CN1950751A - Radiation-sensitive resin composition, spacer, and method of forming the same - Google Patents
Radiation-sensitive resin composition, spacer, and method of forming the same Download PDFInfo
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- CN1950751A CN1950751A CNA2005800139437A CN200580013943A CN1950751A CN 1950751 A CN1950751 A CN 1950751A CN A2005800139437 A CNA2005800139437 A CN A2005800139437A CN 200580013943 A CN200580013943 A CN 200580013943A CN 1950751 A CN1950751 A CN 1950751A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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
-
- 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
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Providing a radiation-sensitive resin composition which has high sensitivity and high resolution, can readily form a patterned thin film excellent in various performances including pattern shape, compression strength, rubbing resistance, and adhesion to transparent substrates, and is inhibited from emitting sublimates upon burning; a spacer formed from the composition; and a method of forming the spacer. The radiation-sensitive resin composition is characterized by comprising (A) a polymer which has carboxy and epoxy groups and in which the ratio of the weight-average molecular weight (Mw) in terms of polystyrene to the number-average molecular weight (Mn) in terms of polystyrene both measured by gel permeation chromatography, (Mw/Mn), is 1.7 or lower, (B) a polymerizable unsaturated compound, and (C) a radiation-sensitive polymerization initiator.
Description
Technical field
The present invention relates to radiation sensitive resin composition, sept and forming method thereof.
Background technology
In the past, in liquid crystal display cells, in order to make two intervals between the transparency carrier keep certain, the beaded glass, plastic bead that use has a regulation particle diameter be composition granule uniformly-spaced, and these spacer particles are dispersed on the transparency carriers such as glass substrate, therefore randomly, there is spacer particles if form the zone in pixel, then produce the phenomenon that spacer particles mirrors, incident light is subjected to scattering, and the contrast of liquid crystal display cells descends.
In order to address these problems, adopted the method that forms sept by photoetch method.This method is that radiation sensitive resin composition is coated on the substrate, through the mask of regulation, and the exposure ultraviolet ray, develop then, form the sept of point-like or strip, only the determined location beyond pixel forms the zone forms sept like this, therefore can address the above problem substantially.
But, the radioactive ray that mercury lamp sent that use as the light source in the photoetch method are near 436nm (g line) usually, near the 404nm (h line), near the 365nm (i line), near the 335nm, near the 315nm (j line), wait near the 303nm and show the strong spectrum of intensity, therefore, usually being chosen in the wavelength region may of the strong spectrum of these intensity and having the constituent of the material of maximum absorption wavelength as radiation sensitive resin composition---the radiation-sensitive polymerization initiator uses, consider that from the angle of the transparency nearly all occasion all is to use the zone below the i line to have the radiation-sensitive polymerization initiator (with reference to TOHKEMY 2001-261761 communique) of maximum absorption wavelength.Use has the radiation-sensitive polymerization initiator of maximum absorption wavelength near than the g line of i line length, h line, then near the wavelength region may of this radiation-sensitive polymerization initiator luminous ray has absorption, therefore the radiation sensitive resin composition that contains this polymerization initiator can be painted, and the transparency of the tunicle of formation reduces.Film is transparent low thoroughly, when then exposing, the film surface produces curing reaction, the curing reaction of tunicle depth direction is insufficient, the result, the shape of sept of back gained of developing becomes back taper (cross sectional shape is the upside-down triangle shape of the limit on film surface than the length of side of substrate-side), after the alignment film rubbing processing time, this becomes the reason that sept is peeled off.
But, comprise TOHKEMY 2001-261761 communique, in the radiation sensitive resin composition in the past, the sublimate that is produced when carrying out sintering in order to form sept can pollute production line or device, so people wish the low radiation sensitive resin composition of sublimate that produces.
Summary of the invention
The present invention is based on above problem and establish.Therefore, the object of the present invention is to provide a kind of radiation sensitive resin composition, by its sept that forms and forming method thereof, wherein said radiation sensitive resin composition is high sensitivity, high image resolution, and can easily form pattern form, compression strenght, friction patience, with the pattern-like film of each excellent performance such as stickiness of transparency carrier, can suppress the generation of sublimate during sintering.
First, above-mentioned purpose of the present invention can realize by radiation sensitive resin composition, it is characterized in that: contain (A) and have carboxyl and epoxy radicals and the weight-average molecular weight through polystyrene conversion (Mw) by gel permeation chromatography and be polymkeric substance below 1.7, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization initiator through the ratio (Mw/Mn) of the number-average molecular weight (Mn) of polystyrene conversion.
" radioactive ray " described in the present invention are meant and comprise ultraviolet ray, far ultraviolet, X ray, electron ray, molecular ray, gamma-rays, synchrotron radioactive ray, proton beam ray etc.
The second, above-mentioned purpose of the present invention can realize by the formation method of sept, it is characterized in that: implement following steps by following order:
(1) on substrate, form above-mentioned radiation sensitive resin composition the step of filming,
(2) to the step of this at least a portion of filming irradiation radioactive ray,
(3) development step and
(4) heating steps.
The 3rd, above-mentioned purpose of the present invention can realize by the sept that is formed by said method.
The accompanying drawing summary
Fig. 1 is the mode chart that exemplifies the cross sectional shape of sept.
The best mode that carries out an invention
Radiation sensitive resin composition
Below, each composition of radiation sensitive resin composition of the present invention is elaborated.
Multipolymer (A)
Multipolymer in the radiation sensitive resin composition of the present invention (A) preferably makes the polymerism potpourri that contains following compound carry out active free radical polymerization and obtains: (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (following they are referred to as " compound (a1) "), (a2) contain the unsaturated compound (hereinafter referred to as " compound (a2) ") of epoxy radicals and (a3) other unsaturated compound (hereinafter referred to as " compound (a3) ").
For example, multipolymer (A) can be prepared as follows: in solvent, in the presence of the polymerization initiator, make the polymerism potpourri that contains compound (a1), compound (a2) and compound (a3) carry out active free radical polymerization.
Carboxyl that above-mentioned gained multipolymer (A) is had and epoxy radicals are respectively from compound (a1) and compound (a2).
The TEMPO system that the initiator system of active free radical polymerization preferably uses people such as Georges for example to find, the thiocarbonylthio compound of putting down in writing in the initiating agent that the constitutes system that proposes by people such as Matyjaszewski, the initiating agent that constitutes system, Japanese Unexamined Patent Application Publication 2000-515181 communique, Japanese Unexamined Patent Application Publication 2002-500251 communique and the Japanese Unexamined Patent Application Publication 2004-518773 communique that propose by people such as Higashimura and the combination of radical initiator etc. by phenixin and ruthenium (II) complex compound by copper bromide, brominated ester compounds.
Can be for obtaining the preferred living polymerization initiating agent of polymkeric substance of the present invention (A) system according to employed monomeric species, suitably select the system of the terminal non-inactivation of growth, but consider the combination of preferred thiocarbonylthio compound and radical initiator from the polymerization efficiency equal angles.Here, thiocarbonylthio compound for example has dithioesters class, dithiocarbonates class, trithiocarbonate class, xanthate class etc.
Its object lesson has the compound shown in the following formula.
Wherein can exemplify: the xanthate that uses in dithioesters that uses in dithiobenzoic acid isopropyl benzene ester, S-cyano methyl-S-dodecyl trithiocarbonate, pyrazoles-1-two bamic acid phenyl-methyl ester, the following synthesis example 5 and the following synthesis example 6.
Radical initiator can use known usually as the compound of radical polymerization initiator, for example has: 2, and 2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, the peroxidating trimethylace tonitric tert-butyl ester, 1,1 '-two-organic peroxides such as (t-butylperoxy) cyclohexane; Hydrogen peroxide; Contain the oxidation-reduction type initiating agent of these superoxide and reductive agent etc.
These polymerization initiators can separately or be use mixing two or more.
In per 100 weight portion polymerization initiators, the preferred 1-10 of the use amount of above-mentioned thiocarbonylthio compound, 000 weight portion, further preferred 10-1,000 weight portion.Per 100 weight portions contain in the monomer mixture of polymerizable unsaturated compound of epoxy radicals, the preferred 0.01-100 weight portion of the use amount of radical polymerization initiator, further preferred 0.1-10 weight portion.Polymerization temperature during to above-mentioned active free radical polymerization is not particularly limited, and preferred 0 ℃-100 ℃, further preferred 10 ℃-85 ℃.
According to the difference of initiating agent system, in order to make the polymerization initiator non-inactivation, can protect the carboxyl of compound (a1) by suitable protecting group, use gained ester compounds (a1 ') carry out polymerization, obtain multipolymer (A) by deprotection then.
Compound (a1) for example has: monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, mono succinate (2-acrylyl oxy-ethyl) ester, mono succinate (2-methylacryoyloxyethyl) ester, hexahydrophthalic acid list (2-acrylyl oxy-ethyl) ester, hexahydrophthalic acid list (2-methylacryoyloxyethyl) ester; Dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The anhydrides of these dicarboxylic acid.
In these compounds (a1), consider preferred acrylic acid, methacrylic acid, maleic anhydride etc. from the angle of copolyreaction and acquisition easily.
Above-claimed cpd (a1) can separately or be use mixing two or more.
In the multipolymer (A), the preferred 5-50% weight of containing ratio of the formation unit of deriving by compound (a1), preferred especially 10-40% weight.At this moment, if the containing ratio of this formation unit is lower than 5% weight, then the compression strenght of gained sept, thermotolerance or chemical proofing have downtrending, if surpass 50% weight, then the storage stability of radiation sensitive resin composition may reduce.
Compound (a2) for example has: glycidyl acrylate, glycidyl methacrylate, the α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid 3,4-epoxy radicals butyl ester, methacrylic acid 3,4-epoxy radicals butyl ester, α-Yi Jibingxisuan 3,4-epoxy radicals butyl ester, acrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 6,7-epoxy radicals heptyl ester, a-ethyl olefin(e) acid 6,7-epoxy radicals heptyl ester, acrylic acid Beta-methyl ethylene oxidic ester, methacrylic acid Beta-methyl ethylene oxidic ester, propenoic acid beta-ethyl ethylene oxidic ester, methacrylic acid β-ethyl ethylene oxidic ester, propenoic acid beta-n-pro-pyl ethylene oxidic ester, methacrylic acid β-n-pro-pyl ethylene oxidic ester, acrylic acid 3,4-epoxy radicals cyclohexyl, methacrylic acid 3, carboxylates such as 4-epoxy radicals cyclohexyl; Adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to ethers such as vinyl benzyl glycidol ethers etc.
In these compounds (a2), consider from the intensity angle that improves copolyreaction and gained sept, preferable methyl glycidyl acrylate, methacrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl, methacrylic acid Beta-methyl ethylene oxidic ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.
Above-claimed cpd (a2) can separately or be use mixing two or more.
In the multipolymer (A), the preferred 10-70% weight of containing ratio of the formation unit of deriving by compound (a2), preferred especially 20-60% weight.At this moment, when the containing ratio of this formation unit was lower than 10% weight, the compression strenght of gained sept, thermotolerance or chemical proofing had the tendency of reduction, and surpassed 70% weight, and then the storage stability of radiation sensitive resin composition has the tendency of decline.
Compound (a3) for example has: alkyl acrylates such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate; Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0
2,6] decane-8-base ester (following general " three ring [5.2.1.0
2,6] decane-8-yl " be called " two cyclopentane bases "), acrylic acid alicyclic ester such as acrylic acid 2-two cyclopentane base oxygen base ethyl esters, isobornyl acrylate, tetrahydrofurfuryl acrylate; The alicyclic fat of methacrylic acids such as cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid two cyclopentane base esters, methacrylic acid 2-two cyclopentane base oxygen base ethyl esters, isobornyl methacrylate, tetrahydrofurfuryl methacrylate; Aryl acrylate such as phenyl acrylate, benzyl acrylate; Metering system such as phenyl methacrylate, benzyl methacrylate acid aryl ester; Dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate; Acrylic acid hydroxyalkyl acrylates such as acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester; Methacrylic acid hydroxyl Arrcostabs such as 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester; Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, to aromatic vinyl compounds such as methoxy styrenes; Or vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexyl maleimide, N-phenylmaleimide, N-benzyl maleimide, N-succinimide base-3-maleimide benzoic ether, N-succinimide base-4-maleimide butyric ester, N-succinimide base-6-maleimide capronate, N-succinimide base-3-maleimide propionic ester, N-(9-acridinyl) maleimide etc.
In these compounds (a3), consider preferred acrylic acid 2-methyl cyclohexane ester, metering system tert-butyl acrylate, methacrylic acid two cyclopentane base esters, styrene, to methoxy styrene, 1,3-butadiene etc. from the angle of copolyreaction.
Above-claimed cpd (a3) can separately or be use mixing two or more.
In the multipolymer (A), the containing ratio of the formation unit of being derived by compound (a3) is preferably 10-80% weight, preferred especially 20-60% weight.At this moment, if the containing ratio of this formation unit is lower than 10% weight, then the storage stability of radiation sensitive resin composition may reduce, and surpasses 80% weight, and then development property may reduce.
Multipolymer used in the present invention (A) by gel permeation chromatography, be below 1.7 through the weight-average molecular weight (hereinafter referred to as " Mw ") of polystyrene conversion with through the ratio (Mw/Mn) of the number-average molecular weight (hereinafter referred to as " Mn ") of polystyrene conversion, preferred below 1.5.If Mw/Mn surpasses 1.7, then the pattern form variation of gained sept.Mw preferred 2 * 10
3-1 * 10
5, more preferably 5 * 10
3-5 * 10
4If Mw is lower than 2 * 10
3, the limit of then developing is insufficient, and the membrane left rate of gained tunicle etc. may reduce, possible deviations such as the pattern form of gained sept, thermotolerance.And Mw surpasses 1 * 10
5, then sensitivity descends, the pattern form variation.Mn preferred 1.2 * 10
3-1 * 10
5, more preferably 2.9 * 10
3-5 * 10
4The radiation sensitive resin composition that contains above-mentioned multipolymer (A) can not produce when developing and develop residually, can easily form the shape of predetermined pattern.
And the multipolymer that uses among the present invention (A) preferably is lower than 5.0% by the levels of residual monomers of gel permeation chromatography, more preferably less than 3.0%, especially preferably is lower than 2.0%.By using the multipolymer of above-mentioned residual monomer content, what sublimate reduced in the time of can obtaining sintering films.
Among the present invention, multipolymer (A) can separately or be use mixing two or more.
The employed solvent of preparation multipolymer (A) for example has: alcohol, ether, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diglycol, propylene glycol one alkyl ether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbon, ketone, ester etc.
Their object lesson is as follows:
The example of alcohol has: methyl alcohol, ethanol, benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol etc.;
The example of ethers has: tetrahydrofuran etc.;
The example of glycol ethers has: glycol monomethyl ether, ethylene glycol monoethyl ether etc.;
The example of ethylene glycol alkyl ether acetic acid esters has: methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid ester, ethylene glycol monoethyl ether acetic acid esters etc.;
The example of diglycol has: diethylene glycol monomethyl ether, carbitol, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl-methyl ether etc.;
The example of propylene glycol one alkyl ether has: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol one propyl ether, propylene glycol monobutyl ether etc.;
The example of propylene glycol alkyl ether propionic ester has: methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.;
The example of propylene glycol alkyl ether acetic acid ester has: methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
The example of aromatic hydrocarbon has: toluene, dimethylbenzene etc.;
The example of ketone has: methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone etc.;
The example of ester has respectively: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, esters such as 3-butoxy butyl propionate.
Wherein, preferred ethylene glycol alkyl ether acetic acid esters, diglycol, propylene glycol one alkyl ether, propylene glycol alkyl ether acetic acid ester, wherein, preferred especially diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, methyl proxitol, methyl proxitol acetate.
(B) polymerizable unsaturated compound
Above acrylate and the methacrylate (hereinafter referred to as " (methyl) acrylate ") of the preferred difunctionality of polymerizable unsaturated compound in the radiation sensitive resin composition of the present invention (B).
Dual functional methacrylate for example has: acrylic acid glycol ester, methacrylic acid glycol ester, diacrylate 1,6-hexanediol ester, dimethacrylate 1,6-hexanediol ester, diacrylate 1,9-nonanediol ester, dimethacrylate 1,9-nonanediol ester, diacrylate tetraethylene glycol ester, dimethacrylate tetraethylene glycol ester, diacrylate polypropylene glycol ester, dimethacrylate polypropylene glycol ester, two phenoxetol fluorenes diacrylate, two phenoxetol fluorenes dimethylacrylates etc.
The commercially available product of dual functional (methyl) acrylate for example has: ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (above is that East Asia synthetic (strain) prepares), KAYARADHDDA, KAYARADHX-220, KAYARADR-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (above is Japanese chemical drug (strain) preparation), PVC ス コ-ト 260, PVC ス コ-ト 312, PVC ス コ-ト 335HP (above is Osaka organic chemistry industry (strain) preparation) etc.
Above (methyl) acrylate of trifunctional for example has: trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, tricresyl phosphate (2-acryloxy ethyl) ester, tricresyl phosphate (2-methacryloxyethyl) ester; Above (methyl) acrylate of nine senses has: the compound that has more than one hydroxyl in the compound that has straight-chain alkyl-sub-and ester ring type structure and have two above isocyanate group and the molecule and have three, four or five acryloxies and/or a methacryloxy reacts the urethane acrylate based compound that obtains etc.
The commercially available product of (methyl) acrylate that trifunctional is above for example has: ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-402, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-1310, ア ロ ニ Star Network ス M-1600, ア ロ ニ Star Network ス M-1960, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, ア ロ ニ Star Network ス M-8100, ア ロ ニ Star Network ス M-8530, ア ロ ニ Star Network ス M-8560, ア ロ ニ Star Network ス M-9050, ア ロ ニ Star Network ス TO-1450 (above is that East Asia synthetic (strain) prepares), KAYARADTMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARADDPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARADMAX-3510 (above is Japanese chemical drug (strain) preparation), PVC ス コ-ト 295, PVC ス コ-ト 300, PVC ス コ-ト 360, PVC ス コ-ト GPT, PVC ス コ-ト 3PA, PVC ス コ-ト 400 (above is Osaka organic chemistry industry (strain) preparation), the urethane acrylate based compound has: ニ ユ-Off ロ Application テ イ ア R-1150 (the first industrial pharmacy (strain) preparation), KAYARAD DPHA-40H (Japanese chemical drug (strain) preparation) etc.
Among the present invention, polymerizable unsaturated compound can separately or be use mixing two or more.
(C) radiation-sensitive polymerization initiator
The radiation-sensitive polymerization initiator is the induction radioactive ray, and generation can cause the composition of the active seed of thing of the polymerization of (B) polymerizable unsaturated compound.
The for example preferred radiation-sensitive radical polymerization initiator of described radiation-sensitive polymerization initiator.
Above-mentioned radiation-sensitive radical polymerization initiator for example has: the α-diketone of benzyl, diacetyl etc.; Acyloins such as benzoin; Acyloin ethers such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Thioxanthones, 2,4-diethyl thioxanthone, thioxanthones-4-sulfonic acid, benzophenone, 4, benzophenones such as 4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone; Acetophenone, to dimethylamino benzoylformaldoxime, 4-(α, α '-dimethoxy acetoxyl group) benzophenone, 2,2 '-dimethoxy-2-phenyl acetophenone, acetanisole, 2-methyl-2-morpholino-1-(4-methyl thio phenyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-acetophenones such as 1-ketone; Anthraquinone, 1, quinones such as 4-naphthoquinones; Phenacyl chloride, trisbromomethyl benzene sulfone, three (trichloromethyl)-halogen compounds such as s-triazine; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4, acylphosphine oxides such as 4-tri-methyl-amyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide; Superoxide such as di-t-butyl peroxide etc.
The commercially available product of radiation-sensitive radical polymerization initiator for example has: IRGACURE-124, IRGACURE-149, IRGACURE-184, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-1000, IRGACURE-1700, IRGACURE-1800, IRGACURE-1850, IRGACURE-2959, Darocur-1116, Darocur-1173, Darocur-1664, Darocur-2959, Darocur-4043 (above) by the preparation of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ company, KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (above) by Japanese chemical drug (strain) preparation, LUCIRIN TPO (BASF AG's preparation), VICURE-10, VICURE-55 (above) by the preparation of STAUFFER company, TRIGONALP1 (preparation of AKZO company), SANDORAY 1000 (preparation of SANDOZ company), DEAP (preparation of APJOHN company), QUANTACURE-PDO, QUANTACURE-ITX, QUANTACURE-EPD (above) etc. by the preparation of WARD DLEKINSOP company.
These radiation-sensitive radical polymerization initiators can separately or be use mixing two or more.
By more than one radiation-sensitive sensitizers are used in combination with above-mentioned radiation-sensitive radical polymerization initiator, the inactivation that can obtain causing because of airborne oxygen reduces, the radiation sensitive resin composition of high sensitivity.
In the radiation sensitive resin composition of the present invention, the use amount of each composition is as follows: with respect to 100 weight portion multipolymers (A), and (B) the preferred 10-150 weight portion of polymerizable unsaturated compound, further preferred 20-120 weight portion; With respect to 100 weight portion multipolymers (A), (C) the preferred 1-40 weight portion of radiation-sensitive polymerization initiator, further preferred 3-35 weight portion.
(B) use amount of polymerizable unsaturated compound is lower than 10 weight portions, and the tendency of filming that is difficult to form uniform film thickness is then arranged, and surpasses 150 weight portions, and then the stickiness with substrate has the tendency of decline.(C) use amount of radiation-sensitive polymerization initiator is lower than 1 weight portion, and then thermotolerance, skin hardness or chemical proofing have the tendency of decline, and surpasses 40 weight portions, and then the transparency has the tendency of decline.
-any adjuvant-
Radiation sensitive resin composition of the present invention can be as required, mix any adjuvant beyond above-mentioned, for example gluing auxiliary agent, surfactant, preserving stabilizer, thermotolerance reinforcing agent etc. in the scope of not damaging effect of the present invention.
Above-mentioned gluing auxiliary agent is the composition that is used to make the tackiness of the sept of formation and substrate to improve.
Described gluing auxiliary agent has: the functional silanes coupling agent with carboxyl, methacryl, vinyl, isocyanate group, epoxy radicals isoreactivity functional group; its example has: trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.
These gluing auxiliary agents can separately or be use mixing two or more.
With respect to 100 weight portion multipolymers (A), below preferred 20 weight portions of the combined amount of gluing auxiliary agent, further below preferred 15 weight portions.At this moment, if the combined amount of gluing auxiliary agent surpasses 20 weight portions, then have to be easy to generate the residual tendency of developing.
Above-mentioned surfactant is the composition that is used to improve coating.
The for example preferred fluorine of described surfactant is surfactant, silicone type surface active agent etc.
Above-mentioned fluorine is that surfactant is preferably terminal, one of them of a main chain and side chain position has the compound of fluoroalkyl and/or fluorine alkylidene, and its example has: 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-pro-pyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol two (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, eight glycol two (1,1,2,2-tetrafluoro-normal-butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, eight propylene glycol two (1,1,2,2-tetrafluoro-normal-butyl) ether, perfluor-n-dodecane sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-ten fluoro-n-dodecanes or fluoroalkyl benzene sodium sulfonate, the fluoroalkyl sodium phosphate, the fluoroalkyl carboxylic acid sodium, diglycerol four (fluoroalkyl polyoxyethylene ether), the fluoroalkyl ammonium iodide, the fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxygenated ethanol, the perfluoroalkyl alkoxide compound, carboxylic acid fluoroalkyl ester etc.
Fluorine is that the commercially available product of surfactant for example has: BM-1000, BM-1100 (above) by the preparation of BM CHEMIE company, メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network F178, メ ガ Off ア Star Network F191, メ ガ Off ア Star Network F471, メ ガ Off ア Star Network F476 (above) by big Japanese ink chemical industry (strain) preparation, Off ロ ラ-De FC-170C, Off ロ ラ-De FC-171, Off ロ ラ-De FC-430, Off ロ ラ-De FC-431 (above) by Sumitomo (strain) preparation, サ-Off ロ Application S-112, サ-Off ロ Application S-113, サ-Off ロ Application S-131, サ-Off ロ Application S-141, サ-Off ロ Application S-145, サ-Off ロ Application S-382, サ-Off ロ Application SC-101, サ-Off ロ Application SC-102, サ-Off ロ Application SC-103, サ-Off ロ Application SC-104, サ-Off ロ Application SC-105, サ-Off ロ Application SC-106 (above) by Asahi Glass (strain) preparation, エ Off ト Star プ EF 301, エ Off ト Star プ EF 303, エ Off ト Star プ EF 352 (above by new autumn fields change into (strain) preparation), Off -ジ エ Application ト FT-100, Off -ジ エ Application ト FT-110, Off -ジ エ Application ト FT-140A, Off -ジ エ Application ト FT-150, Off -ジ エ Application ト FT-250, Off -ジ エ Application ト FT-251, Off -ジ エ Application ト FT-300, Off -ジ エ Application ト FT-310, Off -ジ エ Application ト FT-400S, Off -ジ エ Application ト FTX-218, Off -ジ エ Application ト FTX-251 (above) etc. by ネ オ ス (strain) preparation.
Above-mentioned silicone type surface active agent for example has: with ト-レ シ リ コ-Application DC3PA, ト-レ シ リ コ-Application DC7PA, ト-レ シ リ コ-Application SH11PA, ト-レ シ リ コ-Application SH21PA, ト-レ シ リ コ-Application SH28PA, ト-レ シ リ コ-Application SH29PA, ト-レ シ リ コ-Application SH30PA, ト-レ シ リ コ-Application SH-190, ト-レ シ リ コ-Application SH-193, ト-レ シ リ コ-Application SZ-6032, ト-レ シ リ コ-Application SF-8428, ト-レ シ リ コ-Application DC-57, ト-レ シ リ コ-Application DC-190 (above) by the beautiful DOW CORNING organosilicon in east (strain) preparation, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, the surfactant that TSF-4452 trade names such as (above by GE Toshiba organosilicon (strain) preparation) is sold.
Surfactant except that above-mentioned also has: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene-n-octyl phenyl ether, polyoxyethylene-polyoxyethylene aryl ether such as n-nonyl phenyl ether; The nonionic of polyoxyethylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate etc. is a surfactant, or organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) preparation), (methyl) acrylic acid series copolymer Port リ Off ロ-No.57, Port リ Off ロ-No.95 (above by common prosperity society chemistry (strain) preparation) etc.
These surfactants can separately or be use mixing two or more.
With respect to 100 weight portion multipolymers (A), below preferred 1.0 weight portions of the combined amount of surfactant, further below preferred 0.5 weight portion.At this moment, the combined amount of surfactant surpasses 1.0 weight portions, then is easy to generate the uneven tendency of film.
Above-mentioned preserving stabilizer for example has: sulphur, quinones, hydroquinones, polyoxy compound, amine, nitro nitroso compound etc.Example has more specifically: 4-methoxyl phenol, N-nitroso--N-phenylhydroxylamine aluminium etc.
These preserving stabilizers can separately or be use mixing two or more.
With respect to 100 weight portion multipolymers (A), below preferred 3.0 weight portions of the combined amount of preserving stabilizer, further more than preferred 0.5 weight portion.At this moment, the combined amount of preserving stabilizer surpasses 3.0 weight portions, and then sensitivity descends, the pattern form possible deviation.
Above-mentioned thermotolerance reinforcing agent for example has: N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound, have the compound of the epoxy radicals more than 2 etc.
Above-mentioned N-(alkoxy methyl) glycoluril compounds for example has: 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 etc.
In these N-(alkoxy methyl) glycoluril compounds, preferred N, N, N, N-four (methoxy) glycoluril.
Above-mentioned N-(alkoxy methyl) melamine compound for example has: 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-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 etc.
In these N-(alkoxy methyl) melamine compound, preferred N, N, N, N, N, N-six (methoxy) melamine, its commercially available product for example has: ニ カ ラ Star Network N-2702, ニ カ ラ Star Network MW-30M (more than be three and chemistry (strain) prepare) etc.
Above-mentioned compound with two above epoxy radicals for example has: ethylene glycol diglycidylether, diglycol diglycidyl ether, triethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, dipropylene glycol diglycidyl ether, 3 third glycol diglycidyl ethers, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether etc.
Commercially available product with compound of two above epoxy radicals for example has: エ Port ラ イ ト 40E, エ Port ラ イ ト 100E, エ Port ラ イ ト 200E, エ Port ラ イ ト 70P, エ Port ラ イ ト 200P, エ Port ラ イ ト 400P, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 1600, エ Port ラ イ ト 3002, エ Port ラ イ ト 4000 (above is common prosperity society chemistry (strain) preparation) etc.
These thermotolerance reinforcing agents can separately or be use mixing two or more.
Radiation sensitive resin composition
Radiation sensitive resin composition of the present invention can evenly mix by other composition with above-mentioned multipolymer (A), (B) composition and (C) composition and aforesaid any interpolation and prepare.Radiation sensitive resin composition of the present invention is preferably dissolved in the appropriate solvent, uses with solution state.For example can mix with the ratio of regulation, prepare the radiation sensitive resin composition of solution state by other composition with multipolymer (A), (B) composition and (C) composition and interpolation arbitrarily.
In the preparation of radiation sensitive resin composition of the present invention employed solvent can use can uniform dissolution multipolymer (A), (B) composition and (C) composition and other each composition that becomes to grade of mixing arbitrarily, and not with the solvent of each composition reaction.
Described solvent is the same example that is exemplified in the solvent that uses when (A) with the above-mentioned multipolymer of preparation.
In the described solvent, from the dissolubility of each composition, consider, for example can preferably use alcohol, glycol ethers, ethylene glycol alkyl ether acetic acid esters, ester and diglycol with the reactivity of each composition, the easy degree equal angles that forms of filming.Wherein, for example especially preferably use benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol, ethylene glycol monobutyl ether acetic acid ester, diglycol monoethyl ether acetic acid esters, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, Glycol Monomethyl ether, Glycol Monomethyl ether acetic acid esters, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
And,, high boiling solvent can also be used in combination with above-mentioned solvent in order to improve the inner evenness of thickness.The high boiling solvent that can be used in combination for example has: N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, ethylene glycol monophenyl ether acetic acid esters etc.Wherein preferred N-Methyl pyrrolidone, gamma-butyrolacton, N,N-dimethylacetamide.
As the solvent of radiation sensitive resin composition of the present invention, when using in conjunction with high boiling solvent, its use amount is preferably below 50% weight with respect to the solvent total amount, more preferably below 40% weight, further below preferred 30% weight.The use amount of high boiling solvent surpasses this use amount, and the film thickness uniformity of then filming, sensitivity and membrane left rate may reduce.
When preparing radiation sensitive resin composition of the present invention with solution state, composition beyond the solvent shared ratio in solution, promptly, multipolymer (A), (B) composition and (C) ratio of the total amount of composition and other composition of adding arbitrarily can set arbitrarily according to application target or desirable film thickness value etc., for example be 5-50% weight, preferred 10-40% weight, further preferred 15-35% weight.
It is that millipore filter etc. about 0.5 μ m filters that the composition solution of above-mentioned preparation can use the aperture, uses then.
The formation method of sept
Below, describe for the method for using radiation sensitive resin composition of the present invention to form sept of the present invention.
The formation method of sept of the present invention is characterised in that: implement following steps in the following order.
(1) on substrate, form radiation sensitive resin composition of the present invention the step of filming,
(2) to the step of this at least a portion of filming irradiation radioactive ray,
(3) development step and
(4) heating steps.
Below these each steps in sequence are described.
(1) step of filming of formation radiation sensitive resin composition of the present invention on substrate
Form nesa coating on a face of transparency carrier, the composition solution of coating radiation sensitive resin composition of the present invention on this nesa coating forms tunicle by heating (precuring) coated face then.
Employed transparency carrier for example had glass substrate, resin substrate etc. during sept formed, and had more specifically: glass substrates such as soda-lime glass, alkali-free glass; The resin substrate that contains plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide.
The nesa coating that is provided with on a face of transparency carrier has: contain tin oxide (SnO
2) NESA film (registered trademark of U.S. PPG company), contain indium oxide-tin oxide (In
2O
3-SnO
2) ITO film etc.
Coating process to composition solution is not particularly limited, for example can adopt suitable methods such as spraying process, roll coating process, method of spin coating (spin-coating method), slot die rubbing method, knife coating, ink-jet application method, preferred especially spin-coating method, slot die rubbing method.
The condition of precuring is according to the kind of each composition, blending ratio etc. and different, is generally under 70-120 ℃, about 1-15 minute.
(2) to the step of this at least a portion of filming irradiation radioactive ray
Then, at least a portion of formed tunicle exposure radioactive ray.At this moment, when the part of tunicle is exposed, expose via photomask with predetermined pattern.
The radioactive ray that are used to expose can use luminous ray, ultraviolet ray, far ultraviolet etc.Optimal wavelength especially preferably contains the ultraviolet radioactive ray of 365nm at the radioactive ray of 190-450nm scope.
Exposure is by the value of the intensity of the 365nm wavelength of illuminometer (OAI, model 356, OAI Optical Associates Inc. make) mensuration exposure radioactive ray, is preferably 100-10,000J/m
2, more preferably 1,500-3,000J/m
2
(3) development step
Then,, remove unwanted part, form the pattern of regulation by the tunicle after the exposure is developed.
Employed developer solution for example can use in the development: inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Aliphatic primary amine such as ethamine, n-propylamine; Aliphatic secondary amine such as diethylamine, di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyl diethylamide, dimethylethyl amine, triethylamine; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicyclo [5.4.0]-7-undecylene, 1,5-diazabicyclo [4.3.0]-alicyclic tertiary amines such as 5-nonene; Aromatic uncle amines such as pyridine, trimethylpyridine, lutidines, quinoline; Alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; The aqueous solution of alkali compounds such as quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide.
Can add water-miscible organic solvent and/or surfactant uses such as an amount of methyl alcohol, ethanol in the aqueous solution of above-mentioned alkali compounds.
Developing method can be any methods such as many liquid (liquid is contained り) method, infusion process, spray process, and development time carries out 10-180 about second usually at normal temperatures.
After the development, for example carry out the 30-90 flowing water cleaning of second, for example air-dry then with pressurized air or compressed nitrogen, form desirable pattern thus.
(4) heating steps
Then, the gained pattern is for example passed through heating arrangements such as heating plate, baking oven, with for example 100-160 ℃ of set point of temperature, stipulated time for example on heating plate 5-30 minute, in baking oven for heating (solidify the back), the sept that can obtain stipulating in 30-180 minute.
If employed radiation sensitive resin composition did not carry out heat treated under the temperature more than about 180-200 ℃ during sept formed in the past, then the gained sept can not be given full play to performance, but radiation sensitive resin composition of the present invention can make heating-up temperature lower than in the past, the result, can not cause the xanthochromia or the distortion of resin substrate, the friction patience in the time of can producing compression strenght, liquid crystal aligning, with all excellent sept of each performance such as stickiness of transparency carrier.
Embodiment
Below provide synthesis example, embodiment, further specify the present invention, but the present invention is not limited by following examples.
＜molecular weight by the gel permeation chromatography multipolymer 〉
Device: GPC-101 (clear and electrician's (strain) makes)
Post: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are connected use
Mobile phase: the tetrahydrofuran that contains 0.5% weight percent phosphoric acid
The synthesis example of its polymers (A)
Synthesis example 1
In the flask that possesses condenser pipe, stirrer, add 1 weight portion 2,2 '-azo two (2, the 4-methyl pentane nitrile), 4 weight portion dithiobenzoic acid isopropyl benzene esters, 50 weight portion diglycol ethyl-methyl ethers.Then add 20 parts by weight of styrene, 17 weight portion methacrylic acids, 18 weight portion methacrylic acids, three ring ester in the last of the ten Heavenly stems and 45 weight portion glycidyl methacrylate, carry out the nitrogen displacement, begin slow stirring then.Make the temperature of solution rise to 60 ℃, this temperature was kept 24 hours, append 3 weight portions 2 then, 2 '-azo two (2, the 4-methyl pentane nitrile) further stirred 4 hours at 60 ℃, append 200 weight portion diglycol ethyl-methyl ethers, obtain containing the polymer solution of multipolymer (A-1).The weight-average molecular weight through polystyrene conversion of multipolymer (A-1) (Mw) is 11,000, and molecular weight distribution (Mw/Mn) is 1.4, and residual monomer is 2.0% weight.The solid portion concentration of polymer solution is 28.4% weight.
Synthesis example 2
In the flask that possesses condenser pipe, stirrer, add 1 weight portion 2,2 '-azo two (2, the 4-methyl pentane nitrile), 4 weight portion dithiobenzoic acid isopropyl benzene esters, 50 weight portion diglycol ethyl-methyl ethers.Then add 5 parts by weight of styrene, 16 weight portion methacrylic acids, 34 weight portion methacrylic acids, three ring esters in the last of the ten Heavenly stems, 35 weight portion glycidyl methacrylate and 5 weight portion methacrylic acid methyl ethylene oxidic esters, carry out the nitrogen displacement, begin slow stirring then.Make the temperature of solution rise to 60 ℃, this temperature was kept 24 hours, append 3 weight portions 2 then, 2 '-azo two (2, the 4-methyl pentane nitrile) further stirred 4 hours at 60 ℃, append 200 weight portion diglycol ethyl-methyl ethers, obtain containing the polymer solution of multipolymer (A-2).The Mw of multipolymer (A-2) is 12,000, and molecular weight distribution (Mw/Mn) is 1.4, and residual monomer is 2.0% weight.The solid portion concentration of polymer solution is 28.6% weight.
Synthesis example 3
In the synthesis example 1, use S-cyano methyl-S-dodecyl trithiocarbonate to replace dithiobenzoic acid isopropyl benzene ester, in addition obtain the solution of multipolymer (A-3) according to synthesis example 1.The weight-average molecular weight through polystyrene conversion of multipolymer (A-3) (Mw) is 10,000, and molecular weight distribution (Mw/Mn) is 1.2, and residual monomer is 1.5% weight.The solid portion concentration of polymer solution is 28.2% weight.
Synthesis example 4
In the synthesis example 2, use pyrazoles-1-carbodithioic acid phenyl-methyl ester to replace dithiobenzoic acid isopropyl benzene ester, in addition, obtain containing the polymer solution of multipolymer (A-4) according to synthesis example 2.The weight-average molecular weight through polystyrene conversion of multipolymer (A-4) (Mw) is 12,000, and molecular weight distribution (Mw/Mn) is 1.3, and residual monomer is 1.4% weight.The solid portion concentration of polymer solution is 28.5% weight.
Synthesis example 5
In the synthesis example 1, use following dithioesters to replace dithiobenzoic acid isopropyl benzene ester, in addition, obtain containing the polymer solution of multipolymer (A-5) according to synthesis example 1.The weight-average molecular weight through polystyrene conversion of multipolymer (A-5) (Mw) is 12,000, and molecular weight distribution (Mw/Mn) is 1.2, and residual monomer is 1.4% weight.The solid portion concentration of polymer solution is 28.0% weight.
Synthesis example 6
In the synthesis example 2, use following xanthate to replace dithiobenzoic acid isopropyl benzene ester, in addition, obtain containing the polymer solution of multipolymer (A-6) according to synthesis example 2.The weight-average molecular weight through polystyrene conversion of multipolymer (A-6) (Mw) is 11,500, and molecular weight distribution (Mw/Mn) is 1.3, and residual monomer is 1.4% weight.The solid portion concentration of polymer solution is 28.5% weight.
Compare synthesis example 1
In the flask that possesses condenser pipe, stirrer, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 weight portion diglycol methyl ethyl ethers, then add 20 parts by weight of styrene, 17 weight portion methacrylic acids, 18 weight portion methacrylic acids, two cyclopentane base esters and 45 weight portion glycidyl methacrylate, replace with nitrogen, slowly stir then, make the temperature of reaction solution rise to 70 ℃ simultaneously, this temperature is kept carrying out polymerization in 4 hours, obtain containing the polymer solution of multipolymer (a-1) thus.The Mw of multipolymer (a-1) is 13,000, and molecular weight distribution (Mw/Mn) is 2.4, and residual monomer is 7.1% weight.The solid portion concentration of polymer solution is 29.5% weight.
Embodiment 1
(I) preparation of radiation sensitive resin composition
The solution that contains polymkeric substance (A-1) of amount that will be equivalent to 100 weight portions (solid portion) polymkeric substance (A-1) is as (A) composition synthetic in the above-mentioned synthesis example 1,80 weight portions are as dipentaerythritol acrylate (the trade name KAYARAD DPHA of (B) composition, Japan's chemical drug (strain) preparation), 10 weight portions are as 2 of (C) composition, 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 15 weight portion 2-methyl [4-(methyl sulfo-) phenyl]-2-morpholino-1-acetone (trade name イ Le ガ キ ユ ア 907, the preparation of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ company), 10 weight portions are as 4 of the radiation-sensitive sensitizer, 4 '-two (dimethylamino) benzophenone, 5 weight portion 2-mercaptobenzothiazoles and 5 weight portions are as the γ-glycidoxypropyltrime,hoxysilane of gluing auxiliary agent, 0.5 weight portion is as the FTX-218 (trade name of surfactant, (strain) ネ オ ス preparation), 0.5 weight portion mixes as the 4-methoxyl phenol of preserving stabilizer, be dissolved in the Glycol Monomethyl ether acetic acid esters, making solid portion concentration is 30% weight, be the millipore filter filtration of 0.5 μ m then with the aperture, the preparation composition solution.
(II) formation of sept
Use spin coater to be coated with above-mentioned composition solution on alkali-free glass substrate, carry out precuring in 3 minutes then on 90 ℃ heating plate, forming thickness is the tunicle of 6.0 μ m.
Then, via the foursquare photomask that stays film figure with 10 μ m length of sides, expose 10 second 365nm, intensity be 250W/m
2Ultraviolet ray.Then, developed 60 seconds at 25 ℃, then with pure water washing 1 minute by 0.05% weight potassium hydroxide aqueous solution.Then in baking oven, 150 ℃ of back curing of carrying out 120 minutes, form the sept of predetermined pattern.
(III) evaluation of resolution
When in above-mentioned (II), forming pattern, when the pattern that stays can be separated picture, be evaluated as well (zero), can not separate as the time be bad (*).Evaluation result is as shown in table 2.
(IV) evaluation of sensitivity
For above-mentioned (II) gained pattern, the back membrane left rate (thickness after the development * 100/ initial stage thickness) that develops is 90% to be evaluated as well (zero) when above, is lower than at 90% o'clock and is evaluated as bad (*).Evaluation result is as shown in table 2.
(V) evaluation of pattern form
Cross sectional shape by sem observation above-mentioned (II) gained pattern, estimate by any that meets A-D shown in Figure 1, at this moment, if such to A or B, when pattern edge is positive taper or vertical configuration, we can say that then the pattern form of sept is good.If it is and such to C, sensitivity is not enough, membrane left rate is low, sectional dimension is littler than A and B, and cross sectional shape is bottom surface when being the semi-convex lensing on plane, and then the pattern form of sept is bad, in addition shown in D, if cross sectional shape is a back taper, the possibility that pattern peels off during afterwards friction treatment is very big, so the pattern form of sept is bad.Evaluation result is as shown in table 2.
(VI) evaluation of compression strenght
For above-mentioned (II) gained pattern, use the minute-pressure tester (MCTM-200, (strain) Shimadzu Seisakusho Ltd. make) that contracts, be that son is pressed on the plane of 50 μ m by diameter, measure deflection when applying 10mN load for 23 ℃ down measuring temperature.This value is 0.5 when following, can think that compression strenght is good.Evaluation result is as shown in table 2.
(VII) evaluation of friction patience
On the substrate that has formed above-mentioned (II) gained pattern, use liquid crystal orientation film coating printing machine coating of liquid crystalline alignment agent AL3046 (trade name, JSR (strain) make), then 180 ℃ of dryings 1 hour, the alignment agent that forms dry film thickness and be 0.05 μ m is filmed.Then, using the frictiograph of the roller of the cloth with the polyamide system of having twined, is 1cm/ second with roller revolution 500rpm, translational speed, this is filmed carry out friction treatment.At this moment, whether evaluation pattern generating grinds off or peels off.Evaluation result is as shown in table 2.
(VIII) evaluation of stickiness
Need not stay the mask of film figure, in addition implement, form cured film with above-mentioned (II) is same.Then, in the tack experiment of JRSK-5400 (1900) 8.5, estimate by the 8.5.2 cross-hatching.At this moment, residual number of squares is as shown in table 2 in 100 grids.
(IX) evaluation of sublimate
Use spin coater, coating above-mentioned composition solution on the organosilicon substrate, 90 ℃, precuring 2 minutes on heating plate, forming thickness is filming of 3.0 μ m then.The PLA-501F exposure instrument of making by Canon's (strain) (ultrahigh pressure mercury lamp) is filmed to gained and is exposed, and cumulative exposure is 3,000J/m
2, this organosilicon substrate in baking oven, 220 ℃ of heating 1 hour, is obtained cured film.At interval 1cm installs cooling and use naked silicon wafer above the gained cured film, on heating plate, 230 ℃ of processing 1 hour of heating.Do not change cooling and use naked silicon wafer, with 20 of the processing continuously of the silicon substrate that forms above-mentioned cured film in addition, visual then procuratorial work is attached to having or not of sublimate on the naked silicon wafer.When not seeing sublimate, sublimate is evaluated as well.If estimate as shown in table 2.
Embodiment 2-14 and comparative example 1-3
Use each composition conduct (A)-(C) composition and radiation-sensitive sensitizer shown in the table 1, in addition prepare each composition solution similarly to Example 1, estimate.Evaluation result is as shown in table 2.
In the table 1, multipolymer (A-1), multipolymer (A-2) and multipolymer (a-1) each composition in addition are as described below.
(B) composition
B-1: dipentaerythritol acrylate
(C) composition
C-1:2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole
C-2:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole
C-3:2-methyl [4-(methyl sulfo-) phenyl]-2-morpholino-1-acetone
C-4:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1
(radiation-sensitive sensitizer)
D-1:4,4 '-two (dimethylamino) benzophenone
The D-2:2-mercaptobenzothiazoler
D-3: pentaerythrite four (mercaptoacetate)
Table 1
| Multipolymer | The B composition | The C composition | The radiation-sensitive sensitizer | |||||
| Kind | Weight portion | Kind | Weight portion | Kind | Weight portion | Kind | Weight portion | |
| Embodiment 1 | A-1 | 100 | B-1 | 100 | C-1 | 8 | ||
| Embodiment 2 | A-1 | 100 | B-1 | 100 | C-1/C-3 | 5/20 | D-1/D-2/D-3 | 5/5/2.5 |
| Embodiment 3 | A-1 | 100 | B-1 | 100 | C-1/C-4 | 10/15 | ||
| Embodiment 4 | A-1 | 100 | B-1 | 100 | C-1/C-3/C-4 | 5/10/10 | ||
| Embodiment 5 | A-1 | 100 | B-1 | 80 | C-1 | 5 | D-1/D-2/D-3 | 5/5/2.5 |
| Embodiment 6 | A-2 | 100 | B-1 | 80 | C-1/C-3 | 3/25 | ||
| Embodiment 7 | A-2 | 100 | B-1 | 80 | C-1/C-4 | 5/20 | D-1/D-2/D-3 | 5/5/2.5 |
| Embodiment 8 | A-2 | 100 | B-1 | 100 | C-1/C-3/C | 5/10/10 | D-1/D-2/D-3 | 5/5/2.5 |
| Embodiment 9 | A-2 | 100 | B-1 | 100 | C-1/C-2/C | 4/1/20 | D-1/D-2/D-3 | 2006/6/3 |
| Embodiment 10 | A-2 | 100 | B-1 | 100 | C-1 | 7 | D-1/D-2/D-3 | 2006/6/3 |
| Embodiment 11 | A-3 | 100 | B-1 | 100 | C-1 | 8 | ||
| Embodiment 12 | A-4 | 100 | B-1 | 100 | C-1/C-3 | 5/20 | D-1/D-2/D-3 | 5/5/2.5 |
| Embodiment 13 | A-5 | 100 | B-1 | 100 | C-1 | 8 | ||
| Embodiment 14 | A-6 | 100 | B-1 | 100 | C-1/C-3 | 5/20 | D-1/D-2/D-3 | 5/5/2.5 |
| Comparative example 1 | a-1 | 100 | B-1 | 100 | C-1 | 8 | ||
| Comparative example 2 | a-1 | 100 | B-1 | 100 | C-1/C-3 | 5/20 | D-1/D-2/D-3 | 5/5/2.5 |
| Comparative example 3 | a-1 | 100 | B-1 | 100 | C-1/C-3 | 3/25 | ||
Table 2
| Sensitivity | Resolution | Cross sectional shape | Compression test (μ m) | The friction heat-resistant experiment has or not to be peeled off | Stickiness (/ 100) | Sublimate | |
| Embodiment 1 | ○ | ○ | B | 0.41 | Do not have | 100 | Do not have |
| Embodiment 2 | ○ | ○ | B | 0.42 | Do not have | 100 | Do not have |
| Embodiment 3 | ○ | ○ | A | 0.32 | Do not have | 100 | Do not have |
| Embodiment 4 | ○ | ○ | A | 0.32 | Do not have | 100 | Do not have |
| Embodiment 5 | ○ | ○ | B | 0.38 | Do not have | 100 | Do not have |
| Embodiment 6 | ○ | ○ | B | 0.32 | Do not have | 100 | Do not have |
| Embodiment 7 | ○ | ○ | A | 0.25 | Do not have | 100 | Do not have |
| Embodiment 8 | ○ | ○ | A | 0.27 | Do not have | 100 | Do not have |
| Embodiment 9 | ○ | ○ | A | 0.28 | Do not have | 100 | Do not have |
| Embodiment 10 | ○ | ○ | A | 0.28 | Do not have | 100 | Do not have |
| Embodiment 11 | ○ | ○ | B | 0.32 | Do not have | 100 | Do not have |
| Embodiment 12 | ○ | ○ | B | 0.33 | Do not have | 100 | Do not have |
| Embodiment 13 | ○ | ○ | A | 0.29 | Do not have | 100 | Do not have |
| Embodiment 14 | ○ | ○ | A | 0.31 | Do not have | 100 | Do not have |
| Comparative example 1 | × | ○ | C | 0.57 | Have | 80 | Have |
| Comparative example 2 | × | ○ | A | 0.51 | Do not have | 100 | Have |
| Comparative example 3 | × | ○ | A | 0.50 | Do not have | 100 | Have |
Radiation sensitive resin composition of the present invention has high sensitivity, high image resolution, and can form easily pattern form, compression strenght, friction patience, with all excellent sept of each performance such as stickiness of transparency carrier, in addition, when forming sept, heating-up temperature after the development is reduced, can not cause the xanthochromia or the distortion of resin substrate, sublimate is few, and device or panel contamination of heavy are reduced.
Claims
(according to the modification of the 19th of treaty)
1. radiation sensitive resin composition, it is characterized in that: contain (A) multipolymer, this multipolymer have carboxyl and epoxy radicals and by gel permeation chromatography, be below 1.7 through the weight-average molecular weight (Mw) of polystyrene conversion with through the ratio (Mw/Mn) of the number-average molecular weight (Mn) of polystyrene conversion, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization initiator and be used to form sept.
2. the radiation sensitive resin composition of claim 1, wherein multipolymer (A) obtains the polymerism potpourri active free radical polymerization that contains following compound: (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) contain the unsaturated compound of epoxy radicals and (a3) (a1) composition and (a2) unsaturated compound beyond the composition.
3. claim 1 or 2 radiation sensitive resin composition, wherein multipolymer (A) is the multipolymer by using thiocarbonylthio compound to obtain as the active free radical polymerization of controlling agent.
4. (deletion)
5. the formation method of a sept is characterized in that: implement following steps by following order:
(1) on substrate, form step that the radiation sensitive resin composition of claim 1 films,
(2) to the step of this at least a portion of filming irradiation radioactive ray,
(3) development step and
(4) heating steps.
6. sept, this sept forms by the method for claim 5.
Claims (6)
1. radiation sensitive resin composition, it is characterized in that: contain (A) multipolymer, this multipolymer have carboxyl and epoxy radicals and by gel permeation chromatography, be below 1.7 through the weight-average molecular weight (Mw) of polystyrene conversion with through the ratio (Mw/Mn) of the number-average molecular weight (Mn) of polystyrene conversion, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization initiator.
2. the radiation sensitive resin composition of claim 1, wherein multipolymer (A) obtains the polymerism potpourri active free radical polymerization that contains following compound: (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) contain the unsaturated compound of epoxy radicals and (a3) (a1) composition and (a2) unsaturated compound beyond the composition.
3. claim 1 or 2 radiation sensitive resin composition, wherein multipolymer (A) is the multipolymer by using thiocarbonylthio compound to obtain as the active free radical polymerization of controlling agent.
4. the radiation sensitive resin composition of claim 1, this radiation sensitive resin composition is used to form sept.
5. the formation method of a sept is characterized in that: implement following steps by following order:
(1) on substrate, form step that the radiation sensitive resin composition of claim 1 films,
(2) to the step of this at least a portion of filming irradiation radioactive ray,
(3) development step and
(4) heating steps.
6. sept, this sept forms by the method for claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004137257 | 2004-05-06 | ||
| JP137257/2004 | 2004-05-06 |
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| CN1950751A true CN1950751A (en) | 2007-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800139437A Pending CN1950751A (en) | 2004-05-06 | 2005-02-18 | Radiation-sensitive resin composition, spacer, and method of forming the same |
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| Country | Link |
|---|---|
| JP (1) | JP4650638B2 (en) |
| KR (1) | KR101084384B1 (en) |
| CN (1) | CN1950751A (en) |
| TW (1) | TW200604217A (en) |
| WO (1) | WO2005109100A1 (en) |
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| CN102236259A (en) * | 2010-04-28 | 2011-11-09 | Jsr株式会社 | Radiation sensitivity resin composition for display element, interlayer insulation film, protective film and spacer and forming method thereof |
| CN103221887A (en) * | 2010-11-17 | 2013-07-24 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| CN103336390A (en) * | 2013-06-21 | 2013-10-02 | 合肥京东方光电科技有限公司 | Spacer and manufacturing method thereof, substrate and display device |
| TWI493284B (en) * | 2010-05-27 | 2015-07-21 | Jsr Corp | Radiation-sensitive resin composition for forming cured film, method for producing radiation-sensitive resin composition for forming cured film, cured film, method for forming cured film and display element |
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| JP4923496B2 (en) * | 2005-02-18 | 2012-04-25 | Ｊｓｒ株式会社 | Radiation sensitive resin composition for color filter and color filter |
| KR101250733B1 (en) * | 2005-03-15 | 2013-04-03 | 제이에스알 가부시끼가이샤 | Radiation Sensitive Resin Composition, Protrusion and Spacer Made Therefrom, and Liquid Crystal Display Device Comprising Them |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11133600A (en) * | 1997-10-30 | 1999-05-21 | Jsr Corp | Radiation-sensitive resin composition for display panel spacer |
| JP2000081701A (en) * | 1998-09-03 | 2000-03-21 | Jsr Corp | Radiation sensitive resin composition for protective coat of color filter |
| JP4269115B2 (en) * | 1999-05-10 | 2009-05-27 | Ｊｓｒ株式会社 | Radiation sensitive resin composition, interlayer insulating film and spacer |
| JP2001261761A (en) * | 2000-03-22 | 2001-09-26 | Jsr Corp | Radiation-sensitive resin composition and spacer for display panel |
| JP2003041224A (en) * | 2001-07-31 | 2003-02-13 | Kanegafuchi Chem Ind Co Ltd | Adhesive composition |
| JP3734436B2 (en) * | 2001-09-19 | 2006-01-11 | 奇美実業股▲分▼有限公司 | Photosensitive resin composition for liquid crystal display spacers |
| JP3967947B2 (en) * | 2002-03-29 | 2007-08-29 | 富士フイルム株式会社 | Dye-containing negative curable composition, color filter and method for producing the same |
-
2005
- 2005-02-18 CN CNA2005800139437A patent/CN1950751A/en active Pending
- 2005-02-18 KR KR1020067023101A patent/KR101084384B1/en active IP Right Grant
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| CN102236259A (en) * | 2010-04-28 | 2011-11-09 | Jsr株式会社 | Radiation sensitivity resin composition for display element, interlayer insulation film, protective film and spacer and forming method thereof |
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| CN103221887A (en) * | 2010-11-17 | 2013-07-24 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
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| WO2014201754A1 (en) * | 2013-06-21 | 2014-12-24 | 合肥京东方光电科技有限公司 | Spacer manufacturing method, substrate, display apparatus, and electronic product |
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| Publication number | Publication date |
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| TW200604217A (en) | 2006-02-01 |
| KR101084384B1 (en) | 2011-11-18 |
| WO2005109100A1 (en) | 2005-11-17 |
| JP4650638B2 (en) | 2011-03-16 |
| JPWO2005109100A1 (en) | 2008-03-21 |
| KR20070007895A (en) | 2007-01-16 |
| TWI365196B (en) | 2012-06-01 |
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