CN1841195A - X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof, and liquid crystal display element - Google Patents

X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof, and liquid crystal display element Download PDF

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CN1841195A
CN1841195A CNA2006100670155A CN200610067015A CN1841195A CN 1841195 A CN1841195 A CN 1841195A CN A2006100670155 A CNA2006100670155 A CN A2006100670155A CN 200610067015 A CN200610067015 A CN 200610067015A CN 1841195 A CN1841195 A CN 1841195A
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oxetanes
methyl
sulfonium
liquid crystal
dimethyl
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志保浩司
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JSR Corp
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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
    • G03F7/033—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The object of this invention is to provide a radiation-sensitive resin composition which is suitably used for simultaneously forming protrusions and spacers of a vertical alignment liquid crystal display element. The radiation-sensitive resin composition for simultaneously forming the protrusions and the spacers for the vertical alignment liquid crystal display element contains: a copolymer [A] of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (a1), an unsaturated compound having an epoxy group or an oxetanyl group (a2) and an olefinically unsaturated compound other than (a1) and (a2) (a3); and a photo-cationic polymerization initiator [B].

Description

Radiation sensitive resin composition, the projection that forms by said composition and separator and forming method thereof, and liquid crystal display cells
Technical field
Projection and the separator that the vertical alignment-type liquid crystal display device that the present invention relates to a kind of radiation sensitive resin composition that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator (spacer), is formed by said composition uses, the method that comprises the vertical alignment-type liquid crystal display device of this projection and/or separator and form this projection and/or this separator.
Background technology
Liquid crystal display cells is widely used in flat-panel monitor.In recent years, along with the popularization of OA equipment such as personal computer and word processor and LCD TV etc., the requirement of the display quality of the LCD (TFT-LCD) of TFT (thin film transistor (TFT)) mode is just being become more and more stricter.Among TFT-LCD, TN (Twisted Nematic) type LCD is most popular now.This LCD makes by following method: 2 substrates with transparency electrode (below, be called " transparent electrode substrate ".) two outsides dispose the inclined to one side films that rise that direction of orientation differs 90 degree respectively, and in the inboard configuration of two transparent electrode substrates alignment films; Between two alignment films, dispose nematic crystal, the direction of orientation of liquid crystal is reversed to another electrode side from an electrode side with the angle of 90 degree.When nonpolarized light under this state during incident, the rectilinearly polarized light that has passed a polarizing plate passes liquid crystal, its change of polarized direction, so it can pass another polarizing plate, forms bright state.Then, when making liquid crystal molecule upright when all applying voltage to two electrodes, the rectilinearly polarized light that arrives liquid crystal directly passes, and can not pass another polarizing plate, forms dark state.After this, when stopping to apply voltage, just revert to bright state.
Though, because in recent years technical progress, at aspects such as the contrast in front and color reprodubilities, this TN type LCD become with cathode ray tube (CRT) quite or more superior.But TN type LCD still has a big problem to need to solve, and that is exactly that the visual angle is narrow.As the method that addresses this is that, developed MVA (Multi-domain VerticallyAligned) type LCD (vertical alignment-type liquid crystal display).Such as non-patent literature 1 and patent documentation 1 record, this MVA type LCD is not the optically-active pattern of TN type LCD, but will have the LCD of birefringent mode of the alignment films combination of the negative type liquid crystal of negative dielectric constant anisotropy and vertical direction, use the LCD of this birefringent mode; Even under the state that does not apply voltage, also can roughly keep vertical direction in locational liquid crystal aligning direction near alignment films, therefore, excellences such as contrast, visual angle, and can not make milled processed of liquid crystal aligning etc., also be excellent aspect manufacturing process.
In MVA type LCD, can get a plurality of directions of orientation in order to make liquid crystal at a pixel region, as the region limits method can be to make the electrode that shows side for have the electrode of slit in 1 pixel region, and in the same pixel region on the electrode base board of light incident side, on the position different, form with the slit of electrode have the inclined-plane projection (for example, triangular pyramidal, semi-convex lens shape etc.).In addition, in present LCD, generally be to use resin and ceramic equal sphere or bar-shaped separator, gap (cell gap) (cell gap) maintenance of 2 transparent electrode substrates is certain.When fitting 2 transparent electrode substrates, separator can be dispersed on any one substrate, according to the diameter decision cell gap of separator.
In addition, problem such as the cell gap that causes for fear of the separator diameter difference is inhomogeneous in patent documentation 2, also discloses and has used photoresist to form the method for projection and separator, and this method has following advantage: can microfabrication, control shape easily.But in patent documentation 2, specifically do not put down in writing the composition of photoresist, also do not show the projection of formation and the performance of separator.
[non-patent literature 1] military Tian Youguang, liquid crystal, Japanese liquid crystal association, on April 25th, 1999, Vol.3, No.2,117
[patent documentation 1] spy opens flat 11-258605 communique
[patent documentation 2] spy opens the 2001-201750 communique
The desired performance of using in the projection of using as vertical alignment-type liquid crystal display device and the formation of separator of photoresist, can list following some.Just, projection and separator except section shape is wanted suitably, also require to after alignment films form the endurance of the solvent that uses in the operation, the performances such as endurance, the transparency, resolution, residual film ratio that alignment films formed the heat that operation applies are higher.In addition, also require the excellence such as orientation, voltage retention of the vertical alignment-type liquid crystal display device of gained.The applicant has proposed to be used for forming simultaneously the radiation sensitive resin composition of projection and separator, this resin combination comprises that [A] contains the unsaturated compound of epoxy radicals and (a3) multipolymer that forms of the unsaturated compound outside these, [B] unsaturated polymerization compound and [C] radiation-sensitive polymerization initiator by (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2); The projection and the separator that are formed by this resin combination and the liquid crystal display cells (with reference to patent documentation 3) that comprises this projection and separator have also been proposed.But, just developed the projection of vertical alignment-type liquid crystal display device and the radiation sensitive resin composition that is formed with usefulness of separator, develop with TFT-LCD popularize fast and more and more stricter performance requirement adapts, can form the projection with excellent performance and the novel radiation sensitive resin composition of separator and just become the important techniques problem.
[patent documentation 3] spy opens the 2003-29405 communique
Summary of the invention
The present invention proposes according to above problem, this problem is to be provided for forming the radiation sensitive resin composition of employed projection of vertical alignment-type liquid crystal display device and/or separator, more specifically, provide as photoresist, resolution and residual film ratio are excellent and can form pattern form, thermotolerance, solvent resistance, projection and separator that the transparency etc. are excellent, and can obtain orientation, the radiation sensitive resin composition of the vertical alignment-type liquid crystal display device that voltage retention etc. are excellent, and use this radioactive ray resin combination to form the projection of vertical alignment-type liquid crystal display device use and/or the method for separator.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st is to realize that by a kind of radiation sensitive resin composition that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator this radiation sensitive resin composition is characterised in that: comprise
The multipolymer that [A] obtains following (a1)～(a3) copolymerization (below, be called " multipolymer [A]), wherein (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (below, be called " compound (a1) "),
(a2) be unsaturated compound with epoxy radicals or oxetanyl (below, be called " compound (a2) "),
(a3) be above-mentioned (a1) and (a2) the olefines unsaturated compound beyond the composition (below, be called " compound (a3) "); With
[B] light cationic polymerization initiators.
Objects and advantages of the present invention, the 2nd is to realize by the projection that the vertical alignment-type liquid crystal display device that is formed by above-mentioned radiation sensitive resin composition uses.
Objects and advantages of the present invention, the 3rd is to realize by the separator that the vertical alignment-type liquid crystal display device that is formed by above-mentioned radiation sensitive resin composition uses.
The object of the invention and advantage, the 4th is to realize by the vertical alignment-type liquid crystal display device that comprises above-mentioned projection and/or above-mentioned separator.
Objects and advantages of the present invention, the 5th is to realize by the method that forms projection and/or separator, the method is characterized in that to comprise following operation at least:
(1) on substrate, forms the operation that 1 radiation-ray sensitive composition of being put down in writing is filmed;
(2) to the operation of this at least a portion of filming irradiation radioactive ray;
(3) developing procedure;
(4) heating process.
Be used to form the projection of vertical alignment-type liquid crystal display device use of the present invention and/or the radiation sensitive resin composition of separator, can form resolution and residual film ratio excellence, and projection and/or separator that pattern form, thermotolerance, solvent resistance, the transparency etc. are excellent, but also can provide excellent vertical alignment-type liquid crystal display device such as orientation, voltage retention.In addition, the projection that vertical alignment-type liquid crystal display device of the present invention uses and/or the formation method of separator, can microfabrication, and control shape and size (height and bottom size) easily, can stablize and the productivity highland forms excellent fine projection and separator such as pattern form, thermotolerance, solvent resistance, the transparency, but also can provide excellent vertical alignment-type liquid crystal display device such as orientation, voltage retention.
Description of drawings
A-C is a synoptic diagram of representing the section shape of projection and separator respectively among Fig. 1.
Fig. 2 is the synoptic diagram of section shape that expression has the vertical alignment-type liquid crystal display device of projection and separator.
Embodiment
Below, each composition of radiation sensitive resin composition of the present invention is elaborated.
Multipolymer (A)
Multipolymer [A] is by in solvent, in the presence of polymerization initiator, makes compound (a1), compound (a2) and compound (a3) carry out free radical polymerization and synthesizes.
The multipolymer that uses among the present invention [A] preferably contains the formation unit of 5～40 weight % from compound (a1), especially preferably contains 10～35 weight %.This formation unit is difficult to be dissolved in the alkaline aqueous solution less than the multipolymer of 5 weight %, and in addition, the multipolymer that surpasses 40 weight % has the trend that becomes excessive to the dissolubility of alkaline aqueous solution.
As compound (a1), can list for example monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid, dicarboxylic acids class and their acid anhydrides such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, list [(methyl) acryloxyalkyl] the ester class of 2 yuan of mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] esters etc. or above polybasic carboxylic acid, ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) esters of acrylic acid of the polymkeric substance of carboxyl and hydroxyl etc.Wherein, from copolyreaction, to the dissolubility and the acquisition aspect easily of alkaline aqueous solution, preferably use acrylic acid, methacrylic acid, maleic anhydride etc.They can use separately, also can be used in combination.
The multipolymer that uses among the present invention [A] preferably contains the formation unit of 5～60 weight % from compound (a2), especially preferably contains 10～50 weight %.When this constituted the unit less than 5 weight %, the thermotolerance of filming of gained had the trend of reduction, and on the other hand, if surpass 60 weight %, then the storage stability of multipolymer has the trend of reduction.
Can list the unsaturated compound that contains epoxy radicals or contain the unsaturated compound of oxa-cyclobutyl as compound (a2).
As the unsaturated compound that contains epoxy radicals, can list for example glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, acrylic acid 4-hydroxybutyl ester glycidol ether, acrylic acid 3,4-epoxy butyl ester, acrylic acid 6,7-epoxy heptyl ester, acrylic acid 3, acrylic acid epoxy (ring) alkyl esters such as 4-epoxycyclohexyl ester, glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy butyl ester, methacrylic acid 6,7-epoxy heptyl ester, methacrylic acid 3, methacrylic acid epoxy (ring) alkyl esters such as 4-epoxycyclohexyl ester, the α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan 6,7-epoxy heptyl ester, α-Yi Jibingxisuan 3, other alpha-alkyl acrylic acid epoxy (ring) alkyl esters such as 4-epoxycyclohexyl ester; Neighbour-vinyl benzyl glycidol ether ,-diglycidyl ethers such as vinyl benzyl glycidol ether, right-vinyl benzyl glycidol ether etc.
As the unsaturated compound that contains the oxa-cyclobutyl, can list for example 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-3-methyl oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxy methyl)-2,2-two fluoro oxetanes, 3-(methacryloxy methyl)-2,2,4-three fluoro oxetanes, 3-(methacryloxy methyl)-2,2,4, the 4-tetrafluoro is for oxetanes, 3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-3-ethyl oxetanes, 2-ethyl-3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-2-trifluoromethyl oxetanes, 3-(methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxyethyl)-2-phenyl-oxetanes, 2,2-two fluoro-3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-2,2,4-three fluoro oxetanes, 3-(methacryloxyethyl)-2,2,4, the 4-tetrafluoro is for oxetanes
2-(methacryloxy methyl) oxetanes, 2-methyl-2-(methacryloxy methyl) oxetanes, 3-methyl-2-(methacryloxy methyl) oxetanes, 4-methyl-2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-3-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-3-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-4-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl)-3-phenyl oxetanes, 2-(methacryloxy methyl)-4-phenyl oxetanes, 2,3-two fluoro-2-(methacryloxy methyl) oxetanes, 2,4-two fluoro-2-(methacryloxy methyl) oxetanes, 3,3-two fluoro-2-(methacryloxy methyl) oxetanes, 3,4-two fluoro-2-(methacryloxy methyl) oxetanes, 4,4-two fluoro-2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-3,3,4-three fluoro oxetanes, 2-(methacryloxy methyl)-3,4,4-three fluoro oxetanes, 2-(methacryloxy methyl)-3,3,4, the 4-tetrafluoro is for oxetanes
2-(methacryloxyethyl) oxetanes, methacrylic acid 2-(2-(2-methyl oxa-cyclobutyl)) ethyl ester, methacrylic acid 2-(2-(3-methyl oxa-cyclobutyl)) ethyl ester, 2-(methacryloxyethyl)-2-methyl oxetanes, 2-(methacryloxyethyl)-4-methyl oxetanes, 2-(methacryloxyethyl)-2-trifluoromethyl oxetanes, 2-(methacryloxyethyl)-3-trifluoromethyl oxetanes, 2-(methacryloxyethyl)-4-trifluoromethyl oxetanes, 2-(methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 2-(methacryloxyethyl)-3-pentafluoroethyl group oxetanes, 2-(methacryloxyethyl)-4-pentafluoroethyl group oxetanes, 2-(methacryloxyethyl)-2-phenyl oxetanes, 2-(methacryloxyethyl)-3-phenyl oxetanes, 2-(methacryloxyethyl)-4-phenyl oxetanes, 2,3-two fluoro-2-(methacryloxyethyl) oxetanes, 2,4-two fluoro-2-(methacryloxyethyl) oxetanes, 3,3-two fluoro-2-(methacryloxyethyl) oxetanes, 3,4-two fluoro-2-(methacryloxyethyl) oxetanes, 4,4-two fluoro-2-(methacryloxyethyl) oxetanes, 2-(methacryloxyethyl)-3,3,4-three fluoro oxetanes, 2-(methacryloxyethyl)-3,4,4-three fluoro oxetanes, 2-(methacryloxyethyl)-3,3,4, the 4-tetrafluoro is for methyl acrylic esters such as oxetanes;
3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2-two fluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4-three fluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4, the 4-tetrafluoro is for oxetanes, 3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-3-ethyl-oxetanes, 2-ethyl-3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-2-trifluoromethyl oxetanes, 3-(acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloxy ethyl)-2-phenyl oxetanes, 2,2-two fluoro-3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-2,2,4-three fluoro oxetanes, 3-(acryloxy ethyl)-2,2,4, the 4-tetrafluoro is for oxetanes
2-(acryloyl-oxy ylmethyl) oxetanes, 2-methyl-2-(acryloyl-oxy ylmethyl) oxetanes, 3-methyl-2-(acryloyl-oxy ylmethyl) oxetanes, 4-methyl-2-(acryloyl-oxy ylmethyl) oxetanes, 2-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-3-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-3-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-4-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl)-3-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-phenyl oxetanes, 2,3-two fluoro-2-(acryloyl-oxy ylmethyl) oxetanes, 2,4-two fluoro-2-(acryloyl-oxy ylmethyl) oxetanes, 3,3-two fluoro-2-(acryloyl-oxy ylmethyl) oxetanes, 3,4-two fluoro-2-(acryloyl-oxy ylmethyl) oxetanes, 4,4-two fluoro-2-(acryloyl-oxy ylmethyl) oxetanes, 2-(acryloyl-oxy ylmethyl)-3,3,4-three fluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,4,4-three fluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,3,4, the 4-tetrafluoro is for oxetanes
2-(acryloxy ethyl) oxetanes, methacrylic acid 2-(2-(2-methyl oxa-cyclobutyl)) ethyl ester, methacrylic acid 2-(2-(3-methyl oxa-cyclobutyl)) ethyl ester, 2-(acryloxy ethyl)-2-methyl oxetanes, 2-(acryloxy ethyl)-4-methyl oxetanes, 2-(acryloxy ethyl)-2-trifluoromethyl oxetanes, 2-(acryloxy ethyl)-3-trifluoromethyl oxetanes, 2-(acryloxy ethyl)-4-trifluoromethyl oxetanes, 2-(acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 2-(acryloxy ethyl)-3-pentafluoroethyl group oxetanes, 2-(acryloxy ethyl)-4-pentafluoroethyl group oxetanes, 2-(acryloxy ethyl)-2-phenyl oxetanes, 2-(acryloxy ethyl)-3-phenyl oxetanes, 2-(acryloxy ethyl)-4-phenyl oxetanes, 2,3-two fluoro-2-(acryloxy ethyl) oxetanes, 2,4-two fluoro-2-(acryloxy ethyl) oxetanes, 3,3-two fluoro-2-(acryloxy ethyl) oxetanes, 3,4-two fluoro-2-(acryloxy ethyl) oxetanes, 4,4-two fluoro-2-(acryloxy ethyl) oxetanes, 2-(acryloxy ethyl)-3,3,4-three fluoro oxetanes, 2-(acryloxy ethyl)-3,4,4-three fluoro oxetanes, 2-(acryloxy ethyl)-3,3,4, the 4-tetrafluoro is for esters of acrylic acids such as oxetanes.
Wherein, from the processing procedure wide ranges of the photosensitive polymer combination of gained and can improve the projection of gained and the chemical resistance aspect of separator, as the unsaturated compound that contains epoxy radicals, preferred glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, the methacrylic acid 6 of using, 7-epoxy heptyl ester, acrylic acid 4-hydroxyl butyl ester glycidol ether, neighbour-vinyl benzyl glycidol ether ,-vinyl benzyl glycidol ether, right-the vinyl benzyl glycidol ether; As the unsaturated compound that contains the oxa-cyclobutyl, preferably use 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-3-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-methyl oxetanes etc.They can use separately, also can make up the back and use.
The multipolymer that uses among the present invention [A] preferably contains the formation unit of 10～80 weight % from compound (a3), especially preferably contains 20～70 weight %.When this constituted the unit less than 10 weight %, the storage stability of multipolymer [A] had the trend of reduction, and on the other hand, if surpass 80 weight %, then multipolymer [A] is insoluble in alkaline aqueous solution.
Can list alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate as compound (a3), alkyl-acrylates such as methyl acrylate, isopropyl acrylate; 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-base ester is (as title commonly used in this field, be also referred to as methacrylic acid two cyclopentane bases (ペ Application ニ Le) ester), methacrylic acid cyclic alkyl ester classes such as methacrylic acid two cyclopentane oxygen base ethyl esters, methacrylic acid isophorone ester, 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-base ester is (as title commonly used in this field, be also referred to as acrylic acid two cyclopentane base esters), acrylic acid cyclic alkyl ester class such as acrylic acid two cyclopentane oxygen base ethyl esters, acrylic acid isophorone ester, aryl methacrylate such as phenyl methacrylate, benzyl methacrylate class, acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester class, dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate, hydroxy alkyl ester classes such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxypropyl ester;
Two ring [2.2.1] hept-2-ene"s,
5-methyl bicyclic [2.2.1] hept-2-ene",
5-ethyl two ring [2.2.1] hept-2-ene"s,
5-hydroxyl two ring [2.2.1] hept-2-ene"s,
5-carboxyl two ring [2.2.1] hept-2-ene"s,
5-methylol two ring [2.2.1] hept-2-ene"s,
5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s,
5-methoxyl two ring [2.2.1] hept-2-ene"s,
5-ethoxy two ring [2.2.1] hept-2-ene"s,
5,6-dihydroxy two ring [2.2.1] hept-2-ene"s,
5,6-dicarboxyl two ring [2.2.1] hept-2-ene"s,
5,6-two (methylol) two ring [2.2.1] hept-2-ene"s,
5,6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s,
5,6-dimethoxy two ring [2.2.1] hept-2-ene"s,
5,6-diethoxy two ring [2.2.1] hept-2-ene"s,
5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s,
5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s,
5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene",
5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene"s,
5-methylol-5-methyl bicyclic [2.2.1] hept-2-ene",
5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene",
5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene"s,
5,6-dicarboxyl two ring [2.2.1] hept-2-ene" acid anhydrides (carbic anhydride),
5-tert-butoxycarbonyl two ring [2.2.1] hept-2-ene"s,
5-cyclohexyloxy carbonyl two ring [2.2.1] hept-2-ene"s,
5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s,
5,6-two (tert-butoxycarbonyl) two ring [2.2.1] hept-2-ene"s,
5, two ring unsaturated compound classes such as 6-two (cyclohexyloxy carbonyl) two ring [2.2.1] hept-2-ene"s;
Dicarbapentaborane imide derivative classes such as phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleic acid acid imide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide;
Styrene, α-Jia Jibenyixi, between-methyl styrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1, the 3-butadiene, isoprene, 2,3-dimethyl-1, the 3-butadiene, 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 butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-Yi Jibingxisuan 6,7-epoxy heptyl ester, neighbour-vinyl benzyl glycidol ether, between-the vinyl benzyl glycidol ether, right-vinyl benzyl glycidol ether etc.
Wherein, from copolyreaction with to the dissolubility aspect of alkaline aqueous solution, optimization styrene, metering system tert-butyl acrylate, methacrylic acid two cyclopentane base esters, p-methoxystyrene, acrylic acid 2-methyl cyclohexane ester, 1,3-butadiene, glycidyl methacrylate, neighbour-vinyl benzyl glycidol ether ,-vinyl benzyl glycidol ether, right-the vinyl benzyl glycidol ether, phenyl maleimide, cyclohexyl maleimide, two ring [2.2.1] hept-2-ene"s etc.They use the back alone or in combination.
As mentioned above, the multipolymer that uses among the present invention [A] has carboxyl and/or acid anhydride and oxa-cyclobutyl, and alkaline aqueous solution is had suitable dissolubility, and does not use together also and can easily solidify by heating with specific hardening agent.
The radiation sensitive resin composition that contains above-mentioned multipolymer [A] can not produce and develop residually when developing, and can not occur film yet and reduce, and forms filming of predetermined pattern easily.
Solvent as using when synthetic copolymer [A] particularly, can list for example alcohols such as methyl alcohol, ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether; Ethylene glycol such as methylcellosolve acetate, ethyl cellosolve acetate alkyl ether acetate esters; Diglycol classes such as diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether; Propylene-glycol monoalky lether classes such as methyl proxitol, propylene glycol ethylether, propylene glycol propyl ether, propylene glycol butyl ether; Propylene glycol alkyl ether acetic acid ester classes such as methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Propylene glycol alkyl ether propionic acid esters such as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;
Ketones such as MEK, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone; 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, ester classes such as 3-butoxy butyl propionate.
In addition; the polymerization initiator that uses in the manufacturing as multipolymer [A]; can use known radical polymerization initiator; for example can list 2; 2 '-azoisobutyronitrile, 2; 2 '-azo two-(2; the 4-methyl pentane nitrile), 2; 2 '-azo two-(4-methoxyl-2; the 4-methyl pentane nitrile) azo-compound such as; benzoyl peroxide, lauroyl superoxide, t-butylperoxy pivarate, 1, organic peroxide and hydrogen peroxide such as 1 '-two-(tert-butyl hydroperoxide) cyclohexanes.When using superoxide, superoxide and reductive agent can also be used together, as oxidation-reduction type initiating agent as radical polymerization initiator.
In the manufacturing of multipolymer [A], can use the molecular weight regulator of regulating molecular weight.As its concrete example, can list halogenated hydrocarbons such as chloroform, carbon tetrabromide, thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, mercaptoethanol acid, xanthan classes such as sulfuration dimethyl xanthan, curing diisopropyl xanthan, terpinolene, α-Jia Jibenyixierjuwu etc.
The weight-average molecular weight of the polystyrene conversion of the multipolymer that uses among the present invention [A] (below, be called " Mw "), be generally 2 * 10 3～5 * 10 5, be preferably 5 * 10 3～1 * 10 5If Mw is less than 2 * 10 3, the residual film ratio after then developing has the tendency of reduction, if surpass 5 * 10 5, then generation is developed residual.
Light cationic polymerization initiators [B]
As light cationic polymerization initiators [B], can list  salt. salt constitutes by the  kation with from lewis acidic negative ion.
As aforementioned  kation particularly, can list diphenyl iodine , two (p-methylphenyl) iodine , two (right-tert-butyl-phenyl) iodine , two (right-octyl phenyl) iodine , two (right-the octadecyl phenyl) iodine , two (right-octyloxyphenyl) iodine , two (right-octadecane oxygen base phenyl) iodine , phenyl (right-octadecane oxygen base phenyl) iodine , (right-tolyl) (right-isopropyl phenyl) iodine , methyl naphthalene iodide , ethyl naphthalene iodide , triphenylsulfonium, three (right-tolyl) sulfonium, three (right-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (right-tert-butyl-phenyl) sulfonium, three (right-cyano-phenyl) sulfonium, three (right-chlorophenyl) sulfonium, dimethyl naphthyl sulfonium, diethyl naphthyl sulfonium, dimethyl (methoxyl) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxyl group) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoro methoxyl) sulfonium, dimethyl (2-chloro ethoxy) sulfonium, dimethyl (3-bromo propoxyl group) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium, dimethyl (three (trichloromethyl) methyl) sulfonium etc.Preferably two (right-tolyl) iodine , (right-tolyl) (right-isopropyl phenyl) iodine , two (right-tert-butyl-phenyl) iodine , triphenylsulfonium, three (right-tert-butyl-phenyl) sulfonium etc.
From lewis acidic negative ion, can list hexafluorophosphate, hexafluoro aluminate, hexafluoro antimonate, four (pentafluorophenyl group) borate etc. particularly, preferably hexafluoro antimonate, four (pentafluorophenyl group) borate as aforementioned.
Can be with aforementioned  kation with from lewis acidic negative ion combination in any.
Particularly, as [B] light cationic polymerization initiators, can list diphenyl iodine  hexafluorophosphate, two (p-methylphenyl) iodine  hexafluorophosphate, two (right-tert-butyl-phenyl) iodine  hexafluorophosphate, two (right-octyl phenyl) iodine  hexafluorophosphate, two (right-the octadecyl phenyl) iodine  hexafluorophosphate, two (right-octyloxyphenyl) iodine  hexafluorophosphate, two (right-octadecane oxygen base phenyl) iodine  hexafluorophosphate, phenyl (right-octadecane oxygen base phenyl) iodine  hexafluorophosphate, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluorophosphate, methyl naphthalene iodide  hexafluorophosphate, ethyl naphthalene iodide  hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (right-tolyl) sulfonium hexafluorophosphate, three (right-isopropyl phenyl) sulfonium hexafluorophosphate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluorophosphate, three (right-tert-butyl-phenyl) sulfonium hexafluorophosphate, three (right-cyano-phenyl) sulfonium hexafluorophosphate, three (right-chlorophenyl) sulfonium hexafluorophosphate, dimethyl naphthyl sulfonium hexafluorophosphate, diethyl naphthyl sulfonium hexafluorophosphate, dimethyl (methoxyl) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxyl group) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoro methoxyl) sulfonium hexafluorophosphate, dimethyl (2-chloro ethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromo propoxyl group) sulfonium hexafluorophosphate, dimethyl (4-cyano group butoxy) sulfonium hexafluorophosphate, dimethyl (8-nitro octyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluorophosphate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluorophosphate;
Diphenyl iodine  hexafluoro aluminate, two (p-methylphenyl) iodine  hexafluoro aluminate, two (right-tert-butyl-phenyl) iodine  hexafluoro aluminate, two (right-octyl phenyl) iodine  hexafluoro aluminate, two (right-the octadecyl phenyl) iodine  hexafluoro aluminate, two (right-octyloxyphenyl) iodine  hexafluoro aluminate, two (right-octadecane oxygen base phenyl) iodine  hexafluoro aluminate, phenyl (right-octadecane oxygen base phenyl) iodine  hexafluoro aluminate, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluoro aluminate, methyl naphthalene iodide  hexafluoro aluminate, ethyl naphthalene iodide  hexafluoro aluminate, triphenylsulfonium hexafluoro aluminate, three (right-tolyl) sulfonium hexafluoro aluminate, three (right-isopropyl phenyl) sulfonium hexafluoro aluminate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro aluminate, three (right-tert-butyl-phenyl) sulfonium hexafluoro aluminate, three (right-cyano-phenyl) sulfonium hexafluoro aluminate, three (right-chlorophenyl) sulfonium hexafluoro aluminate, dimethyl naphthyl sulfonium hexafluoro aluminate, diethyl naphthyl sulfonium hexafluoro aluminate, dimethyl (methoxyl) sulfonium hexafluoro aluminate, dimethyl (ethoxy) sulfonium hexafluoro aluminate, dimethyl (propoxyl group) sulfonium hexafluoro aluminate, dimethyl (butoxy) sulfonium hexafluoro aluminate, dimethyl (octyloxy) sulfonium hexafluoro aluminate, dimethyl (octadecane oxygen base) sulfonium hexafluoro aluminate, dimethyl (isopropoxy) sulfonium hexafluoro aluminate, dimethyl (tert-butoxy) sulfonium hexafluoro aluminate, dimethyl (cyclopentyloxy) sulfonium hexafluoro aluminate, dimethyl (cyclohexyloxy) sulfonium hexafluoro aluminate, dimethyl (fluoro methoxyl) sulfonium hexafluoro aluminate, dimethyl (2-chloro ethoxy) sulfonium hexafluoro aluminate, dimethyl (3-bromo propoxyl group) sulfonium hexafluoro aluminate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro aluminate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro aluminate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro aluminate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro aluminate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro aluminate;
Diphenyl iodine  hexafluoro antimonate, two (p-methylphenyl) iodine  hexafluoro antimonate, two (right-tert-butyl-phenyl) iodine  hexafluoro antimonate, two (right-octyl phenyl) iodine  hexafluoro antimonate, two (right-the octadecyl phenyl) iodine  hexafluoro antimonate, two (right-octyloxyphenyl) iodine  hexafluoro antimonate, two (right-octadecane oxygen base phenyl) iodine  hexafluoro antimonate, phenyl (right-octadecane oxygen base phenyl) iodine  hexafluoro antimonate, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluoro antimonate, methyl naphthalene iodide  hexafluoro antimonate, ethyl naphthalene iodide  hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (right-tolyl) sulfonium hexafluoro antimonate, three (right-isopropyl phenyl) sulfonium hexafluoro antimonate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro antimonate, three (right-tert-butyl-phenyl) sulfonium hexafluoro antimonate, three (right-cyano-phenyl) sulfonium hexafluoro antimonate, three (right-chlorophenyl) sulfonium hexafluoro antimonate, dimethyl naphthyl sulfonium hexafluoro antimonate, diethyl naphthyl sulfonium hexafluoro antimonate, dimethyl (methoxyl) sulfonium hexafluoro antimonate, dimethyl (ethoxy) sulfonium hexafluoro antimonate, dimethyl (propoxyl group) sulfonium hexafluoro antimonate, dimethyl (butoxy) sulfonium hexafluoro antimonate, dimethyl (octyloxy) sulfonium hexafluoro antimonate, dimethyl (octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (isopropoxy) sulfonium hexafluoro antimonate, dimethyl (tert-butoxy) sulfonium hexafluoro antimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro antimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoro antimonate, dimethyl (fluoro methoxyl) sulfonium hexafluoro antimonate, dimethyl (2-chloro ethoxy) sulfonium hexafluoro antimonate, dimethyl (3-bromo propoxyl group) sulfonium hexafluoro antimonate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro antimonate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro antimonate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro antimonate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro antimonate;
Diphenyl iodine  four (pentafluorophenyl group) borate, two (p-methylphenyl) iodine  four (pentafluorophenyl group) borate, two (right-tert-butyl-phenyl) iodine  four (pentafluorophenyl group) borates, two (right-octyl phenyl) iodine  four (pentafluorophenyl group) borates, two (right-the octadecyl phenyl) iodine  four (pentafluorophenyl group) borate, two (right-octyloxyphenyl) iodine  four (pentafluorophenyl group) borates, two (right-octadecane oxygen base phenyl) iodine  four (pentafluorophenyl group) borate, phenyl (right-octadecane oxygen base phenyl) iodine  four (pentafluorophenyl group) borate, (right-tolyl) (right-isopropyl phenyl) iodine  four (pentafluorophenyl group) borate, methyl naphthalene iodide  four (pentafluorophenyl group) borate, ethyl naphthalene iodide  four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (right-tolyl) sulfonium four (pentafluorophenyl group) borates, three (right-isopropyl phenyl) sulfonium four (pentafluorophenyl group) borates, three (2, the 6-3,5-dimethylphenyl) sulfonium four (pentafluorophenyl group) borate, three (right-tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borates, three (right-cyano-phenyl) sulfonium four (pentafluorophenyl group) borates, three (right-chlorophenyl) sulfonium four (pentafluorophenyl group) borates, dimethyl naphthyl sulfonium four (pentafluorophenyl group) borate, diethyl naphthyl sulfonium four (pentafluorophenyl group) borate, dimethyl (methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (ethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (tert-butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclopentyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclohexyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (fluoro methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-chloro ethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (3-bromo propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (4-cyano group butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (8-nitro octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-hydroxyl isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (three (trichloromethyl) methyl) sulfonium four (pentafluorophenyl group) borate etc.
Two (right-tolyl) iodine  hexafluorophosphate preferably, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluorophosphate, two (right-tert-butyl-phenyl) iodine  hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (right-tert-butyl-phenyl) sulfonium hexafluorophosphate, two (right-tolyl) iodine  hexafluoro aluminate, (right-tolyl) (p-isopropyl phenyl) iodine  hexafluoro aluminate, two (right-tert-butyl-phenyl) iodine  hexafluoro aluminate, triphenylsulfonium hexafluoro aluminate, three (right-tert-butyl-phenyl) sulfonium hexafluoro aluminate, two (right-tolyl) iodine  hexafluoro antimonate, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluoro antimonate, two (right-tert-butyl-phenyl) iodine  hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (right-tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (right-tolyl) iodine  four (pentafluorophenyl group) borates, (right-tolyl) (right-isopropyl phenyl) iodine  four (pentafluorophenyl group) borate, two (right-tert-butyl-phenyl) iodine  four (pentafluorophenyl group) borates, triphenylsulfonium four (pentafluorophenyl group) borate, three (right-tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borates etc.
Two (right-tolyl) iodine  hexafluoro antimonate more preferably, (right-tolyl) (right-isopropyl phenyl) iodine  hexafluoro antimonate, two (right-tert-butyl-phenyl) iodine  hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (right-tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (right-tolyl) iodine  four (pentafluorophenyl group) borates, (right-tolyl) (right-isopropyl phenyl) iodine  four (pentafluorophenyl group) borate, two (right-tert-butyl-phenyl) iodine  four (pentafluorophenyl group) borates, triphenylsulfonium four (pentafluorophenyl group) borate, three (right-tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borates etc.
With respect to 100 weight portion multipolymers [A], the usage ratio of [B] composition is 0.01～15 weight portion, is preferably 0.1～10 weight portion.In aforementioned benchmark, if this consumption is 0.01～15 weight portion, just can improve the curing rate of exposed portion, the film of pattern reduces when suppressing to develop, and improves residual film ratio, so be preferred.
Thioxanthones compounds [C]
As [C] thioxanthones compounds, can list for example thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,3-diethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro-thioxanthones, 1-chloro-4-propoxyl group thioxanthones, 2-cyclohexyl thioxanthones, 4-cyclohexyl thioxanthones etc.
With respect to 100 weight portion multipolymers [A], the usage ratio of [C] composition is 15 weight portions or following normally, are preferably 0.01～15 weight portion, more preferably 0.1～10 weight portion.When the content of [C] composition is 0.01～15 weight portion, can improve the curing rate when solidifying to light cationic polymerization initiators enhanced sensitivity, the resolution when suppressing to solidify reduces, and then improves the solvent resistance of cured film, so be preferred.
Other composition
Radiation sensitive resin composition of the present invention contains above-mentioned multipolymer [A] and [B] composition, and perhaps [C] composition is a neccessary composition, can also contain [D] crosslinking chemical, [E] polymerizable monomer, [F] surfactant or [G] bonding agent as required.
Above-mentioned [D] crosslinking chemical is at the composition as formation cross-linked structure between the specific alkaline bleach liquor soluble molecular resin of [A] composition.As this crosslinking chemical can use urea and formaldehyde condensation product (below, be called " urea-formaldehyde condensation products "), the condensation product of melamine and formaldehyde (below, be called " condensation product of carbamide "), the hydroxymethyl urea alkyl ether that obtains by these condensation products and alcohols and melamine methylol alkyl ether etc.
As the object lesson of aforementioned urea-formaldehyde condensation products, can list monomethylol urea, dihydroxymethyl urea etc.
As the object lesson of aforementioned carbamide condensation product, can list hexamethylolmelamine, can use the product of melamine and the condensation of formaldehyde part in addition.
Part or all of methylol in aforementioned hydroxymethyl urea alkyl ether urea-formaldehyde condensation products and alcohol reaction obtain, and its concrete example can list monomethylol urea methyl ether, dihydroxymethyl urea methyl ether etc.
The reaction of alcohols such as part or all of the methylol of aforementioned melamine methylol alkyl ether carbamide condensation product and methyl alcohol, normal butyl alcohol obtains, the compound that its concrete example can list hexamethylolmelamine hexamethyl ether, hexamethylolmelamine six n-butyl ether, have the structure that the hydrogen atom of the amino of melamine replaces with methylol and methoxy has the compound of the structure that the hydrogen atom of the amino of melamine replaces with butoxymethyl and methoxy etc.
Wherein, the preferred melamine methylol alkyl ether that uses can list " サ イ メ Le 300 ", " サ イ メ Le 370 " that Mitsui サ イ テ Star Network Co., Ltd. makes, " サ イ メ Le 232 ", " マ イ コ one ト 505 " etc. as the commercially available product of this melamine methylol alkyl ether.
With respect to 100 weight portions [A] composition, the usage ratio of [D] crosslinking chemical is preferably 50 weight portions or following, more preferably 30 weight portions or following.
When this ratio surpassed 50 weight portions, in development treatment, the thickness that does not shine the radioactive ray part of filming significantly reduced, and the transparency of filming of gained reduces.
As [E] polymerizable monomer, for example can use the polymerizable monomer that is subjected to heat energy free radical polymerization, the polymerizable monomer of energy cationic polymerization etc.
Polymerizable monomer as energy free radical polymerization, can list the compound that for example has the polymerism carbon-to-carbon unsaturated bond, can be the simple function polymerizable monomer, also can be 2 officials can polymerizable monomer, 3 officials can or polyfunctional polymerizable monomer such as more polyfunctional polymerizable monomer.
As the polymerizable monomer of simple function, can list for example nonyl phenyl carbitol acrylate, nonyl phenyl carbitol methacrylate, acrylic acid 2-hydroxyl-3-phenoxy propyl ester, methacrylic acid 2-hydroxyl-3-phenoxy propyl ester, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, N-vinyl pyrrolidone etc.
Polymerizable monomer as 2 officials energy, for example can list 1,6-hexanediyl ester, 1, two (acryloxy ethyl) ether of 6-hexanediol dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bisphenol-A, 3-methyl pentanediol diacrylate, 3-methyl pentanediol dimethylacrylate etc.
As above-mentioned 3 officials can or above polymerizable monomer, can enumerate for example trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, pentaerythrite five acrylate, pentaerythrite pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate etc.In aforementioned polymerizable monomer, preferably use 2 officials can or 3 officials can or above polymerizable monomer.Particularly, be preferably tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc., more preferably dipentaerythritol acrylate.In addition, also can with 2 officials can or 3 officials can or above polymerizable monomer and the polymerizable monomer of simple function use together.
As polymerizable monomer that can cationic polymerization, can list for example have vinyl ether group, the polymerizable monomer of cationically polymerizable functional groups such as propenyl ether, epoxy radicals, oxa-cyclobutyl.Particularly, as the compound that contains vinyl ether group, can list for example triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxy butyl vinyl ether, dodecyl vinyl etc.; As the compound that contains the propenyl ether, can list 4-(1-propenyloxy group methyl)-1,3-dioxolanes-2-ketone etc.; As the compound that contains epoxy radicals, can list bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, cresols phenolic resin varnish type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, heterocyclic-type epoxy resin; As the compound that contains the oxa-cyclobutyl, can list two { 3-(3-ethyl oxa-cyclobutyl) methyl } ether, 1,4-two { 3-(3-ethyl oxa-cyclobutyl) methoxyl } benzene, 1,4-two { 3-(3-ethyl oxa-cyclobutyl) methoxyl } toluene, 1,4-two { 3-(3-ethyl oxa-cyclobutyl) methoxyl } cyclohexane, 1,4-two { 3-(3-ethyl oxa-cyclobutyl) methoxyl } methylcyclohexane, 3-(3-ethyl oxa-cyclobutyl) methylates novolac resin etc.
When using aforementioned polymerizable monomer, can distinguish separately and use, also can multiple use together.With respect to 100 weight portion multipolymers [A], the addition of [E] polymerizable monomer in the radiation sensitive resin composition of the present invention is preferably 30 weight portions or following.
Can use above-mentioned [F] surfactant with further raising coating in the radiation sensitive resin composition of the present invention.[F] used herein surfactant can use fluorine surfactant, silicone based surfactant and nonionic surfactant.
As the object lesson of fluorine surfactant, can enumerate 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro butyl) ether, six ethylene glycol (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, the perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3,3-hexafluoro decane, and fluoro-alkyl benzene sulfonic acid sodium salt class, fluoro-alkyl oxygen ethene ethers, iodate fluoro-alkyl ammonium class, the fluoro-alkyl polyethenoxy ether class, perfluoroalkyl poly oxyethanol class, perfluoroalkyl alkoxide class, fluoroalkyl ester class etc.In addition, as their commercially available product, can list BM-1000, BM-1100 (above BM Chemie society system), 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 (more than, big Japanese ink chemical industry (strain) system), Off ロ ラ one De FC-170C, FC-171, FC-430, FC-431 (more than, Sumitomo ス リ one エ system (strain) system), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (more than, Asahi Glass (strain) system), エ Off ト Star プ EF301, エ Off ト Star プ EF 303, エ Off ト Star プ EF 352 (more than, new autumn fields changes into (strain) system), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (eastern レ シ リ コ one Application (strain) system) etc.
In addition, as the silicone surfactant, can enumerate for example with ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application FS-1265-300 (above eastern 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, trade name product solds such as TSF-4452 (more than, GE Toshiba シ リ コ one Application (strain) system).
As above-mentioned nonionic surfactant, can use for example polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl acyl group ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene nonylplenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate etc., and (methyl) acrylic copolymer Port リ Off ロ one No.57,95 (common prosperity society chemistry (strain) systems) etc.
These surfactants can separately or mix 2 kinds or above use.
With respect to 100 weight portion multipolymers [A], surfactant [F] preferably uses 5 weight portions or following, more preferably 2 weight portions or following.At this moment, surfactant [F] if consumption surpass 5 weight portions, on substrate, form when filming, filming, it is coarse that film takes place easily.
In addition, in order further to improve the cohesive with substrate, can be in radiation sensitive resin composition of the present invention hybrid bonding auxiliary agent [G].
As this bonding agent [G], preferably use the functional silanes coupling agent, for example can list have carboxyl, methacryl, isocyanate group, the substituent silane coupling agent of epoxy radicals isoreactivity.Particularly, can list trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.With respect to 100 weight portion multipolymers [A], the combined amount of this bonding agent [G] is preferably 20 weight portions or following, more preferably 10 weight portions or following.When the amount of bonding agent surpasses 20 weight portions, in developing procedure, be easy to generate the development image retention.
Radiation sensitive resin composition
Radiation sensitive resin composition of the present invention can prepare by above-mentioned multipolymer [A], [B] composition and as above any other composition that adds are evenly mixed.Usually, radioactive ray resin combination of the present invention is to be dissolved in the appropriate solvent, with the state use of solution.For example, other composition with multipolymer [A], [B] composition and interpolation arbitrarily mixes the radiation sensitive resin composition of preparation solution state with institute's certainty ratio.
As the solvent that uses in the radiation sensitive resin composition of the present invention preparation, can use the various compositions of other composition that can dissolve multipolymer [A], [B] composition equably and add arbitrarily, and not with the solvent of each composition reaction.
Can enumerate the identical solvent of illustrated solvent when making above-mentioned multipolymer [A] as this solvent.
In these solvents,, preferably use glycol ethers, ethylene glycol alkyl ether acetate esters, ester class and diglycol class from the dissolving energy of each composition, with the reactive of each composition with the viewpoint of the easiness that forms of filming.Wherein, especially preferably use diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
When the radiation sensitive resin composition of the present invention of preparation solution state, composition beyond the solvent in the solution (just, the total amount of multipolymer [A], [B] composition and any other composition that adds) ratio, can set arbitrarily according to application target and desirable film thickness value etc., be generally 5～50 weight %, be preferably 10～40 weight %, 15～35 weight % more preferably.
Zhi Bei composition solution uses with filtration backs such as the millipore filters about the 0.2 μ m of aperture like this.
The formation of projection and/or separator
Then, to form with radiation sensitive resin composition of the present invention projection of the present invention and or the method for separator describe.The formation method of projection of the present invention and/or separator comprises following operation at least.
(1) on substrate, forms the operation that radiation sensitive resin composition of the present invention is filmed.
(2) operation of irradiation radioactive ray on this at least a portion of filming.
(3) developing procedure.
(4) heating process.
(1) on substrate, forms the operation that radiation sensitive resin composition of the present invention is filmed
In above-mentioned (1) operation, composition solution of the present invention is applied to substrate surface, prebake conditions is removed and is desolvated, and forms radiation sensitive resin composition and films.
As the kind of the substrate that uses among the present invention, the substrate that can list glass substrate, silicon circular wafer and form various metals on their surfaces.
As forming the method that photosensitive polymer combination of the present invention is filmed, for example can adopt (1) rubbing method, (2) dry film method.
As the coating process of composition solution, for example can adopt suitable method such as spray-on process, roll coating process, method of spin coating (spin-coating method), slot coated method, scraper rubbing method, ink-jet application method, preferred especially method of spin coating, slot coated method.
In addition, when (2) the dry film method of employing forms filming of photosensitive polymer combination of the present invention, this dry film is at substrate film, is preferably on the flexual substrate film, (below, be called " photonasty dry film ") that the photosensitive layer that lamination is formed by photosensitive polymer combination of the present invention forms.
The dry film of above-mentioned photonasty is after being coated with photosensitive polymer combination of the present invention on the substrate film, being preferably liquid composition, drying, and the laminated photosensitive layer forms.Substrate film as the dry film of photonasty for example can use film of synthetic resin such as polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate, Polyvinylchloride.That the thickness of substrate film is suitable is 15～125 μ m.The thickness of the photosensitive layer of gained is preferably about 1～30 μ m.
In addition, the dry film of photonasty can be preserved by further lamination diaphragm on this photosensitive layer when not using.This diaphragm is not peeled off when using, and can easily peel off in use, so suitable release property must be arranged.As the diaphragm that satisfies this condition, for example can list on the surface of synthetic resin such as PET film, polypropylene film, polyethylene film, polyvinyl chloride film, apply or film that the silicone based remover of sintering forms.The thickness of diaphragm is generally about 25 μ m and gets final product.The condition of prebake conditions is according to the kind of each composition, usage ratio etc. and different.For example, can be to carry out under 60～110 ℃ about 30 second～15 minute.
(2) to the operation of this at least a portion of filming irradiation radioactive ray
In above-mentioned (2) operation, by having the mask of predetermined pattern, behind the irradiation radioactive ray, use developer solution to carry out development treatment and remove the radiation exposure part, form film on Butut.Radioactive ray as use this moment can list for example ultraviolet ray, far ultraviolet, X ray, charged particle beam etc.
As above-mentioned ultraviolet ray, can list for example g line (wavelength 436nm), i line (wavelength 365nm) etc.As far ultraviolet, can list for example KrF excimer laser etc.As X ray, can list for example synchrotron radioactive ray etc.As charged particle beam, can list for example electron beam etc.
Wherein, preferred ultraviolet ray is preferably the radioactive ray that contain g line and/or i line especially.
Pattern mask and the exposing operation used during as exposure can be: (1) uses a kind of photomask of two patterns with jut and separator part, the method of the single exposure (position that the part of mask is more little, can not ignore the influence of the light that sees through more, melt flows during with baking is corresponding, forms difference in height); (2) use the photomask that has only jut and 2 kinds of photomasks that have only separator, the method for carrying out 2 exposures.In addition, the pattern mask that uses in the method as (1), the mask that also can use jut and separator partly to have different transmitances.But, in the present invention, according to circumstances, also can on substrate, only form a kind of in projection and the separator, in this case, can adopt (3) to have only any of the photomask of jut and the photomask that has only the separator part, carry out the method for single exposure.In addition, in this case, projection that must be residual in vertical alignment-type liquid crystal display device or separator form by existing known method.
(3) developing procedure
As the developer solution that uses in the development treatment, can use NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia, ethamine, n-propylamine, diethylamine, DEAE diethylaminoethanol, di-n-propyl amine, triethylamine, methyl diethylamide, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrroles, piperidines, 1,8-diazabicyclo [5,4,0]-7-undecylene, 1,5-diazabicyclo [4,3,0]-aqueous solution of bases such as 5-nonane.In addition, in above-mentioned alkaline aqueous solution, can suitably add water-miscible organic solvent and surfactant formation aqueous solution such as methyl alcohol, ethanol, will form aqueous solution, the various organic solvents that perhaps dissolve composition of the present invention use as developer solution.In addition, as developing method, can be contain liquid method, infusion process, shake infusion process, towards suitable methods such as pouring methods.The development time of this moment is generally about 30～180 seconds according to the composition of composition and different.
(4) heating process
Behind (3) developing procedure that as above carries out, preferably the film to Butut carries out drenching processing based on dashing of flowing water washing, again preferably by comprehensive irradiation radioactive ray (post-exposure) such as high-pressure mercury-vapor lamps, to in this film residual 1, after the 2-quinone di-azido compound carries out resolution process, by heating arrangements such as hot plate, baking ovens this film is carried out heat treated (back baking processing), this film is cured processing.Exposure in the above-mentioned post-exposure operation is preferably 2,000～5,000J/m 2About.In addition, the firing temperature that this solidify to be handled for example is 120～250 ℃, and when for example carrying out heat treated on hot plate, be 5～30 minutes heat time heating time according to the kind of well heater and different, when carrying out heat treated in baking oven, is 30-90 minute.At this moment, also can use and carry out 2 times or the substep baking of above heating process etc.
So, can form and the projection of target and/or the film of the corresponding pattern-like of separator at substrate surface.
The height of the projection that forms like this is 0.1～3.0 μ m normally, is preferably 0.5～2.0 μ m, is preferably 1.0～1.5 μ m especially; And the height of separator 1～10 μ m normally, be preferably 2～8 μ m, be preferably 3～5 μ m especially.
According to the projection of such vertical alignment-type liquid crystal display device use of the present invention and/or the formation method of separator, can microfabrication, and control shape and size (height and bottom size) easily, can stablize and the productivity highland forms excellent fine projection and separator such as pattern form, thermotolerance, solvent resistance, the transparency, but also can provide excellent vertical alignment-type liquid crystal display device such as orientation, voltage retention.
[embodiment]
Below, show synthesis example and embodiment, be described more specifically the present invention, but the present invention is not limited to these embodiment.
The synthesis example of multipolymer [A]
Synthesis example 1
In the flask that possesses cooling tube, stirrer, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 weight portion diglycol methyl ethyl ethers, add 18 weight portion methacrylic acids, 40 weight portion glycidyl methacrylate, 5 parts by weight of styrene, 32 weight portion methacrylic acids, three ring [5.2.1.0 again 2.6] decane-8-base, after the nitrogen displacement, adding 5 weight portion 1,3-butadienes, the limit is slowly stirred on the limit makes solution temperature rise to 70 ℃, remains on the polymerization in 5 hours of this temperature, obtains the solution of multipolymer [A-1].
The solid component concentration of this solution is 33.0 weight %, and the Mw of multipolymer [A-1] is 11,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 1.8.In addition, weight-average molecular weight and number-average molecular weight are to use the GPC (mean molecular weight of the polystyrene conversion that gel permeation chromatography (eastern ソ one (strain) makes HLC-8020) is measured.
Synthesis example 2
In the flask that possesses cooling tube, stirrer, add 7 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 220 weight portion propylene glycol monomethyl ether.Add 20 parts by weight of styrene, 25 weight portion methacrylic acids, 20 weight portion phenyl maleimides, 35 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, 1.5 parts of α-Jia Jibenyixierjuwus again, limit nitrogen displacement, the limit begins slow stirring.Make solution temperature rise to 70 ℃,, obtain containing the polymer solution of multipolymer [A-2] this temperature heating 5 hours.The solid component concentration of the polymer solution of gained is 31.0%, and the weight-average molecular weight of polymkeric substance is 21,000, and molecular weight distribution is 2.1.
Synthesis example 3
In the flask that possesses cooling tube, stirrer, add 7 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 220 weight portion propylene glycol monomethyl ether.Add 28 parts by weight of styrene, 18 weight portion methacrylic acids, 54 parts of 3-(methacryloxy methyl)-3-ethyl oxetanes again, the displacement of limit nitrogen, the limit begins slow stirring.Make solution temperature rise to 70 ℃,, obtain containing the polymer solution of multipolymer [A-3] this temperature heating 5 hours.The solid component concentration of the polymer solution of gained is 31.2%, and the weight-average molecular weight of polymkeric substance is 23,000, and molecular weight distribution is 2.6.
Embodiment 1
[preparation of radiation sensitive resin composition]
The solution that contains polymkeric substance [A-1] that will be equivalent to synthetic [A] composition of the above-mentioned synthesis example of the conduct of amount of 100 parts by weight polymer [A-1] (solid constituent) 1, mix with two (right-tolyl) the iodine  hexafluoro antimonates (B-1) of 3 weight portions as composition [B], be dissolved in the diglycol ethyl-methyl ether, after making solid component concentration be 30 weight %, with bore is the membrane filter filtration of 0.2 μ m, preparation radiation sensitive resin composition solution (S-1).
Embodiment 2～4
Except in embodiment 1, beyond [A] composition of the kind that use table 1 is put down in writing, amount, [B] composition and [C] composition, carry out processing similarly to Example 1, the solution (S-2)～(S-4) of preparation radiation sensitive resin composition.
In addition, the abbreviation of the composition in the table 1 is expressed as follows compound.
(B-1): two (right-tolyl) iodine  hexafluoro antimonate
(B-2): (right-tolyl) (right-isopropyl phenyl) iodine  four (pentafluorophenyl group) borate [Rhodorsil Photoinitiator 2074 (ロ one デ イ ア society system)]
(C-1): 2,4-dimethyl thioxanthones
[table 1]
The combination name Multipolymer [A] [B] composition [C] composition
Kind Amount (weight portion) Kind Amount (weight portion) Kind Amount (weight portion)
Embodiment 1 (S-1) [A-1] 100 [B-1] 3
Embodiment 2 (S-2) [A-2] 100 [B-2] 3
Embodiment 3 (S-3) [A-3] 100 [B-1] 2.5
Embodiment 4 (S-4) [A-1] 100 [B-1] 3 [C-1] 2
Use the as above radiation sensitive resin composition of preparation, following formation projection and separator are estimated various character.
[formation of projection and separator]
After being coated on above-mentioned composition on the silicon substrate with spinner, prebake conditions formed filming of thickness 4.0 μ m in 2 minutes on hot plate under 90 ℃.Afterwards, by having the wide pattern of the residue 5 μ m that are equivalent to jut and being equivalent to the photomask of pattern of point of the residue 30 μ m of separator part, by the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) of キ ヤ ノ Application (strain) system, change the time shutter, expose.Afterwards, by 25 ℃ developer solution kind, solution level, developing method of record in the table, after carrying out developing in 100 seconds, with pure water washing 1 minute, drying formed pattern on circular wafer.Mensuration is used to form the wide pattern of the residue 5 μ m that are equivalent to jut and is equivalent to the needed exposure of pattern of point of the residue 30 μ m of separator part.Should be worth, in table, represent as sensitivity.This value is at 3500J/m 2Or when following, it is good to be referred to as sensitivity.
[evaluation of the section shape of projection]
When giving a definition, observing the section shape of the projection that form by scanning electron microscope at section shape A, the B of projection or C, is " well " with the situation of A or B, is " bad " with the situation of C.The A of the section shape of projection, B and C diagram ground illustration in Fig. 1.
A: bottom size is greater than the situation of 5 μ m smaller or equal to 7 μ m,
B: bottom size is greater than the situation of 7 μ m,
C: irrelevant with bottom size, be the situation of platform shape shape.
[evaluation of the section shape of separator]
When giving a definition, observing the section shape of the separator that form by scanning electron microscope at section shape A, the B of separator or C, is " well " with the situation of A or C, is " bad " with the situation of C.The A of the section shape of separator, B and C diagram ground illustration in Fig. 1.
A: bottom size is greater than the situation of 30 μ m smaller or equal to 36 μ m,
B: bottom size is greater than the situation of 36 μ m,
C: irrelevant with bottom size, be the situation of platform shape shape.
[solvent resistance evaluation]
After being coated on composition on the silicon substrate with spinner, prebake conditions formed filming of thickness 3.0 μ m in 2 minutes on hot plate under 90 ℃.Afterwards, the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) by キ ヤ ノ Application (strain) system is with cumulative exposure 3,000J/m 2Filming of gained exposed.This silicon substrate in the cleaning baking oven, under 220 ℃, was heated 1 hour, obtain cured film.Measure the thickness (T1) of the cured film of gained.Then, the silicon substrate of this formation cured film is controlled to be in 70 ℃ the dimethyl sulfoxide (DMSO) dipping in temperature measures the thickness (t1) of this cured film after 20 minutes, calculate the Thickness Variation rate that dipping causes | t1-T1|/T1} * 100 (%).The result is as shown in table 2.In this value is 5% or when following, thinks that solvent resistance is good.
In addition, in the evaluation of solvent resistance, owing to do not need film Butut to forming, so can omit the irradiation process and the developing procedure of radioactive ray, being used for only filming forms the evaluation of operation, back roasting procedure and heating process.
[thermotolerance evaluation]
Similarly form cured film with above-mentioned solvent resistance evaluation, measure the thickness (T2) of the cured film of gained.Then, this cured film substrate in the cleaning baking oven, appending baking under 240 ℃ after 1 hour, is measured the thickness (t2) of this cured film, calculate the Thickness Variation rate of appending baking and causing | t2-T2|/T2} * 100 (%).The result is as shown in table 2.In this value is 5% or when following, thinks that thermotolerance is good.
[transparency is estimated]
In above-mentioned solvent resistance is estimated, except using glass substrate " コ one ニ Application グ 7059 " (コ one ニ Application グ society system) replacement silicon substrate, similarly on glass substrate, form cured film." 150-20 type ダ Block Le PVC one system ((strain) Hitachi system) under the wavelength of 400～800nm, is measured the light transmission rate of the glass substrate with this cured film to use spectrophotometer.At this moment, minimum light penetration is as shown in table 2.This value is 90% or when above, thinks that the transparency is good.
[evaluation of orientation and voltage retention]
Use composition solution, on the electrode surface of glass substrate, similarly form projection and separator with preceding method with ITO (indium oxide of coating tin) film as electrode.Afterwards, by liquid crystal orientation film coating printing machine, on the glass substrate that forms projection and separator behind the AL1H659 (trade name, ジ エ イ エ ス ア one Le (strain) is made) of coating as aligning agent for liquid crystal, drying is 1 hour under 180 ℃, forms filming of thickness 0.05 μ m.In addition, use printing machine by the liquid crystal orientation film coating, coating is as the AL1H659 of aligning agent for liquid crystal on the electrode surface of another piece glass substrate with ITO film, and drying is 1 hour under 180 ℃, forms filming of thickness 0.05 μ m.Then, on the outside surface of each liquid crystal orientation film of the two substrates of gained, the serigraphy coating adds the epoxy adhesive of the glass fibre of diameter 5 μ m, so that the liquid crystal orientation film surface relatively overlaps, bonding agent is solidified the two substrates pressing.Afterwards, between two substrates, fill the liquid crystal MLC-6608 (trade name) that メ Le Network society makes from liquid crystal injecting port, after by epoxy adhesive liquid crystal injecting port being sealed, at two substrates outside surface applying polarizing plate, make its polarization direction quadrature, make vertical alignment-type liquid crystal display device.The longitudinal section of the vertical alignment-type liquid crystal display device of diagram expression gained in Fig. 2, wherein label 1 expression separator, label 2 expression projections, label 3 expression liquid crystal, label 4 expression liquid crystal orientation films, label 5 expression color filters, label 6 expression glass substrates.
Then, the orientation of the vertical alignment-type liquid crystal display device of following evaluation gained and voltage retention.
The evaluation of orientation is when open and close voltage, whether can produce abnormal area by polarized light microscope observing in liquid crystal cell, to confirm the not having situation of abnormal area to be " well ".In addition, when estimating voltage retention, be after applying 5V voltage on the liquid crystal display cells, disconnecting circuit, the sustaining voltage after measuring 16.7 milliseconds calculates sustaining voltage with respect to the apply voltage ratio of (5V).This value is 98% or when above, thinks good.
[table 2]
The composition kind Developing method Developer solution Sensitivity is estimated Section shape Solvent resistance Thermotolerance The transparency (%) Orientation Voltage retention (%)
Solution level (weight %) Sensitivity J/m 2 Projection Separator Solidify back thickness (μ m) Thickness Variation rate (%) Solidify back thickness (μ m) Thickness Variation rate (%)
Embodiment 1 (S-1) Contain the liquid method TMAH 0.4 2800 A C 2.4 2 2.4 3 94 Well 99.7
Embodiment 2 (S-2) Contain the liquid method KOH 0.1 2500 A C 2.4 2 2.4 3 94 Well 99.7
Embodiment 3 (S-3) Towards the pouring method TMHA 0.4 2200 A C 2.5 2 2.5 3 94 Well 99.7
Embodiment 4 (S-4) Towards the pouring method TMAH 0.4 2800 A C 2.4 1 2.4 1 95 Well 99.7

Claims (6)

1. radiation sensitive resin composition that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator is characterized in that: comprises,
The multipolymer that [A] obtains following (a1)～(a3) copolymerization, wherein (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,
(a2) be unsaturated compound with epoxy radicals or oxetanyl,
(a3) be above-mentioned (a1) and (a2) in addition olefines unsaturated compound; With
[B] light cationic polymerization initiators.
2. the radiation sensitive resin composition of putting down in writing according to claim 1 that is used to form employed projection of vertical alignment-type liquid crystal display device and/or separator is characterized in that: further contain [C] thioxanthones compounds.
3. the projection used of a vertical alignment-type liquid crystal display device, this projection is to be formed by claim 1 or 2 radiation sensitive resin compositions of being put down in writing.
4. the separator that uses of a vertical alignment-type liquid crystal display device, this separator is to be formed by claim 1 or 2 radiation sensitive resin compositions of being put down in writing.
5. vertical alignment-type liquid crystal display device, this vertical alignment-type liquid crystal display device comprise the separator that projection that claim 3 is put down in writing and/or claim 4 are put down in writing.
6. method that forms projection and/or separator is characterized in that: comprise following operation at least,
(1) operation of filming of the radiation-ray sensitive composition that formation claim 1 is put down in writing on substrate;
(2) to the operation of this at least a portion of filming irradiation radioactive ray;
(3) developing procedure;
(4) heating process.
CNA2006100670155A 2005-04-01 2006-03-31 X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof, and liquid crystal display element Pending CN1841195A (en)

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Cited By (2)

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CN106970504A (en) * 2016-01-14 2017-07-21 东友精细化工有限公司 Photosensitive polymer combination, photocuring pattern and image display device
CN107329330A (en) * 2017-07-28 2017-11-07 武汉华星光电技术有限公司 Liquid crystal display panel and preparation method thereof, cylindrical spacer

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Publication number Priority date Publication date Assignee Title
JP2008216290A (en) * 2007-02-28 2008-09-18 Sanyo Chem Ind Ltd Photosensitive resin composition
CN101872123B (en) * 2009-04-27 2013-07-24 Jsr株式会社 Radioactive rays sensitive resin compound, distance piece or protection film for liquid crystal display and forming method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106970504A (en) * 2016-01-14 2017-07-21 东友精细化工有限公司 Photosensitive polymer combination, photocuring pattern and image display device
CN106970504B (en) * 2016-01-14 2020-09-22 东友精细化工有限公司 Photosensitive resin composition, photocured pattern and image display device
CN107329330A (en) * 2017-07-28 2017-11-07 武汉华星光电技术有限公司 Liquid crystal display panel and preparation method thereof, cylindrical spacer
CN107329330B (en) * 2017-07-28 2020-05-19 武汉华星光电技术有限公司 Liquid crystal display panel, manufacturing method thereof and columnar spacer

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