaded glass with regulation particle diameter, plastic bead etc. always; But these septs, because there is sept in random distribution on transparency carriers such as glass substrate if form the zone at pixel; Will produce sept mirror phenomenon or incident light receives scattering, and the problem that the contrast of liquid crystal cell is reduced.
In order to address these problems, adopted photoetching process to form the method for sept.This method is that radiation sensitive resin composition is coated on the substrate; Mask through regulation; Carry out for example developing behind the ultraviolet exposure; Form point-like or strip sept,, therefore can solve aforesaid problem basically owing to can only form sept at the regulation position that pixel forms outside the zone.
In recent years, consider that mother glass substrate develops (for example: 1,500 * 1,800mm is further 1,870 * 2, about 200mm) to the maximization direction from the large tracts of landization that realizes liquid crystal display cells and the equal angles of enhancing productivity.But, in the substrate size in the past,, but in large substrate, possibly prepare the mask suitable hardly, so be difficult to be suitable for the single exposure mode with this substrate size because substrate size less than mask size, can adopt the single exposure mode corresponding.
Therefore, as the Exposure mode that possibly be applicable to large substrate, advocate and use the substep Exposure mode.But in the substep Exposure mode, a substrate carries out multiexposure, multiple exposure, and when making public, aligned position or will expend time in when moving between the step so compare with the single exposure mode, the problem that its throughput rate reduces occurred at every turn.
In addition, in the single exposure mode, exposure can reach 3,000J/m 2About, but in the substep Exposure mode, must reduce the exposure of each time, in the formation of sept, in the used existing radiation sensitive resin composition, be difficult in 1,200J/m 2Or the sept shape that improves under the following exposure and enough thickness.
On the other hand, consider, introduced the engineering " ODF (instillation) method " that before liquid crystal material is dripped to glass surface at the liquid crystal panel glass gluing from the aspect of enhancing productivity.
Utilize this method, can significantly shorten the time.For example when 30 inches panels of preparation, be filling liquid crystal material, needs are about 5 days under classic method, and employing ODF method then needs got final product in about 2 hours, can significantly boost productivity.
In existing laminating type, when tft array and color filter are fitted,, thereby keep the homogeneity of sept height because imposed load evenly pushes sept through this load.But in the ODF method, because the load and the atmospheric pressure that only utilize substrate weight to produce are fitted, compare with classic method at first, the applying load at initial stage is less.Therefore, though under less load, push sept, also through evenly push manifest the height homogeneity, this point is important.Sept just must have flexibility for this reason.If the height heterogeneity of sept just can't guarantee the homogeneity of cel-gap, liquid crystal cell is inner to produce the gap, thereby causes that demonstration is inhomogeneous.Therefore, need have flexibility and the spacer material of high response rate under the compressive load simultaneously.
Open in the 2003-173025 communique the spy; Proposed in photosensitive polymer combination; The optical polymerism functional group that use obtains with copolymerization property resin through having imide and hydroxyl and the reaction of (methyl) acryloyloxyalkyl isocyanate compound is as the copolymerization property resin of structural unit, thereby can realize that high sensitivity, high response rate etc. have improved the sept of performance.But, do not consider the problem of flexibility aspect.
As stated; In existing radiation sensitive resin composition; Use and have the copolymerization property resin of optical polymerism functional group as structural unit; Though can realize high sensitivity and high response rate, and not mentioned providing further has the material of the sept of flexibility fully concurrently except high sensitivity and high response rate.
Summary of the invention
Even problem of the present invention is to provide high sensitivity 1,200J/m 2Or the sept shape that also improves under the following exposure, can form flexibility and high response rate, rub resistance, with equal radiation sensitive resin composition of excellent used for liquid crystal display element sept such as the tack of transparency carrier, thermotolerance.
Another problem of the present invention is to provide can be as the side chain unsaturated polymer of the resinous principle of this radiation sensitive resin composition etc.
Another problem of the present invention is to provide the liquid crystal display that formed by above-mentioned radiation sensitive resin composition with sept and the liquid crystal display cells that possesses this sept.
Another problem of the present invention is to provide the formation method of above-mentioned liquid crystal display with sept.
According to the present invention, above-mentioned problem at first be through:
(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,
(a2) be selected from following formula (1)～(4) at least a compound of the group formed of hydroxyl unsaturated compound of expression respectively, and
(a3) except that (a1) and the polymkeric substance that obtains of the isocyanate compound shown in the multipolymer of other unsaturated compounds (a2) and the following formula (5) reaction (below be called polymkeric substance [A]) realize.
Figure G06164736020070124D000031
(in the formula, R representes hydrogen atom or methyl, and a is 5 or above integer.)
Figure G06164736020070124D000032
(in the formula, R representes hydrogen atom or methyl, and b, c are 1～12 integer independently of one another.)
(in the formula, R representes hydrogen atom or methyl, and d, e are 1～12 integer independently of one another.)
(in the formula, R representes hydrogen atom or methyl, and f, g are 0～6 integer independently of one another, and W is the divalent group of the ester ring type structure that has arbitrary following formula (I)～(IV) institute and represent respectively.)
Figure G06164736020070124D000042
Figure G06164736020070124D000043
(in the formula, R representes hydrogen atom or methyl, and h is 1～12 integer.)
According to the present invention, above-mentioned problem second realizes that through radiation sensitive resin composition the characteristic of this radiation sensitive resin composition is to contain polymkeric substance [A], polymerizable unsaturated compound [B] and radiation-sensitive polymerization initiator [C].
According to the present invention; Above-mentioned problem the 3rd realizes that through radiation sensitive resin composition (below be called " the liquid crystal display cells sept is used radiation sensitive resin composition ") this radiation sensitive resin composition comprises above-mentioned radiation sensitive resin composition, is used to form the used for liquid crystal display element sept.
According to the present invention, above-mentioned problem the 4th realizes that through the used for liquid crystal display element sept this used for liquid crystal display element sept is formed with radiation sensitive resin composition by the used for liquid crystal display element sept.
According to the present invention, above-mentioned problem the 5th is that the formation method through the used for liquid crystal display element sept realizes, the method is characterized in that according to following order to comprise following at least operation:
(1) on substrate, form the operation of used for liquid crystal display element sept with the radiation sensitive resin composition tunicle,
The operation of (2) at least a portion of this tunicle being made public,
The operation of (3) this tunicle after the exposure being developed, and
(4) operation that this tunicle after developing is heated.
According to the present invention, above-mentioned problem the 6th realizes that through liquid crystal display cells this liquid crystal display cells possesses above-mentioned used for liquid crystal display element sept.
Description of drawings
Fig. 1 is the synoptic diagram of a liquid crystal display cells configuration example of expression.
Fig. 2 is the synoptic diagram of another liquid crystal display cells configuration example of expression.
Fig. 3 is the infrared spectrogram of the polymer solution [α-1] of synthetic example 1.
Fig. 4 is the infrared spectrogram of the polymer solution [α-1] of synthetic example 1 at reaction solution after 1 hour under 60 ℃.
Fig. 5 is the infrared spectrogram of the polymer solution [α-1] of synthetic example 1 at reaction solution after 2 hours under 60 ℃.
Fig. 6 is the synoptic diagram that illustrates the sept cross sectional shape.
Fig. 7 illustrates when estimating elastic recovery rate the figure of the load when loading and off-loading-deflection curve.
Embodiment
Below the present invention is elaborated.
Radiation sensitive resin composition
-polymkeric substance [A]-
Polymkeric substance of the present invention comprises by unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (a1); Be selected from above-mentioned formula (1)～(4) at least a compound of the group formed of hydroxyl unsaturated compound of expression respectively; And the polymkeric substance that obtains of the multipolymer formed of other unsaturated compounds (a3) except that (a1) and (a2) (below be called multipolymer [α]) and the isocyanate compound shown in the above-mentioned formula (5) (below be called " unsaturated isocyanate compound (5) ") reaction (below be called " polymkeric substance [A] ").
In each composition that constitutes polymkeric substance [α]; As unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (a1) (following it is referred to as " unsaturated carboxylic acid compounds (a1) "), for example can enumerate out the monocarboxylic acid of acrylic acid, methacrylic acid, butenoic acid, 2-acrylyl oxy-ethyl succinic acid, 2-methylacryoyloxyethyl succinic acid, 2-acrylyl oxy-ethyl hexahydrophthalic acid, 2-methylacryoyloxyethyl hexahydrophthalic acid etc.; And like the dicarboxylic acids of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.; The acid anhydrides of above-mentioned dicarboxylic acids etc.
From copolyreaction property, resulting polymers [A] viewpoint that the dissolubility and the raw material of alkaline-based developer is easy to get is considered; In these unsaturated carboxylic acid compounds (a1), preferably use acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl hexahydrophthalic acid etc.
In multipolymer [α], unsaturated carboxylic acid compounds (a1) can use separately, also can two or more mix use.
In the multipolymer [α], derive from the containing ratio of the repetitive of unsaturated carboxylic acid compounds (a1), be preferably 1～50 weight % based on multipolymer [α], more preferably 5～40 weight % are preferably 10～30 weight % especially.Be lower than 1 weight % if derive from the content of the repetitive of unsaturated carboxylic acid compounds (a1); Then react the reduction of the tendency polymkeric substance that obtains has to(for) the dissolubility of alkaline-based developer with unsaturated isocyanate compound (5); If surpass 50 weight % on the other hand, then might make this polymkeric substance that the dissolubility of alkaline-based developer is become excessive.
In addition; As be selected from above-mentioned formula (1)～(4) the hydroxyl unsaturated compound (a2) of unsaturated compound group of expression respectively; For example; As above-mentioned (1) represented compound, can enumerate out acrylic acid hydroxyalkyl acrylates such as acrylic acid 5-hydroxyl pentyl ester, the own ester of acrylic acid 6-hydroxyl, acrylic acid 7-hydroxyl heptyl ester, acrylic acid 8-hydroxyl monooctyl ester, acrylic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems, acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, acrylic acid 11-hydroxyl undecyl ester, acrylic acid 12-hydroxyl dodecyl ester; Methacrylic acid hydroxyl Arrcostabs such as methacrylic acid 5-hydroxyl pentyl ester, the own ester of methacrylic acid 6-hydroxyl, methacrylic acid 7-hydroxyl heptyl ester, methacrylic acid 8-hydroxyl monooctyl ester, methacrylic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems, methacrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, methacrylic acid 11-hydroxyl undecyl ester, methacrylic acid 12-hydroxyl dodecyl ester etc.;
In addition; As the represented compound of above-mentioned formula (2), for example can enumerate out acrylic acid (6-hydroxyl hexylyloxy) Arrcostabs such as acrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, acrylic acid 3-(6-hydroxyl hexylyloxy) propyl ester, acrylic acid 4-(6-hydroxyl hexylyloxy) butyl ester, acrylic acid 5-(6-hydroxyl hexylyloxy) pentyl ester, the own ester of acrylic acid 6-(6-hydroxyl hexylyloxy); Methacrylic acid (6-hydroxyl hexylyloxy) Arrcostabs such as methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, methacrylic acid 3-(6-hydroxyl hexylyloxy) propyl ester, methacrylic acid 4-(6-hydroxyl hexylyloxy) butyl ester, methacrylic acid 5-(6-hydroxyl hexylyloxy) pentyl ester, the own ester of methacrylic acid 6-(6-hydroxyl hexylyloxy).
In addition, as the commercially available article of the potpourri of methacrylic acid (6-hydroxyl hexylyloxy) Arrcostab and methacrylic acid 2-hydroxyl ethyl ester, can enumerate out commodity PLACCEL FM1D by name, FM2D (ダ イ セ Le chemical industry (strain) system) etc.
In addition; As the compound shown in the above-mentioned formula (3); For example can enumerate out acrylic acid 2-(3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) ethyl ester, acrylic acid 3-(3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) propyl ester, acrylic acid 4-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) butyl ester, acrylic acid 5-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) acrylic acid (3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) Arrcostab such as pentyl ester, the own ester of acrylic acid 6-(3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base); Methacrylic acid 2-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) ethyl ester, methacrylic acid 3-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) propyl ester, methacrylic acid 4-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) butyl ester, methacrylic acid 5-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) methacrylic acid (3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) such as pentyl ester, the own ester of methacrylic acid 6-(3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) Arrcostab etc.
In addition, as the commercially available article of the potpourri of (methyl) acrylic acid (3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) Arrcostab and methacrylic acid 2-hydroxyl ethyl ester, can enumerate out commodity HEMAC1 (ダ イ セ Le chemical industry (strain) system) by name etc.
In addition; As the compound shown in the above-mentioned formula (4); For example can enumerate out acrylic acid 4-hydroxyl cyclohexyl, acrylic acid 4-methylol-cyclohexyl methyl esters, acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, acrylic acid 3-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, acrylic acid 3-methylol-dicyclo [2.2.1] heptan-5-alkene-2-base methyl esters, acrylic acid 3-hydroxyethyl-dicyclo [2.2.1] heptan-5-alkene-2-base ethyl ester, acrylic acid 8-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, acrylic acid 2-hydroxyl-octahydro-4; 7-methylene-indenes-5-base ester, acrylic acid 2-carboxyl methyl-octahydro-4; 7-methylene-indenes-5-base methyl esters, acrylic acid 2-hydroxyethyl-octahydro-4,7-methylene-indenes-5-base ethyl ester, acrylic acid 3-hydroxyl-diamantane-1-base ester, acrylic acid 3-methylol-diamantane-1-base methyl esters, acrylic acid 3-hydroxyethyl-diamantane-1-base ethyl ester etc. contain the acrylic acid hydroxyalkyl acrylate of ester ring type structure; Methacrylic acid 4-hydroxyl cyclohexyl, methacrylic acid 4-methylol-cyclohexyl methyl esters, methacrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, methacrylic acid 3-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, methacrylic acid 3-methylol-dicyclo [2.2.1] heptan-5-alkene-2-base methyl esters, methacrylic acid 3-hydroxyethyl-dicyclo [2.2.1] heptan-5-alkene-2-base ethyl ester, methacrylic acid 8-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, methacrylic acid 2-hydroxyl-octahydro-4; 7-methylene-indenes-5-base ester, methacrylic acid 2-methylol-octahydro-4; 7-methylene-indenes-5-base methyl esters, methacrylic acid 2-hydroxyethyl-octahydro-4,7-methylene-indenes-5-base ethyl ester, methacrylic acid 3-hydroxyl-diamantane-1-base ester, methacrylic acid 3-methylol-diamantane-1-base methyl esters, methacrylic acid 3-hydroxyethyl-diamantane-1-base ethyl ester etc. contain the methacrylic acid hydroxyl Arrcostab of ester ring type structure;
Above-mentioned formula (1)～(4) respectively the expression these hydroxyl unsaturated compounds in; Consider from copolyreaction property and with the reactivity of isocyanate compound; The preferred own ester of acrylic acid 6-hydroxyl, the own ester of methacrylic acid 6-hydroxyl, acrylic acid 2-(6-hydroxyethyl hexylyloxy) ethyl ester, methacrylic acid 2-(6-hydroxyethyl hexylyloxy) ethyl ester, acrylic acid 2-(3-hydroxyl-2; 2-dimethyl-propoxycarbonyl oxygen base) ethyl ester, methacrylic acid 2-(3-hydroxyl-2,2-dimethyl-propoxycarbonyl oxygen base) ethyl ester, (methyl) acrylic acid 4-methylol-cyclohexyl methyl esters, acrylic acid 3-methylol-diamantane-1-base methyl esters, methacrylic acid 3-methylol-diamantane-1-base methyl esters etc.
In multipolymer (α), hydroxyl unsaturated compound (a2) can use separately, also can two kinds or two or more mixing use.
In the multipolymer [α], derive from the containing ratio of the repetitive of hydroxyl unsaturated compound (a2), be preferably 1～50 weight % based on multipolymer [α], more preferably 3～40 weight % further are preferably 5～30 weight %, preferred especially 10-30 weight %.Be lower than 1 weight % if derive from the content of the repetitive of hydroxyl unsaturated compound (a2); Then the importing rate on the polymkeric substance of unsaturated isocyanate compound (5) can descend; Make sensitivity that the tendency of decline arranged; If surpass 50 weight % on the other hand, the bin stability of the polymkeric substance that then obtains with unsaturated isocyanate compound (5) reaction has the tendency of decline.
In addition, as other unsaturated compound (a3), for example can enumerate out alkyl acrylates such as methyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate;
Glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, 4-hydroxybutyl acrylic ester glycidol ether, acrylic acid 3; 4-epoxy radicals butyl ester, acrylic acid 6; 7-epoxy radicals heptyl ester, acrylic acid 3, acrylic acid epoxy base (ring) Arrcostabs such as 4-epoxy radicals cyclohexyl;
GMA, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy radicals butyl ester, methacrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 3, methacrylic acid epoxy radicals (ring) Arrcostabs such as 4-epoxy radicals cyclohexyl;
α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan 6; 7-epoxy radicals heptyl ester, α-Yi Jibingxisuan 3, other alpha-alkyl acrylic acid epoxy (ring) Arrcostab such as 4-epoxy radicals cyclohexyl;
Adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to glycidol ethers such as vinyl benzyl glycidol ethers;
Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring 5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, acrylic acid 2-(three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base oxygen) acrylate cyclic esters such as ethyl ester, IBOA;
Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, methacrylic acid 2-(three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base oxygen) methacrylic acid alicyclic esters such as ethyl ester, isobornyl methacrylate;
Acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester or aralkyl ester;
Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate or aralkyl ester;
Acrylic acid hydroxyalkyl acrylates such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxypropyl acrylate, acrylic acid 3-hydroxyl butyl ester;
Methacrylic acid hydroxyl Arrcostabs such as methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 3-hydroxyl butyl ester;
Unsaturated dicarboxylic acid dialkyls such as diethyl maleate, DEF, diethyl itaconate;
Acrylic acid tetrahydrofuran-2-ester, acrylic acid oxinane-2-ester, acrylic acid 2-methyl oxinane-2-ester etc. have the acrylic ester that contains the oxygen five-ring heterocycles or contain 6 yuan of heterocycles of oxygen;
Methacrylic acid tetrahydrofuran-2-ester, methacrylic acid oxinane-2-ester, methacrylic acid 2-methyl oxinane-2-ester etc. have the methacrylate that contains the oxygen five-ring heterocycles or contain 6 yuan of heterocycles of oxygen;
Styrene, AMS, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrenes;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate dienes compound;
In addition, can also enumerate for example vinyl cyanide, methacrylonitrile, acrylic amide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc.
In these other unsaturated compound (a3); From copolyreaction property and resulting polymkeric substance (A) dissolubility of aqueous alkali is considered, preferably used n-BMA, methacrylic acid 2-methyl ethylene oxidic ester, benzyl methacrylate, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, styrene, to methoxy styrene, methacrylic acid tetrahydrofuran-2-ester, 1,3-butadiene etc.
In multipolymer (α), other unsaturated compound (a3) can use separately also can two or more mix use.
In the multipolymer [α], derive from the containing ratio of the repetitive of other unsaturated compounds (a3), be preferably 10～70 weight % based on multipolymer [α], more preferably 20～60 weight % are preferably 30～50 weight % especially.Be lower than 10 weight % if derive from the content of the repetitive of other unsaturated compounds (a3); The bin stability of the polymkeric substance that then obtains with unsaturated isocyanate compound (5) reaction has the tendency of reduction; If surpass 70 weight % on the other hand, this polymkeric substance has the tendency of reduction to the dissolubility of alkaline-based developer.In addition, when using (methyl) acrylic acid epoxy (ring) alkyl esters, preferably below 10 weight %, its bin stability has the tendency of reduction to containing ratio more than 10 weight %.
Multipolymer (α) for example can pass through unsaturated carboxylic acid compounds (a1), hydroxyl unsaturated compound (a2) and other unsaturated compound (a3) in appropriate solvent, under the condition that radical polymerization initiator exists, carry out polymerization and make.
As the solvent that uses in the above-mentioned polymerization, can enumerate out for example ethers such as tetrahydrofuran 、 diox;
Ethylene glycol monoalkyl ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, glycol monomethyl-positive propyl ether, glycol monomethyl-n-butyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, glycol monomethyl-positive propyl ether acetic acid esters, glycol monomethyl-ethylene glycol monoalkyl ether acetates such as n-butyl ether acetic acid esters;
Glycol monoethyl ether propionic ester, ethylene glycol monoethyl ether propionic ester, glycol monomethyl-positive propyl ether propionic ester, glycol monomethyl-ethylene glycol monoalkyl ether propionic esters such as n-butyl ether propionic ester;
Diglycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl methyl ether;
Propylene-glycol monoalky lethers such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-positive propyl ether, propylene glycol list-n-butyl ether;
DPG alkyl ethers such as dipropylene glycol monomethyl ether, DPG list ether, DPG dimethyl ether, DPG diethyl ether, DPG ethyl methyl ether;
Propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list-positive propyl ether acetic acid esters, propylene glycol list-propylene-glycol monoalky lether acetic acid esters such as n-butyl ether acetic acid esters;
Propylene glycol monomethyl ether propionic ester, dihydroxypropane single-ether propionic ester, propylene glycol list-positive propyl ether propionic ester, propylene glycol list-propylene-glycol monoalky lether propionic esters such as n-butyl ether propionic ester;
Aromatic hydrocarbon such as toluene, xylene;
Ketones such as MEK, 2 pentanone, propione, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone;
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-positive propoxy methyl propionate; 2-positive propoxy ethyl propionate; 2-positive propoxy propionic acid n-propyl; 2-positive propoxy n-butyl propionate; 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; Alkoxypropan acid alkyl esters such as 3-n-butoxy n-butyl propionate;
Other esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy methyl acetate, hydroxyl ethyl acetate, glycolic acid n-propyl, the positive butyl ester of glycolic acid, acetate 4-methoxyl butyl ester, acetate 3-methoxyl butyl ester, acetate 2-methoxyl butyl ester, acetate 3-ethoxy butyl ester, acetate 3-propoxyl group butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 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, methoxyacetic acid ethyl ester, methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, positive propoxy methyl acetate, positive propoxy ethyl acetate, positive propoxy n-propyl acetate, positive propoxy n-butyl acetate, n-butoxy methyl acetate, n-butoxy ethyl acetate, n-butoxy n-propyl acetate, n-butoxy n-butyl acetate, or the like.
In these solvents, preferred diglycol alkyl ether, propylene-glycol monoalky lether acetic acid esters, alkoxypropan acid alkyl ester, acetic acid esters or the like.
Above-mentioned solvent can use separately also can two or more mix use.
In addition, with regard to above-mentioned radical polymerization initiator, not special the qualification for example can enumerate 2; 2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2; 2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl-2; 2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1, organic peroxides such as 1-two (t-butyl peroxy) cyclohexane; Hydrogen peroxide or the like.
In addition, when using superoxide, can also itself and reductive agent be used simultaneously, as the oxidation-reduction type initiating agent as radical polymerization initiator.
These radical polymerization initiators can use separately, also can two or more mix use.
The multipolymer that so obtains (α) both can directly be used for the preparation of polymkeric substance (A) with the form of solution, offer the preparation of polymkeric substance (A) after also can from solution, separating earlier again.
Measure the polystyrene conversion weight-average molecular weight (below be called " Mw ") of multipolymer (α) through gel permeation chromatography (GPC), preferred 2,000～100,000; More preferably 5,000～50,000.In this case, if Mw less than 2,000, then the alkali-developable of resultant tunicle, residual film ratio etc. all reduce, or also might make pattern form, thermotolerance etc. impaired; On the other hand,, then can reduce resolution, maybe possibly make pattern form impaired if surpass 100,000.
Polymkeric substance among the present invention (A) obtains through unsaturated isocyanate compound (5) and multipolymer (α) are reacted.
As unsaturated isocyanate compound (5), can enumerate:
Acrylic acid derivatives such as 2-acryloxy ethyl isocyanate, 3-acryloxy propyl group isocyanates, 4-acryloxy butyl isocyanate, 6-acryloxy hexyl isocyanates, 8-acryloxy octyl group isocyanates, 10-acryloxy decyl isocyanates;
Methacrylic acid derivatives such as 2-methylacryoyloxyethyl isocyanates, 3-methacryloxypropyl isocyanates, 4-methacryloxy butyl isocyanate, 6-methacryloxy hexyl isocyanates, 8-methacryloxy octyl group isocyanates, 10-methacryloxy decyl isocyanates.
As commercially available 2-acryloxy ethyl isocyanate; Can enumerate the product of commodity カ レ Application ズ AOI by name (clear and electrician's (strain) system); As commercially available 2-methylacryoyloxyethyl isocyanates, can enumerate out the product of commodity カ レ Application ズ MOI by name (clear and electrician's (strain) system).
In these unsaturated isocyanate compounds (5), from consider preferred 2-acryloxy ethyl isocyanate, 2-methylacryoyloxyethyl isocyanates etc. with the reactivity of multipolymer (α).
In polymkeric substance (A), unsaturated isocyanate compound (5) can use separately also and can two or more mix use.
Among the present invention; The reaction of multipolymer (α) and unsaturated isocyanate compound (5); For example can be through in multipolymer (α) solution that contains polymerization inhibitors such as di-n-butyltin dilaurate catalyzer such as (IV) or p methoxy phenol; Under room temperature or heating condition, add unsaturated isocyanate compound (5) and implement while stir.
During preparation polymkeric substance (A); With respect to the amount of hydroxyl unsaturated compound (a2) in the multipolymer (α), perhaps using under the situation of hydroxy-containing compounds as other unsaturated compound (a3), with respect to the total amount of this amount with hydroxyl unsaturated compound (a2); The use amount of unsaturated isocyanate compound (5); Be preferably 0.1～90 weight %, more preferably 10～80 weight %, preferred especially 25～75 weight %.If the use amount of unsaturated isocyanate compound (5) is lower than 0.1 weight %, then for the weak effect that improves sensitivity and elastic property; If surpass 90 weight % on the other hand, then can remaining unreacted unsaturated isocyanate compound (5), the bin stability of resulting polymer solution or radiation sensitive resin composition has the tendency of reduction.
Polymkeric substance (A) has carboxyl and/or acid anhydride and polymerism unsaturated link; And alkaline-based developer had suitable dissolubility; Even be not used in combination special hardening agent, also can be easy to make it solidify through heating, contain the radiation sensitive resin composition of polymkeric substance (A); When developing, can not produce the phenomenon residual and the film attenuate of developing, be easy to just can form the sept of regulation shape.
Radiation sensitive resin composition of the present invention contains polymkeric substance (A) polymerizable unsaturated compound (B) and radiation-sensitive polymerization initiator (C) is a neccessary composition.
-polymerizable unsaturated compound (B)-
Polymerizable unsaturated compound (B) is included under the condition of radiation-sensitive polymerization initiator existence, through the unsaturated compound of radioactive ray exposure polymerization.
For this polymerizable unsaturated compound (B), not special the qualification, for example simple function, difunctionality, trifunctional or its above (methyl) acrylic ester are considered preferred because copolymerization property is good from the angle that improves gained sept intensity.
As above-mentioned simple function (methyl) acrylic ester, can enumerate for example 2-hydroxyethylmethacry,ate, 2-hydroxyethyl methacrylate, carbiphene acrylic ester, carbiphene methacrylate, iso-bornyl acrylate, isobornyl methacrylate, 3-methoxyl butylacrylic acid ester, 3-methoxyl butyl methyl acrylic ester, (2-acryloxy ethyl) (2-hydroxypropyl) phthalic ester, (2-methylacryoyloxyethyl) (2-hydroxypropyl) phthalic ester, ω-carboxyl polycaprolactone single-acrylate or the like.Can enumerate out commodity ア ロ ニ Star Network ス M-101 by name, M-111, M-114, M-5300 (above is that (strain) manufacturing is synthesized in East Asia) as commercially available; KAYARADTC-110S, TC-120S (above is Japanese chemical drug (strain) manufacturing), PVC ス コ one ト 158,2311 products such as (above are Osaka organic chemistry industry (strain) manufacturing).
As above-mentioned difunctional (methyl) acrylic ester; Can enumerate out for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1; 6-hexanediyl ester, 1; 6-hexanediol dimethacrylate, 1; 9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate, two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes dimethylacrylates etc.Can enumerate commodity ア ロ ニ Star Network ス M-210 by name, M-240, M-6200 (above is that (strain) manufacturing is synthesized in East Asia) as commercially available; KAYARAD HDDA, HX-220, R-604 (above is Japanese chemical drug (strain) manufacturing), PVC ス コ one ト 260,312,335HP products such as (above be Osaka organic chemistry industry (strain) manufacturing).
And then; As above-mentioned trifunctional or above (methyl) acrylic ester; Can enumerate out for example trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylic ester, dipentaerythritol five acrylic ester, dipentaerythritol pentamethyl acrylic ester, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylic ester, three (2-acryloxy ethyl) phosphate, three (2-methylacryoyloxyethyl) phosphate; Or have straight-chain alkyl-sub-and alicyclic structure and have in compound and the molecule of 2 or above isocyanate groups and have 1 or above hydroxyl, and has multifunctional ammonia ester acrylic ester compound that the compound reaction of 3,4 or 5 acryloxies and/or methacryloxy obtains etc.
As 3 commercially available officials can or above (methyl) esters of acrylic acid; Can enumerate out commodity ア ロ ニ Star Network ス M-309 by name, M-400, M-405, M-450, M-7100, M-8030, M-8060, TO-1450, TO-1382 (above is that (strain) manufacturing is synthesized in East Asia); KAYARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above is Japanese chemical drug (strain) manufacturing); PVC ス コ one ト 295,300,360, GPT, 3PA, 400 products such as (above are Osaka organic chemistry industry (strain) manufacturing) contain multifunctional ammonia ester acrylic ester compound and can enumerate ニ ユ one Off ロ Application テ イ ア R-1150 (the first industrial pharmacy (strain) manufacturing), KAYARAD DPHA-40H products such as (Japanese chemical drug (strain) manufacturings) as commercially available.
In these simple functions, difunctionality, trifunctional or above (methyl) acrylic ester; Preferred trifunctional or above (methyl) acrylic ester, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate and contain the commercially available prod etc. of multifunctional ammonia ester acrylic ester compound.
Above-mentioned simple function, difunctionality, trifunctional or above (methyl) acrylic ester can use separately also and can two or more mix use.
In the radiation sensitive resin composition of the present invention, with respect to 100 parts by weight polymer (A), the consumption of polymerizable unsaturated compound (B) is preferably 1～200 weight portion, more preferably 3～180 weight portions.If the consumption of polymerizable unsaturated compound (B) is lower than 1 weight portion, the residual problem of might developing when then developing; On the other hand, if surpass 200 weight portions, then the tack of gained sept has the tendency of reduction.
-radiation-sensitive polymerization initiator (C)-
Radiation-sensitive polymerization initiator (C) is included under the exposure effect of rays such as visible light, ultraviolet ray, far ultraviolet, charged particle ray, X ray, produces the composition of the spike of ability initiated polymerization property unsaturated compound (B) polymerization.
As such radiation-sensitive polymerization initiator (C), can enumerate out for example O-acyl group oxime compound, acetophenone compounds, bisglyoxaline compounds, benzoin compounds, Benzophenones compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, phosphine compound, compound in triazine class etc.
As O-acyl group oxime compound, the O-acyl group oxime type polymerization initiator of preferred 9.H.-carbazoles.Can enumerate out for example 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-nonane-1; 2-nonane-2-oxime-O-benzoic ether, 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-nonane-1; 2-nonane-2-oxime-O-acetic acid esters, 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-pentane-1; 2-pentane-2-oxime-O-acetic acid esters, 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-Xin-1-ketoxime-O-acetic acid esters, 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-benzoic ether, 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters, 1-(9-ethyl-6-(1; 3,5-trimethylbenzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-benzoic ether, 1-(9-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-benzoic ether, 1-(9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters, 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters or the like.
In these O-acyl group oxime compounds, preferred especially 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters, 1-(9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters.
Above-mentioned O-acyl group oxime compound can use separately also and can two or more mix use.In the present invention through using O-acyl group oxime compound, though exposure 1,200J/m 2Or the sept that also can obtain to have good sensitivity, tack below it.
As above-mentioned acetophenone compounds, for example can enumerate out alpha-hydroxy ketones, alpha-amido ketone compounds etc.
As above-mentioned alpha-hydroxy ketones, can enumerate out for example 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-hydroxycyclohexylphenylketone or the like.In addition; As above-mentioned alpha-amido ketone compounds; Can enumerate out for example 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-Ding-1-ketone etc.; Other compounds except that these compounds for example can enumerate 2,2-dimethoxy-acetophenone, 2; 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.
In these acetophenone compounds, preferred especially 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino third-1-ketone, 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-Ding-1-ketone.Through being used in combination acetophenone compounds, might further improve sensitivity, sept shape and compression strenght among the present invention.
In addition, as above-mentioned bisglyoxaline compounds, can enumerate out for example 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1; 2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 '; 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 '; 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1; 2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2; 2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline or the like.
In these bisglyoxaline compounds, preferably use 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2; 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2; 4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline or the like, preferred especially 2; 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
Through being used in combination the bisglyoxaline compounds, might further improve sensitivity, resolution and tack among the present invention.
In addition, when being used in combination the bisglyoxaline compounds, in order to increase its sensitivity, can add aliphatic category with dialkyl amido or aromatic series compounds (below be called " amino type sensitizer ").
As amino type of sensitizer, can enumerate for example N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, to the dimethylamino ethyl benzoate, to dimethylamino benzoic acid isopentyl ester or the like.
In these amino type sensitizers, preferred especially 4,4 '-two (diethylamino) benzophenone.
Above-mentioned amino type sensitizer can use separately also and can two or more mix use.
In addition, when being used in combination the bisglyoxaline compounds,, can add sulfur alcohol compound as the hydrogen supply compound with amino type of sensitizer.The bisglyoxaline compounds; Under the effect of above-mentioned amino type sensitizer, its sensitivity improves and fracture, produces imidazole radical; But this free radical can not directly manifest high polymerization initiating power, makes the gained sept form unfavorable shapes such as back taper in many cases.But in bisglyoxaline compounds and the simultaneous system of amino class sensitizer; Through adding sulfur alcohol compound; To imidazole radical the hydroperoxyl radical from sulfur alcohol compound is provided, the result makes imidazole radical be converted into neutral imidazoles, produces the composition of the sulphur free radical with high polymerization initiating power simultaneously; Through the effect of this composition, can make the shape of sept form even more ideal positive taper.
As above-mentioned sulfur alcohol compound; Can enumerate for example 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatic series compounds such as 5-methoxyl benzo imidazoles; The single mercaptan of aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester; 3; 6-dioxa-1,8-octane two mercaptan, pentaerythrite four (mercaptoacetate), the above aliphatic category mercaptan of pentaerythrite four difunctionalitys such as (3-mercaptopropionic acid esters).
In these sulfur alcohol compounds, preferred especially 2-mercaptobenzothiazole.
In the radiation sensitive resin composition of the present invention, the use amount of polymerization initiator [C] is with respect to polymkeric substance [A] 100 weight portions; Be preferably the 0.05-30 weight portion, if more preferably 0.1-30 weight portion is less than 0.05 weight portion; The possibility residual film ratio is not enough when then developing; On the other hand, if surpass 30 weight portions, then the shape of gained sept maybe be impaired.
In the radiation sensitive resin composition of the present invention; Total body radiation line susceptibility polymerization initiator with respect to 100 weight portions; The usage rate of other radiation-sensitive polymerization initiators is preferably at 100 weight portions or following; More preferably 80 weight portions or following, preferred especially 60 weight portions or following.In this case, if the addition of other radiation-sensitive polymerization initiators surpasses 100 weight portions, then might damage the effect that the present invention expects.
When being used in combination the bisglyoxaline compounds with amino type of sensitizer, with respect to the bisglyoxaline compounds of 100 weight portions, the addition of amino type sensitizer is preferably 0.1～50 weight portion, more preferably 1～20 weight portion.If the addition of amino type of sensitizer is lower than 0.1 weight portion, then sensitivity, resolution and adhesion improves the tendency that effect has reduction; On the other hand, if surpass 50 weight portions, the sept shape that then obtains has impaired tendency.
In addition, when being used in combination the bisglyoxaline compounds with amino type of sensitizer, with respect to the bisglyoxaline compounds of 100 weight portions, the addition of sulfur alcohol compound is preferably 0.1～50 weight portion, more preferably 1～20 weight portion.If the addition of sulfur alcohol compound is lower than 0.1 weight portion, then the sept shape improves the effect reduction or is easy to generate the film attenuate; On the other hand, if surpass 50 weight portions, the sept shape that then obtains has impaired tendency.
-adjuvant-
In radiation sensitive resin composition of the present invention; In the scope of not damaging effect that the present invention expects; As required, except that mentioned component, can also mix adjuvants such as adding surfactant, adhesive aid, bin stability, thermotolerance improving agent.
Above-mentioned surfactant is for having the composition of the effect that improves coating, preferred fluorine class surfactant and siloxane type surfactants.
As above-mentioned fluorine class surfactant, preferred endways, have the compound of fluoro-alkyl or fluoro alkylidene on main chain and the arbitrary at least position of side chain, as instantiation, for example 1,1,2; 2-tetrafluoro octyl group (1,1,2,2-tetrafluoro n-pro-pyl) ether, 1,1,2; 2-tetrafluoro n-octyl (n-hexyl) ether, eight glycol two (1,1,2,2-tetrafluoro normal-butyl) ether, hexaethylene glycol two (1,1,2; 2,3,3-hexafluoro n-pentyl) ether, eight propylene glycol two (1,1,2; 2-tetrafluoro normal-butyl) ether, six propylene glycol two (1,1,2,2,3; 3-hexafluoro n-pentyl) ether, 1,1,2,2,3; 3-hexafluoro n-decane, 1,1,2,2,8; 8,9,9,10,10-ten fluorine n-dodecanes, perfluor dodecyl sodium sulfonate, fluoro-alkyl benzene sulfonic acid sodium salt, fluoro-alkyl Alendronate, fluoro-alkyl carboxylic acid sodium, fluoro-alkyl polyoxyethylene ether, two glycerine four (fluoro-alkyl polyoxyethylene ether), fluoro-alkyl ammonium iodide, fluoro-alkyl betaine, fluoro-alkyl polyoxyethylene ether, perfluoroalkyl poly oxyethanol, perfluoroalkyl alcoxylates, fluorine class Arrcostab or the like.
In addition; As commercially available fluorine class surfactant; In trade name; For example can enumerate out BM-1000,1100 (the above BM of being CHEMIE manufactured); メ ガ Off ア Star Network F142D, F172, F173, F183, F178, F191, F471, F476 (above big Japanese イ Application キ chemical industry (strain) manufacturing); Off ロ ラ one De FC170C, FC-171, FC-430, FC-431 (above is the manufacturing of ス リ one エ system (strain) in Sumitomo); サ one Off ロ Application S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above Asahi Glass (strain) manufacturing), エ Off ト Star プ EF301, EF303, EF352 (above is that new autumn fields changes into (strain) manufacturing), Off タ one ジ エ Application ト FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above is that (strain) ネ オ ス makes) or the like.
As above-mentioned siloxane type surfactants; As commercially available article; In trade name; For example can enumerate out ト one レ シ リ コ one Application DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (more than; East レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (more than, GE Toshiba シ リ コ one Application (strain) system) etc.
In addition; As the surfactant except that above-mentioned surfactant; Can enumerate out the for example polyethylene oxide alkyl ethers of polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ether like polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Like the non-ionics of the polyoxyethylene dialkyl of polyoxyethylene dilaurate, polyoxyethylene distearate etc., or commercially available, the product of commodity KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) by name, Port リ Off ロ one No.57, No.95 (common prosperity society chemistry (strain) is made) etc. for example.
Above-mentioned surfactant can use separately, also can two or more mix use.
With respect to the polymkeric substance (A) of 100 weight portions, the combined amount of surfactant is preferably 5 weight portions or following, further is preferably 2 weight portions or following.If the combined amount of surfactant surpasses 5 weight portions, film becomes coarse easily when then being coated with.
Above-mentioned adhesive aid is for having the further composition that improves the effect of the tack between sept and the substrate, preferred functional silanes coupling agent.
As above-mentioned functional silanes coupling agent, can enumerate for example have carboxyl, the compound of methacryl, vinyl, NCO, epoxy radicals isoreactivity functional group.Concrete have trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-NCO propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane or the like.
These adhesive aids can use separately also and can two or more mix use.
With respect to the polymkeric substance (A) of 100 weight portions, the combined amount of adhesive aid is preferably 20 weight portions or following, further is preferably 10 weight portions or following.If the combined amount of adhesive aid surpasses 20 weight portions, it is residual then to be easy to generate development.
As above-mentioned stable storage agent, can enumerate for example sulphur, quinones, hydroquinones, polyoxy compound, amine, nitro nitroso compound or the like.Be 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium or the like more specifically.
These stable storage agent can be used separately also and can two or more mix use.
With respect to the polymkeric substance (A) of 100 weight portions, the combined amount of stable storage agent is preferably 3 weight portions or following, further is preferably 0.001～0.5 weight portion.If the combined amount of stable storage agent surpasses 3 weight portions, sensitivity is descended, make pattern form impaired.
As above-mentioned thermotolerance improving agent, can enumerate for example N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound.
As above-mentioned N-(alkoxy methyl) glycoluril compounds, can enumerate for example N, N, N ', N '-four (methoxy) glycoluril, N; N, N ', N '-four (ethoxyl methyl) glycoluril, N, N, N '; N '-four (n-propoxymethyl) glycoluril, N, N, N ', N '-four (isopropoxy methyl) glycoluril, N, N; N ', N '-four (n-butoxy methyl) glycoluril, N, N, N ', N '-four (tert-butoxy methyl) glycoluril or the like.
In these N-(alkoxy methyl) glycoluril compounds, preferred especially N, N, N ', N '-four (methoxy) glycoluril.
In addition, as above-mentioned N-(alkoxy methyl) melamine compound, can enumerate for example N, N, N ', N ', N "; N "-six (methoxy) melamine, N, N, N ', N ', N ", N "-six (ethoxyl methyl) melamine, N, N; N ', N ', N ", N "-six (n-propoxymethyl) melamine, N, N, N ', N '; N ", N " and-six (isopropoxy methyl) melamine, N, N, N ', N ', N "; N "-six (n-butoxy methyl) melamine, N, N, N ', N ', N ", N "-six (tert-butoxy methyl) melamine or the like.
In these N-(alkoxy methyl) melamine compound, preferred especially N, N; N ', N ', N "; N "-six (methoxy) melamine, as commercially available have commodity be called ニ カ ラ Star Network N-2702, MW-30M (above by three and chemistry (strain) make) product or the like.
These thermotolerance improving agents can use separately also and can two or more mix use.
With respect to the polymkeric substance (A) of 100 weight portions, the combined amount of thermotolerance improving agent is preferably 30 weight portions or following, further is preferably 20 weight portions or following.If the combined amount of thermotolerance improving agent surpasses 30 weight portions, then the bin stability of radiation sensitive resin composition might descend.
Radiation sensitive resin composition of the present invention preferably is dissolved in it in appropriate solvent, supplies with the form of composition solution and uses.
As above-mentioned solvent; Use uniform dissolution to constitute each composition of radiation sensitive resin composition; And do not react, have suitable volatile solvent with each composition; From to the dissolving power of each composition, with the reactive of each composition and form the angle of filming easily and consider; Preferred alcohols, ethylene glycol monoalkyl ether acetate, diglycol monotertiary alkyl ether acetic acid esters, diglycol alkyl ether, propylene-glycol monoalky lether acetic acid esters, DPG alkyl ether, alkoxypropan acid alkyl ester, acetic acid esters or the like, preferred especially phenmethylol, 2-phenylethanol, 3-phenyl-1-propyl alcohol, glycol monomethyl n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, DPG dimethyl ether, acetic acid 3-methoxyl butyl ester, acetic acid 2-methoxyl ethyl ester or the like.
Above-mentioned solvent can use separately also and can two or more mix use.
Can also and use high boiling solvent when in the present invention, stating solvent in the use.
As above-mentioned high boiling solvent; Can enumerate for example N-NMF, N; Dinethylformamide, N-methyl formyl aniline, N-methylacetamide, DMAC N,N, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzyl ether, two n-hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, phenmethylol, phenylmethyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, glycol monomethyl phenyl ether acetic acid esters or the like.
These high boiling solvents can use separately also and can two or more mix use.
In addition, the composition solution of modulation as stated above also can via hole diameter be to be used further to use after filtration such as millipore filter about 0.5 μ m.
Radiation sensitive resin composition of the present invention particularly is suitable for forming the used for liquid crystal display element sept very much.
The formation method of sept
Below describe to the method for using radiation sensitive resin composition of the present invention to form sept of the present invention.
Sept formation method of the present invention comprises the following at least operation according to following order:
(1) operation of formation radiation sensitive resin composition tunicle of the present invention on substrate,
The operation of (2) at least a portion of this tunicle being made public,
The operation of (3) this tunicle after the exposure being developed, and
(4) operation that this tunicle after developing is heated.
Describe successively in the face of this each operation down.
-operation (1)-
One side through at transparency carrier forms nesa coating, on this nesa coating, preferably with the form coating radiation sensitive resin composition of composition solution, then coated face is heated (prebake conditions), and formation is filmed.
As the transparency carrier that is used to form sept; Can enumerate glass substrate, resin substrate etc.; Can enumerate out for example glass substrate such as soda-lime glass, alkali-free glass more specifically, the resin substrate that plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide constitute.
As the nesa coating on the one side that is arranged on transparency carrier, can use to comprise tin oxide (SnO 2) NESA film (U.S. PPG register of company trade mark), comprise indium oxide-tin oxide (In 2O 3-SnO 2) ITO film or the like.
As the coating process of composition solution, can adopt proper methods such as spraying process, rolling method, method of spin coating, slit die rubbing method, the excellent rubbing method that winds the line, ink-jet application method.Preferred especially method of spin coating, slit die rubbing method.
As the condition of prebake conditions, different and different according to the kind of each composition, mixture ratio etc., normally carrying out about 1～15 minute under 70～120 ℃.
In addition, also can adopt the dry film method to replace above-mentioned coating process to form tunicle.
When adopting the dry film method, this dry film is (below be called " photosensitive dry film ") who at basement membrane, preferably has that flexible basement membrane superimposed layer comprises that the photographic layer of photosensitive polymer combination of the present invention obtains.
Above-mentioned photosensitive dry film, can through with photosensitive polymer combination of the present invention, that preferably its fluid composition is coated on the basement membrane back is dry, the lamination photographic layer forms then.The basement membrane of photosensitive dry film can use for example synthetic resin films such as polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate, PVC.The thickness of basement membrane is comparatively suitable between 15～125 μ m.The thickness of the photographic layer that obtains is preferably about 1～30 μ m.
In addition, photosensitive dry film, can be on its photographic layer when not using further the lamination protective seam to store.For making this protective seam when using, not come off, can relatively easily peel off again when using, must have suitable fissility.Satisfy the diaphragm of this condition, for example can use on the surface of synthetic resin films such as PET film, polypropylene screen, polyethylene film, polychloroethylene film, polyurethane film coating or sintering type siloxane remover and the film that obtains.The thickness of diaphragm is preferably about 5～30 μ m usually.These diaphragms as required also can the two-layer or three layers of use of lamination.
-operation (2)-
Then at least a portion of the tunicle that forms is made public.At this moment, when a tunicle part is made public, carry out by means of photomask usually with predetermined pattern.
As the employed ray of exposure, can adopt like visible light, ultraviolet ray, far ultraviolet, electron ray, X ray or the like.Preferred wavelength range especially preferably contains the ultraviolet ray of 365nm at the ray of 190～450nm.
With measure through illumination appearance (OAI model 356, OAI Optical Associates Inc. make) exposure with beam wavelength at the intensity level at 365nm place as exposure, preferably 100～10,000J/m 2, but even radiation sensitive resin composition of the present invention is 1,200J/m 2Also can use under the following exposure, for example at 500-1200J/m 2Exposure under also can form desired pattern.
-operation (3)-
Then,, remove unwanted part, form the pattern of regulation through the tunicle after the exposure is developed.
As used developer solution in developing, be preferably alkaline developer.Inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia for example; Armeen such as ethamine, n-propylamine; Secondary aliphatic amine such as diethylamine, di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyl-diethyl-amine, dimethyl amine, triethylamine, pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicylo (5.4.0)-7-hendecene, 1; 5-diazabicylo (4.3.0)-alicyclic tertiary amines such as 5-nonene; Aromatic nitrile bases such as pyridine, collidine, lutidine, quinoline, alkanolamines such as dimethylamino ethanol amine, methyldiethanolamine, triethanolamine, the WS of alkali compounds such as quaternary ammonium salt such as TMAH, tetraethyl ammonium hydroxide.
In the above-mentioned alkali compounds WS, the water-miscible organic solvent and the surfactant that can also add in right amount like methyl alcohol, ethanol etc. use.
As developing method, can adopt liquid to contain any means such as り method, infusion process, spray process, development time is preferably about 10～180 seconds.
After the development, carry out cleaning like 30～90 seconds flowing water, air-dry with carrying out then like pressurized air or compressed nitrogen, form desirable pattern.
-operation (4)-
Then through heating arrangements such as heating plate, baking ovens in set point of temperature for example under 80～160 ℃; The gained pattern is carried out the heating (afterwards baking) of given time; Like time heating 5～30 minutes, heated 30～180 minutes the sept that just can obtain stipulating during with baking oven with hot plate.
Be used to form the radiation sensitive resin composition of sept in the past; If do not carrying out heat treated about 180～200 ℃ or under the temperature conditions more than it; The gained sept just can not be given full play to its performance; But radiation sensitive resin composition of the present invention compared with prior art, can reduce heating-up temperature; Its result can not cause the xanthochromia or the distortion of resin substrate, the rub resistance in the time of can forming compression strenght, liquid crystal aligning and with the various performances such as tack of transparency carrier good sept all.
Liquid crystal display cells
Liquid crystal display cells of the present invention is the element that possesses by as above operating the sept of the present invention that forms.
With regard to the structure of liquid crystal cell of the present invention; Not special the qualification; For example can enumerate as shown in Figure 1ly, have on transparency carrier the color filter layer of formation and sept, the structure of two alignment films that are provided with through liquid crystal layer, relative transparency electrode, relative transparency carrier etc.In addition, as shown in Figure 1, as required, also can form polaroid or on color filter layer, form diaphragm.
In addition, as shown in Figure 2, on transparency carrier, form color filter layer and sept, through alignment films and liquid crystal layer, make it relative with thin film transistor (TFT) (TFT) array, also can form TN-TFT type liquid crystal display cells.In such cases, also can form polaroid as required or on color filter layer, form diaphragm.
As above, radiation sensitive resin composition of the present invention has high sensitivity and high resolving power, even at 1200J/m 2Or under the following exposure; Also obtain complete pattern form; Can form elastic recovery, rub resistance, with all excellent used for liquid crystal display element septs such as the tack of transparency carrier, thermotolerance; And when forming sept, can reduce the back baking temperature after the development, can not cause the xanthochromia and the distortion of resin substrate.
Liquid crystal display cells of the present invention, possess pattern form, elastic recovery, rub resistance, with all excellent septs of all performances such as the tack of transparency carrier, thermotolerance, can in long-term, show high reliability.
Embodiment
Through enumerating embodiment embodiment of the present invention are further specified below, wherein part and % all are benchmark with weight.
Synthetic example 1
In flask with cooling tube, stirring machine, add 5 part 2,2 '-azoisobutyronitrile, 250 parts of acetic acid 3-methoxyl butyl esters then add 18 parts of methacrylic acids, 30 parts of methacrylic acid three ring [5.2.1.0 26] last of the ten Heavenly stems-8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 6-hydroxyl cyclohexyls, 17 parts of methacrylic acid tetrahydrofuran-2-esters; Carry out after the nitrogen replacement, Yi Bian slowly stir, Yi Bian make solution temperature rise to 80 ℃; Under this temperature, kept 4 hours; Rise to 100 ℃ then, under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-1) solution of solid content 27.5%.
The Mw value of measuring resulting multipolymer (α-1) through GPC (gel permeation chromatography) HLC-8020 (trade name, eastern ソ-(strain) system) is 14,000.
Then in the solution of above-mentioned multipolymer (α-1); Add 14 parts of 2-methylacryoyloxyethyl isocyanates (trade names; カ レ Application ズ MOI, clear and electrician's (strain) system), behind 0.08 part of 4-metoxyphenol; Under 60 ℃, stir and made its reaction in 2 hours, confirm to carry out situation from the NCO of 2-methylacryoyloxyethyl isocyanates and the reaction of multipolymer (α-1) hydroxyl through IR (infrared absorption) spectrum.Fig. 3,4,5 shown in respectively be polymkeric substance (α-1) solution, 60 ℃ down reaction after 1 hour solution and react 2 hours after solution IR spectrum separately.Can find out that the NCO that derives from 2-methylacryoyloxyethyl isocyanates is 2 along with the carrying out of reaction, 270cm -1Near peak reduces.Obtain polymkeric substance (A) solution of solid content 30.5%.This polymkeric substance (A) is designated as polymkeric substance (A-1).
Synthetic example 2
In 100 parts of above-mentioned multipolymers (α-1) solution; Add 14 parts of 2-acrylyl oxy-ethyl isocyanates (trade name, カ レ Application ズ AOI, clear and electrician's (strain) system), 0.08 part of 4-metoxyphenol; 60 ℃ of following stirring reactions 2 hours, obtain polymkeric substance (A) solution of solid content 30.5% then.This polymkeric substance (A) is designated as polymkeric substance (A-2).
Synthetic example 3
In flask with cooling tube, stirring machine, add 7.5 part 2,2 '-azoisobutyronitrile, 100 parts of acetic acid 3-methoxyl butyl esters and 100 parts of propylene glycol methyl ether acetates then add 18 parts of methacrylic acids, 30 parts of methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester (trade name PLACCEL FM1D (ダ ィ セ Le chemical industry (strain) system), 17 parts of methacrylic acid tetrahydrofuran-2-esters; Carry out after the nitrogen replacement, Yi Bian slowly stir, Yi Bian make solution temperature rise to 80 ℃; Under this temperature, kept 4 hours; Rise to 100 ℃ then, under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-2) solution of solid content 33.0%.
The Mw value that records resulting multipolymer (α-2) through GPC is 15,000.
Then, example 1 is the same with synthesizing, and the solution of above-mentioned multipolymer (α-2) and 2-methylacryoyloxyethyl isocyanates are reacted.Example 1 is the same with synthesizing, and confirms that through IR spectrum situation is carried out in the reaction of NCO and multipolymer.Obtain polymkeric substance (A) solution of solid content 35.0%.This polymkeric substance (A) is designated as polymkeric substance (A-3).
Synthetic example 4
Example 2 is the same with synthesizing, and 100 parts of above-mentioned multipolymers (α-2) solution and 2-acrylyl oxy-ethyl isocyanates are reacted, and obtains polymkeric substance (A) solution of solid content 35.0%.This polymkeric substance (A) is designated as polymkeric substance (A-4).
Synthetic example 5
In flask with cooling tube, stirring machine, add 5 part 2,2 '-azoisobutyronitrile, 250 parts of propylene glycol methyl ether acetates then add 18 parts of methacrylic acids, 30 parts of methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 2-(3-hydroxyls-2; 2-dimethyl-propoxycarbonyl oxygen base) potpourri of ethyl ester and methacrylic acid 2-hydroxyl ethyl ester (trade name HEMACl (ダ イ セ Le chemical industry (strain) system)), 17 parts of methacrylic acid tetrahydrofuran-2-esters; Carry out after the nitrogen replacement, Yi Bian slowly stir, Yi Bian make solution temperature rise to 80 ℃; Under this temperature, kept 4 hours; Rise to 100 ℃ then, under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-3) solution of solid content 28.2%.
The Mw value that records resulting multipolymer (α-3) through GPC is 15,000.
Then, example 1 is the same with synthesizing, and the solution of above-mentioned multipolymer (α-3) and 2-methylacryoyloxyethyl isocyanates are reacted, and is the same with synthetic routine 1, confirms that through IR spectrum situation is carried out in the reaction of NCO and multipolymer.Obtain polymkeric substance (A) solution of solid content 31.0%.This polymkeric substance (A) is designated as polymkeric substance (A-5).
Synthetic example 6
Example 2 is the same with synthesizing, and 100 parts of above-mentioned multipolymers (α-3) solution and 2-acrylyl oxy-ethyl isocyanates are reacted, and obtains polymkeric substance (A) solution of solid content 31.0%.This polymkeric substance (A) is designated as polymkeric substance (A-6).
Synthetic example 7
In flask with cooling tube, stirring machine, add 5 part 2,2 '-azoisobutyronitrile, 250 parts of propylene glycol methyl ether acetates then add 18 parts of methacrylic acids, 10 parts of methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 3-methylol-diamantane-1-base methyl esters, 37 parts of methacrylic acid tetrahydrofuran-2-esters; Carry out after the nitrogen replacement, Yi Bian slowly stir, Yi Bian make solution temperature rise to 80 ℃; Under this temperature, kept 4 hours; Rise to 100 ℃ then, under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-4) solution of solid content 28.2%.
The Mw value of utilizing GPC to measure resulting multipolymer (α-4) is 17,000.
Then, example 1 is the same with synthesizing, and the solution of above-mentioned multipolymer (α-4) and 2-methylacryoyloxyethyl isocyanates are reacted.The same with synthetic routine 1, confirm that through IR spectrum situation is carried out in the reaction of NCO and multipolymer.Obtain polymkeric substance (A) solution of solid content 32.0%.This polymkeric substance (A) is designated as polymkeric substance (A-7).
Synthetic example 8
In 100 parts of above-mentioned multipolymers (α-4) solution, example 2 is the same with synthesizing, and reacts with 2-acrylyl oxy-ethyl isocyanates, obtains polymkeric substance (A) solution of solid content 32.0%.This polymkeric substance (A) is designated as polymkeric substance (A-8).
Synthetic example 9
In flask with cooling tube, stirring machine, add 5 part 2,2 '-azoisobutyronitrile, 250 parts of propylene glycol methyl ether acetates then add 18 parts of methacrylic acids, 10 parts of methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 2-hydroxyl ethyl esters, 37 parts of methacrylic acid tetrahydrofuran-2-esters; Carry out after the nitrogen replacement, Yi Bian slowly stir, Yi Bian make solution temperature rise to 80 ℃; Under this temperature, kept 4 hours; Rise to 100 ℃ then, under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-5) solution of solid content 28.8%.
The Mw value of utilizing GPC to measure resulting multipolymer (α-5) is 17,000.
Then, example 1 is the same with synthesizing, and the solution of above-mentioned multipolymer (α-5) and 2-methylacryoyloxyethyl isocyanates are reacted.The same with synthetic routine 1, confirm that through IR spectrum situation is carried out in the reaction of NCO and its polymers.Obtain polymkeric substance (A) solution of solid content 32.0%.This polymkeric substance (A) is designated as polymkeric substance (A-9).
Synthetic example 10
Example 2 is the same with synthesizing, and 100 parts of above-mentioned multipolymers (α-5) solution and 2-acrylyl oxy-ethyl isocyanates are reacted, and obtains polymkeric substance (A) solution of solid content 32.0%.This polymkeric substance (A) is designated as polymkeric substance (A-10).
Synthetic example 11
In flask with cooling tube, stirring machine, add 7.5 part 2,2 '-azoisobutyronitrile, 100 parts of acetic acid 3-methoxyl butyl esters and 100 parts of propylene glycol methyl ether acetates then add 18 parts of methacrylic acids, 30 parts of methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-potpourri (trade name PLACCEL FM1D (ダ イ セ Le chemical industry (strain) system), 17 parts of methacrylic acid tetrahydrofuran-2-esters of 8-ester, 5 parts of styrene, 5 parts of butadiene, 25 parts of methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl esters and methacrylic acid 2-hydroxyl ethyl ester; Carry out after the nitrogen replacement; Slowly stir on one side; Make solution temperature rise to 80 ℃ on one side, under this temperature, kept 4 hours, rise to 100 ℃ then; Under this temperature, keep carrying out polymerization in 1 hour, obtain multipolymer (α-6) solution of solid content 33.5%.
The Mw value of utilizing GPC to measure resulting multipolymer (α-6) is 16,000.
Then, example 1 is the same with synthesizing, and the solution of above-mentioned multipolymer (α-6) and 2-methylacryoyloxyethyl isocyanates are reacted.Example 1 is the same with synthesizing, and confirms that through IR spectrum situation is carried out in the reaction of NCO and multipolymer.Obtain polymkeric substance (A) solution of solid content 36.0%.This polymkeric substance (A) is designated as polymkeric substance (A-11).
Embodiment 1
The preparation of composition solution
As composition [A], polymkeric substance (A) solution that uses gained in the synthetic example 1 is in 100 parts in polymkeric substance (A-1); As composition (B), use 80 parts of dipentaerythritol acrylates (trade name KAYARADDPHA, Japanese chemical drug (strain) is made); As composition (C); Use 5 parts of 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters (trade name CGI-242; Ciba Speciality Chemicals manufactured), 10 parts of 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-Ding-1-ketone (trade name イ Le ガ キ ユ ア 379, Ciba Speciality Chemicals manufactured); As adhesive aid, use 5 parts of γ-glycidoxypropyltrime,hoxysilane; As surfactant, use 0.5 part of FTX-218 (trade name, (strain) ネ オ ス system); As the stable storage agent, use 0.5 part of 4-metoxyphenol; Mentioned component is mixed, and it is dissolved in the propylene glycol methyl ether acetate, make solid content reach 30%, using the aperture then is the millipore filter filtration of 0.5 μ m, makes composition solution.
(1) evaluation of sensitivity
Use spinner coating above-mentioned composition solution on the alkali-free glass substrate of band ITO film, prebake 3 minutes on 90 ℃ hot plate then, forming thickness is the tunicle of 4.0 μ m.
Then pass through the photomask of the remaining pattern of 15 μ m figures, so that intensity is 250W/m at the 365nm place 2Ultraviolet ray be that variable makes public with the time shutter to the gained tunicle.Potassium hydroxide aqueous solution through 0.05 weight % developed for 60 seconds down at 25 ℃ then, cleaned 1 minute with pure water then, in 220 ℃ baking oven, heated 60 minutes again, formed sept.At this moment, with the residual film ratio (thickness after the development * 100/ initial film thickness after developing.Down with) reach 90% or above minimum exposure amount as sensitivity.When this exposure 1,200J/m 2Or when following, think that its sensitivity is good.
(2) evaluation of resolution
In the evaluation of above-mentioned (1) sensitivity; Except use has photomask that the line of various sizes adds intermittent pattern as photomask; And use exposure corresponding to the sensitivity that is determined in " evaluation of (1) sensitivity " as outside the exposure, and carry out same operation, on substrate, form pattern.With the minimum pattern size that at this moment can differentiate as resolution.
(3) formation of sept
In the evaluation of above-mentioned (1) sensitivity, except using exposure corresponding to the sensitivity that is determined in " evaluation of (1) sensitivity ", carry out same operation as the exposure, forming highly is the sept of 3.5 μ m.
(4) evaluation of cross sectional shape
Through scanning electron microscope the cross sectional shape of resulting sept is observed, through judging that observations is equivalent among Fig. 6 among A～D any situation and estimates.At this moment, if the same with A or B, pattern edge is positive cone or vertical configuration, thinks that then its cross sectional shape is good.In contrast, if the same with C, sensitivity is not enough, residual film ratio is low, sectional dimension is littler than A and B, when the bottom surface is the semi-convex lensing in plane, and then cross sectional shape is bad; In addition, if the same with D when being back taper (in the cross sectional shape, the upside-down triangle shape that the limit on film surface is also longer than the limit of substrate one side), because when the friction treatment of back, the possibility that pattern is peeled off would be very big, so it is bad to be regarded as cross sectional shape.
(5) evaluation of compression performance
Use miniature compression test (trade name FISCHER SCOPE H100C; (strain) FischerInstruments manufactured), be the plane pressure head of 50 μ m through diameter, make loading speed and off-loading speed be 2.6mN/ second; To the loading of gained sept to 50mN; Kept for 5 seconds, off-loading then, the load the when load when obtaining loading-deflection curve and off-loading-deflection curve.At this moment as shown in Figure 7, the deflection difference when deflection when load is 50mN during loading and load are 5mN is designated as L1; Deflection difference when deflection when load is 50mN during off-loading and load are 5mN is designated as L2, draws elastic recovery rate according to computes.
Elastic recovery rate (%)=L2 * 100/L1
In addition, big like L1, then we can say flexibility.
(6) evaluation of rub resistance and tack
Use printing machine through liquid crystal orientation film coating, on the substrate that forms sept coating as the AL3046 (trade name, JSR (strain) makes) of aligning agent for liquid crystal, then 180 ℃ dry 1 hour down, formation thickness is that the aligning agent for liquid crystal of 0.05 μ m is filmed.
Then with rubbing machine, with the platform translational speed of the roller rotating speed of 500rpm, 1cm/ second this is filmed and to carry out friction treatment with the roller that twines polyamide fabric.The situation that evaluation pattern generating had or not fragmentation or peeled off this moment.
(7) stable on heating evaluation
Except not using the photomask; Other all according to aforementioned formation sept identical operations, form cured film, heating 60 minutes in 240 ℃ baking oven then; Measure the film thickness of heating front and back, estimate according to residual film ratio (thickness after the heating * 100/ initial film thickness).
Embodiment 2～22, comparative example 1～7
Among the embodiment 1; With each composition shown in the table 1 and 5 parts of γ-glycidoxypropyltrime,hoxysilane, 0.5 part of FTX-218 as surfactant as adhesive aid; 0.5 part 4-metoxyphenol as the stable storage agent mixes, and it is dissolved in the propylene glycol methyl ether acetate, makes solid content reach 30%; Millipore filter with aperture 0.5 μ m filters then, makes composition solution.Then according to forming sept with embodiment 1 identical operations and estimating equally with embodiment 1.Evaluation result is as shown in table 2.
Embodiment 23
Except replacing spin-coating method, and use the dry film method to process outside the filming of fluid composition (S-23) of radiation sensitive resin composition, as embodiment 1～22, process the pattern-like film and estimate.Each composition is as shown in table 1.In addition, before exposure process, peel off and remove basement membrane.Its evaluation result is as shown in table 2.In addition, the evaluation result of following transfer printing property is also as shown in table 2.
The making of dry film and transfer printing are carried out according to following steps.
On polyethylene terephthalate (PET) film of thickness 38 μ m; Use the fluid composition (S-1) of spreader coating radiation sensitive resin composition; Heat down at 100 ℃ then and filmed 5 minutes, obtain the radiation-sensitive dry film (J-1) of thickness 4 μ m.Then, at glass baseplate surface, the overlapping radiation-sensitive transfer printing of the mode dry film with over against contact radiation-sensitive transfer printing layer surface is transferred to radiation-sensitive dry film (J-1) on the glass substrate with pressure sintering.
The evaluation of-dry film transfer printing property on glass substrate-
When being transferred to the radiation-sensitive dry film on the glass substrate with pressure sintering; Dry film is designated as " O " in the time of can evenly being transferred on the glass substrate, and residual on the basement membrane have that dry film is designated as " * " on part dry film or the glass substrate when dry film such as close attachment evenly is not transferred on the glass substrate.
Embodiment 24
Except the fluid composition that uses the radiation sensitive resin composition shown in the table 1 replace embodiment 23 used, the same with embodiment 23, behind the making radiation-sensitive dry film (J-2), estimate.Each composition is as shown in table 1.Evaluation result is as shown in table 2.The evaluation result of transfer printing property in addition, is also as shown in table 2.
Each composition in the table 1 except that polymkeric substance is as follows.
(B) composition
B-1: dipentaerythritol acrylate (trade name KAYARAD DPHA)
B-2: the commercially available product (trade name KAYARADDPHA-40H) that contains multifunctional ammonia ester acrylic ester compound
(C) composition
C-1:1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters (trade name CGI-242, Ciba Speciality Chemicals manufactured),
C-2:1-(9-ethyl-6-(2-methyl-4-oxinane methoxybenzoyl base)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-acetic acid esters,
C-3:2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino third-1-ketone (trade name イ Le ガ キ ユ ア 907, Ciba Speciality Chemicals manufactured),
C-4:2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-Ding-1-ketone (trade name イ Le ガ キ ユ ア 379, Ciba Speciality Chemicals manufactured),
C-5:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
C-6:4,4 '-two (diethylamino) benzophenone,
The C-7:2-mercaptobenzothiazoler.
Table 1
Table 2
Figure G06164736020070124D000351

Claims (7)

1. a polymkeric substance is characterized in that: be through making
(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,
(a2) the represented hydroxyl unsaturated compound of following formula (2), and
(a3) be selected from alkyl acrylate; Alkyl methacrylate; Acrylic acid epoxy base (ring) Arrcostab; Alpha-alkyl acrylic acid epoxy (ring) Arrcostab; The vinyl benzyl glycidol ether; The acrylate cyclic ester; The methacrylic acid alicyclic esters; The acrylic acid aryl ester; The acrylic acid aralkyl ester; Aryl methacrylate; The methacrylic acid aralkyl ester; The acrylic acid hydroxyalkyl acrylate; Methacrylic acid hydroxyl Arrcostab; The unsaturated dicarboxylic acid dialkyl; Has the acrylic ester that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen; Has the methacrylate that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen; Styrene; AMS; Between methyl styrene; P-methylstyrene; To methoxy styrene; Conjugated diene compound; Vinyl cyanide; Methacrylonitrile; Acrylic amide; Methacrylamide; Vinyl chloride; Isocyanate compound reaction shown in the multipolymer of at least a unsaturated compound of vinylidene chloride and vinyl acetate and the following formula (5) obtains
Wherein alpha-alkyl acrylic acid epoxy (ring) Arrcostab in (a3) comprises methacrylic acid epoxy (ring) Arrcostab and other alpha-alkyl acrylic acid epoxy (ring) Arrcostab,
Figure FSB00000667282800011
In the formula, R representes hydrogen atom or methyl, and b is 1～12 integer, and c is 1,
Figure FSB00000667282800012
In the formula, R representes hydrogen atom or methyl, and h is 1～12 integer.
2. the manufacturing approach of the said polymkeric substance of claim 1; It is characterized in that: make the represented hydroxyl unsaturated compound of (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) following formula (2) and (a3) be selected from alkyl acrylate, alkyl methacrylate, acrylic acid epoxy base (ring) Arrcostab, alpha-alkyl acrylic acid epoxy (ring) Arrcostab, vinyl benzyl glycidol ether, acrylate cyclic ester, methacrylic acid alicyclic esters, acrylic acid aryl ester, acrylic acid aralkyl ester, aryl methacrylate, methacrylic acid aralkyl ester, acrylic acid hydroxyalkyl acrylate, methacrylic acid hydroxyl Arrcostab, unsaturated dicarboxylic acid dialkyl, have the acrylic ester that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen, have the methacrylate that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen, styrene, AMS, a methyl styrene, p-methylstyrene, to the multipolymer and the reaction of the isocyanate compound shown in the following formula (5) of at least a unsaturated compound of methoxy styrene, conjugated diene compound, vinyl cyanide, methacrylonitrile, acrylic amide, Methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate, wherein alpha-alkyl acrylic acid epoxy (ring) Arrcostab in (a3) comprises methacrylic acid epoxy (ring) Arrcostab and other alpha-alkyl acrylic acid epoxy (ring) Arrcostab.
3. a radiation sensitive resin composition is characterized in that: comprise the described polymkeric substance of claim 1 (A), polymerizable unsaturated compound (B) and radiation-sensitive polymerization initiator (C).
4. be used to form the radiation sensitive resin composition of used for liquid crystal display element sept, it comprises the described radiation sensitive resin composition of claim 3.
5. used for liquid crystal display element sept, it is formed by the described radiation sensitive resin composition of claim 3.
6. the formation method of used for liquid crystal display element sept is characterized in that: comprise following operation at least according to following order:
(1) operation of the said radiation sensitive resin composition tunicle of formation claim 3 on substrate,
The operation of (2) at least a portion of this tunicle being made public,
The operation of (3) this tunicle after the exposure being developed, and
(4) operation that this tunicle after developing is heated.
7. liquid crystal display cells, it possesses the described sept of claim 5.
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