CN101784958A - Photosensitive composition, cured film formed therefrom, and device having cured film - Google Patents

Photosensitive composition, cured film formed therefrom, and device having cured film Download PDF

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Publication number
CN101784958A
CN101784958A CN200880103680A CN200880103680A CN101784958A CN 101784958 A CN101784958 A CN 101784958A CN 200880103680 A CN200880103680 A CN 200880103680A CN 200880103680 A CN200880103680 A CN 200880103680A CN 101784958 A CN101784958 A CN 101784958A
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polysiloxane
cured film
group
weight
acid
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CN101784958B (en
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妹尾将秀
冈沢彻
诹访充史
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Toray Industries Inc
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Toray Industries Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035—Materials
    • G02B2006/12069—Organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133357—Planarisation layers
    • G—PHYSICS
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
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    • G02F2202/023—Materials and properties organic material polymeric curable

Abstract

Disclosed is a photosensitive composition containing a polysiloxane (a), an acrylic resin (b), a quinonediazide compound (c) and a solvent (d). In this photosensitive composition, the mixing ratio between the polysiloxane (a) and the acrylic resin (b), namely polysiloxane/acrylic resin is from 80/20 to 20/80 in weight ratio, and the polysiloxane (a) is synthesized by reacting one or more organosilanes represented by the following general formula (1). (In the formula, R1 represents a hydrogen, an alkyl group having 1-10 carbon atoms, an alkenyl group having 2-10 carbon atoms or an aryl group having 6-15 carbon atoms, and a plurality of R1's may be the same as or different from each other; R2 represents a hydrogen, an alkyl group having 1-6 carbon atoms, an acyl group having 2-6 carbon atoms, or an aryl group having 6-15 carbon atoms, and a plurality of R2's may be the same as or different from each other; and n represents an integer of 0-3.) The photosensitive composition enables to obtain a cured film which has high heat resistance and high transparency, while exhibiting good adhesion to a substrate. This photosensitive composition is used for forming a planarization film for TFT substrates, an interlayer insulating film, or a core or cladding material for optical waveguides.

Description

Photosensitive composite, the cured film that forms by said composition and element with cured film
Technical field
The present invention relates to be used to form thin film transistor (TFT) (TFT) substrates such as liquid crystal display cells and/or organic EL display element with the core of the interlayer dielectric of planarization films, semiconductor element or optical waveguide and/or coat the photosensitive composite of material, cured film that forms by said composition and element with this cured film.
Background technology
In recent years, as in LCD and/or OLED display etc., realizing more high-fineness, more high-resolution method, the method for the aperture opening ratio of known raising display device (referring to Patent Document 1).This method is provided with transparent planarization film as diaphragm by the top at the TFT substrate, can make data line and pixel electrode overlapping, thereby improve aperture opening ratio than prior art.
As the material of such TFT substrate with planarization film, need have the characteristic of high-fire resistance, high transparent, and, need to form the sectional hole patterns about 50 μ m～number μ m in order to connect TFT electrode of substrate and ITO electrode, use the positive light sensitivity material usually.As representational material, the known material that in acryl resin, makes up quinone di-azido compound (referring to Patent Document 2,3), but these material thermal resistance are insufficient, exist because the pyroprocessing of substrate causes the such problem of the painted and transparent reduction of cured film.
In addition, as the other materials of characteristic with high-fire resistance, high transparent, known polysiloxane, and the known material (referring to Patent Document 4) that has made up quinone di-azido compound in order to make polysiloxane have positive light sensitivity therein.This material transparency is high, even and also do not reduce through the pyroprocessing transparency of substrate, can obtain high transparent cured film.But the adhesiveness of this material and substrate is low, even the above-mentioned material of being made by acryl resin also exists and the insufficient such problem of the adhesiveness of substrate.
In addition, the system of uniting use as polysiloxane and acryl resin, the known material of being made by polysiloxane, (methyl) acrylic acid series polymeric compounds and latent acid catalyst (referring to Patent Document 5) has the material (referring to Patent Document 6) that sour polysiloxane, the acryl resin that contains silicon-containing group and the acid agent that decomposes the organic group of group made by comprising.But, if use quinone di-azido compound as latent acid catalyst in these materials and/or acid agent, then because the compatibility of polysiloxane and/or acryl resin and quinone di-azido compound is poor, thereby the albefaction of can filming, the transparent film of height can not be obtained.In addition, the also known material of making by water repellency silicone resin, acryl resin and quinone di-azido compound (referring to Patent Document 7), but because the water repellency height on film surface, thereby the low such problem of the adhesiveness of existence and sealant.
Patent documentation 1: the spy opens flat 9-152625 communique (claim 1)
Patent documentation 2: the spy opens 2001-281853 communique (claim 1)
Patent documentation 3: the spy opens 2001-281861 communique (claim 1)
Patent documentation 4: the spy opens 2006-178436 communique (claim 1)
Patent documentation 5: the spy opens 2001-55554 communique (claim 6)
Patent documentation 6: the spy opens 2005-221714 communique (claim 7)
Patent documentation 7: the spy opens 2004-4733 communique (claim 1)
Summary of the invention
The problem that invention will solve
The present invention is based on above-mentioned situation and proposes, and its objective is that providing a kind of can access the characteristic with high-fire resistance, high transparent, and with the photosensitive composite of the cured film of the good adhesion of substrate.In addition, another object of the present invention provides the TFT substrate that formed by above-mentioned photosensitive composite with planarization film, interlayer dielectric, core and/or coat cured film such as material, and the elements such as display element, semiconductor element, optical waveguide with this cured film.
The method that is used to deal with problems
Promptly, the present invention relates to a kind of photosensitive composite, contain (a) polysiloxane, (b) acryl resin, (c) quinone di-azido compound, (d) solvent, wherein, (a) polysiloxane/(b) mixture ratio of acryl resin counts 80/20～20/80 with weight ratio, and (a) polysiloxane is to react synthetic polysiloxane by the organosilane shown in the general formula (1) more than a kind
In the following formula, R 1Expression hydrogen atom, carbon number are that 1～10 alkyl, carbon number are that 2～10 alkenyl, carbon number are any in 6～15 the aryl, a plurality of R 1Can be the same or different respectively; R 2Expression hydrogen atom, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any in 6～15 the aryl, a plurality of R 2Can be the same or different respectively; N represents 0～3 integer.
The invention effect
Utilize photosensitive composite of the present invention, can access characteristic with high-fire resistance, high transparent, and with the cured film of the good adhesion of substrate.In addition, the cured film that obtains is suitable as TFT substrate planarization film and/or interlayer dielectric.
Embodiment
Photosensitive composite of the present invention is the photosensitive composite that contains (a) polysiloxane, (b) acryl resin, (c) quinone di-azido compound, (d) solvent.
There is the low problem of adhesiveness with substrate in polysiloxane.This can think owing to following reason.Promptly, be because the hydroxyl of silanol group in the polysiloxane and substrate surface reacts when heat curing and forms chemical bond, still, because the retractility of polysiloxane is low, if thereby apply external force, then force localization is on the interface of cured film and substrate and peel off easily.On the other hand, because the retractility height of acryl resin, even thereby apply external force and also can alleviate acting force by stretching of cured film.Therefore, relatively good with the adhesiveness of substrate.But, owing between substrate and cured film, do not form chemical bond, thereby adhesiveness is insufficient.
Relative therewith, use polysiloxane and acryl resin by uniting, between substrate and film, form chemical bond, and improve the retractility of film, thus the adhesiveness of raising and substrate.But the compatibility of polysiloxane and acryl resin is poor, is separated easily.Therefore, film generation gonorrhoea and can not obtain high transparent cured film under a lot of situations.Therefore, need to select only polysiloxane and acryl resin, so that be not separated.
In photosensitive composite of the present invention, (a) polysiloxane and the mixture ratio of (b) acryl resin are in weight ratio, and polysiloxane/acryl resin is 20/80～80/20, more preferably polysiloxane/acryl resin=75/25～30/70.If acryl resin is less than 20%, then can not obtain to improve fully the adhering effect of substrate and cured film.On the other hand, if polysiloxane is less than 20%, then can not obtain to improve fully the adhering effect of substrate and cured film, and the transmissivity of cured film reduces also.
Photosensitive composite of the present invention contains (a) polysiloxane, and polysiloxane used in the present invention is to react synthetic polysiloxane by the organosilane shown in the general formula (1) more than a kind.
Figure GPA00001029901900041
(in the formula, R 1Expression hydrogen atom, carbon number are that 1～10 alkyl, carbon number are that 2～10 alkenyl, carbon number are any in 6～15 the aryl, a plurality of R 1Can be the same or different respectively.R 2Expression hydrogen atom, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any in 6～15 the aryl, a plurality of R 2Can be the same or different respectively.N represents 0～3 integer.)
In the organosilane shown in the general formula (1), R 1Expression hydrogen atom, carbon number are that 1～10 alkyl, carbon number are that 2～10 alkenyl, carbon number are any in 6～15 the aryl, a plurality of R 1Can be the same or different respectively.In addition, any in these alkyl, alkenyl, the aryl all can be any in no substituent, the substituent, can select according to the characteristic of composition.
As the concrete example of alkyl, can enumerate following group.Promptly, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl, trifluoromethyl, 3,3,3-trifluoro propyl, 3-glycidoxy propyl group, 2-(3, the 4-epoxycyclohexyl) ethyl, ((3-ethyl-3-oxetanyl) methoxyl) propyl group, 3-aminopropyl, 3-sulfydryl propyl group, 3-isocyanate group propyl group etc.
As the concrete example of alkenyl, can enumerate following group.That is, can enumerate vinyl, 3-acryloyl-oxy propyl group, 3-methacryloxypropyl.As the concrete example of aryl, be phenyl, tolyl, p-hydroxybenzene, 1-(p-hydroxybenzene) ethyl, 2-(p-hydroxybenzene) ethyl, 4-hydroxyl-5-(p-hydroxybenzene ketonic oxygen base) amyl group, naphthyl etc.
The R of general formula (1) 2Expression hydrogen atom, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any in 6～15 the aryl, a plurality of R 2Can be the same or different respectively.In addition, any in these alkyl, acyl group, the aryl all can be any in no substituent, the substituent, can select according to the characteristic of composition.As the concrete example of alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl.As the concrete example of acyl group, can enumerate acetyl group.As the concrete example of aryl, can enumerate phenyl.
The n of general formula (1) represents 0～3 integer.Being 4 functional silanes when n=0, is 3 functional silanes when n=1, is 2 functional silanes when n=2, is 1 functional silanes when n=3.
As the concrete example of the organosilane shown in the general formula (1), can enumerate following organosilane.Promptly, tetramethoxy-silicane, tetraethoxysilane, the tetrem acyloxy silane, 4 functional silanes such as tetraphenoxy-silicane alkane, methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, methyl three n-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl trimethoxy silane, the n-hexyl triethoxysilane, the decyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloyl-oxy propyl trimethoxy silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, the p-hydroxybenzene trimethoxy silane, 1-(p-hydroxybenzene) ethyl trimethoxy silane, 2-(p-hydroxybenzene) ethyl trimethoxy silane, 4-hydroxyl-5-(p-hydroxybenzene ketonic oxygen base) amyltrimethoxysilane, the trifluoromethyl trimethoxy silane, the trifluoromethyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, ((3-ethyl-3-oxetanyl) methoxyl) propyl trimethoxy silicane, ((3-ethyl-3-oxetanyl) methoxyl) propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3 functional silanes such as 3-trimethoxy-silylpropyl succinic acid, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diacetoxy silane, di-n-butyl dimethoxy silane, dimethoxydiphenylsilane, (3-glycidoxy propyl group) methyl dimethoxysilane, 2 functional silanes such as (3-glycidoxy propyl group) methyldiethoxysilane, the trimethyl methoxy silane, three normal-butyl Ethoxysilanes, (3-glycidoxy propyl group) dimethyl methyl TMOS, 1 functional silanes such as (3-glycidoxy propyl group) dimethylethoxysilane etc.In addition, these organosilanes may be used alone, two or more kinds can also be used in combination.In these organosilanes,, preferably use 3 functional silanes from the splitting resistance of cured film and the viewpoint of hardness.
In addition, as the form of polysiloxane used in the present invention, can use by organosilane shown in the above-mentioned general formula (1) and silicon dioxide granule reaction more than a kind and come synthetic polysiloxane.By reacting, can improve pattern resolution with silicon dioxide granule.Its reason can think, by mix silicon dioxide granule in polysiloxane, the glass transition temperature of film raises, thereby the pattern during heat curing caves in and is suppressed.
The number average bead diameter of silicon dioxide granule is preferably 2nm～200nm, more preferably 5nm～70nm.If less than 2nm, the effect that then improves pattern resolution is insufficient, if greater than 200nm, and then cured film generation light scattering and the transparency reduces.Wherein, number average bead diameter for silicon dioxide granule, under the situation of using specific surface area method scaled value, silicon dioxide granule is carried out drying, burn till then, measure the specific surface area of the particle of gained, then particle is assumed to spheroid, try to achieve particle diameter by specific surface area, obtain mean grain size as number average bead diameter.To the not restriction especially of employed instrument, can use ア サ Star プ 2020 (trade name, Micromeritics society makes) etc.
As the concrete example of silicon dioxide granule, can enumerate following particle.Promptly; with the isopropyl alcohol is the IPA-ST of the particle diameter 12nm of dispersion medium; with the methyl isobutyl ketone is the MIBK-ST of the particle diameter 12nm of dispersion medium; with the isopropyl alcohol is the IPA-ST-L of the particle diameter 45nm of dispersion medium; with the isopropyl alcohol is the IPA-ST-ZL of the particle diameter 100nm of dispersion medium; the PGM-ST that with the propylene glycol monomethyl ether is the particle diameter 15nm of dispersion medium (abovely is trade name; daily output chemical industry (strain) is made); with the gamma-butyrolacton is the オ ス カ Le 101 of the particle diameter 12nm of dispersion medium; with the gamma-butyrolacton is the オ ス カ Le 105 of the particle diameter 60nm of dispersion medium; with the diacetone alcohol is the オ ス カ Le 106 of the particle diameter 120nm of dispersion medium; dispersion soln is that カ タ ロ イ De-S of the particle diameter 5～80nm of water is (above for trade name; catalyst changes into industry (strain) manufacturing); with the propylene glycol monomethyl ether is the Network オ one ト ロ Application PL-2L-PGME of the particle diameter 16nm of dispersion medium; with the gamma-butyrolacton is the Network オ one ト ロ Application PL-2L-BL of the particle diameter 17nm of dispersion medium; with the diacetone alcohol is the Network オ one ト ロ Application PL-2L-DAA of the particle diameter 17nm of dispersion medium; dispersion soln is the Network オ one ト ロ Application PL-2L of the particle diameter 18～20nm of water; GP-2L (above is trade name, and Japan's chemical industry (strain) is made); particle diameter is the silicon dioxide (SiO of 100nm 2) SG-SO100 (trade name, upright altogether マ テ リ ア Le (strain) is made), particle diameter be レ オ ロ シ one Le (trade name, (strain) ト Network ヤ マ makes) of 5～50nm etc.In addition, these silicon dioxide granules may be used alone, two or more kinds can also be used in combination.
Restriction especially of mixture ratio when using silicon dioxide granule is below 50% in Si atomic molar number with respect to the Si atomic molar number of whole polymkeric substance preferably.If silicon dioxide granule is more than 50%, the then compatibility variation of polysiloxane and quinone di-azido compound, thereby the transparency of cured film reduces.In addition, the Si atomic molar number of silicon dioxide granule can be in IR with respect to the mol ratio of the Si atomic molar number of whole polymkeric substance by trying to achieve from the peak of Si-C key and integration ratio from the peak of Si-O key.More and can't ask when calculating at overlap of peaks, can pass through 1H-NMR, 13C-NMR, IR, TOF-MS etc. determine the structure of the monomer except that particle, and then (suppose all be SiO by gas that produces in the elemental microanalysis method and residual ash content 2) ratio try to achieve.
In addition, in polysiloxane used in the present invention, improve with the compatibility of acryl resin, to form uniform cured film under situation about not being separated be important.Therefore, the containing ratio of phenyl is preferably 30 moles more than the % with respect to the Si atom in the polysiloxane, more preferably 40 moles more than the %.If the containing ratio of phenyl is lower than 30 moles of %, then polysiloxane and acryl resin are separated in coating, drying, heat curing etc. easily, cause the film gonorrhoea, and the cured film transmissivity reduces.In addition, as the higher limit of phenyl containing ratio, be preferably 70 moles below the %.If the containing ratio of phenyl is higher than 70 moles of %, then crosslinked insufficient during heat curing causes the chemical-resistant of cured film to reduce.The phenyl containing ratio can be by for example measuring polysiloxane 29Si-NMR, by bonding the peak area of Si of phenyl try to achieve with the ratio of the peak area of the Si of bonding phenyl not.
In addition, in polysiloxane used in the present invention, further raising is important with the compatibility of acryl resin.Therefore, preferably use the organosilane copolymerization that contains epoxy radicals and the polysiloxane that gets.Carry out copolymerization by the organosilane that contains epoxy radicals, polymerization and polysiloxane contain the alcoholic extract hydroxyl group that epoxy radicals or epoxy radicals hydrolysis form.Interact by the carbonyl position in these groups and the acryl resin and to improve the compatibility of polysiloxane and acryl resin.The copolymerization ratio that comprises the organosilane of epoxy radicals is preferably 1～20 mole of %, more preferably 3～15 moles of %.If the copolymerization ratio of epoxy radicals is lower than 1 mole of %, the effect that then improves compatibility is insufficient, if be higher than 20 moles of %, then the water wettability of polysiloxane raises, thereby the film impairment of unexposed portion increases the film uniformity variation of cured film when developing.
The preferred concrete example of organosilane that contains epoxy radicals is as follows.Promptly, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-dimethyl methoxy silane, 3-glycidoxy propyl-dimethyl Ethoxysilane etc.In addition, these organosilanes may be used alone, two or more kinds can also be used in combination.In these organosilanes,, preferably use 3 functional silanes from the splitting resistance of cured film and the viewpoint of hardness.
In addition, to the restriction especially of the weight-average molecular weight (Mw) of polysiloxane used in the present invention, preferably the polystyrene conversion weight-average molecular weight by GPC (gel permeation chromatography) mensuration is 1000～100000, more preferably 2000～50000.If Mw is less than 1000, filming property variation then, if greater than 100000, the dissolubility variation when then pattern forms in developer solution.
Polysiloxane among the present invention can synthesize by monomer hydrolysis such as the organosilane shown in the general formula (1) and part condensation.When hydrolysis and part condensation, can use common method.For example, in potpourri, add solvent, water, and add catalyzer as required, 50～150 ℃ of following heated and stirred about 0.5～100 hour.In addition, when stirring, can be as required, separate accessory substance alcohol such as () methyl alcohol and/or condensation by-product (water) by heating up in a steamer to anhydrate.
As the not restriction especially of above-mentioned reaction dissolvent, can use usually and the same solvent of aftermentioned (d) solvent.The addition of solvent is 10～1000 weight portions with respect to monomers such as 100 weight portion organosilanes preferably.In addition, the addition of employed water is 0.5～2 mole with respect to 1 mole of hydrolization group preferably in the hydrolysis reaction.
To the not restriction of adding as required especially of catalyzer, preferably use acid catalyst, base catalyst.As the concrete example of acid catalyst, can enumerate hydrochloric acid, nitric acid, sulfuric acid, hydrofluorite, phosphoric acid, acetate, trifluoroacetic acid, formic acid, polybasic carboxylic acid or its acid anhydrides, ion exchange resin.As the concrete example of base catalyst, can enumerate following compound.That is, triethylamine, tripropyl amine (TPA), tri-butylamine, three amylamines, three hexyl amines, three heptyl amine, trioctylphosphine amine, diethylamine, triethanolamine, diethanolamine, NaOH, potassium hydroxide, alkoxy silane, ion exchange resin etc. with amino.The addition of catalyzer is preferably 0.01～10 weight portion with respect to monomers such as 100 weight portion organosilanes.
In addition, the viewpoint from the storage stability of composition does not preferably contain catalyzer in the polysiloxane solution after hydrolysis, part condensation.Therefore, can remove catalyzer as required.As not restriction especially of the method for removing, preferably enumerate washing and/or TREATMENT OF ION EXCHANGE RESINS.So-called washing is meant with suitable hydrophobic solvent dilution polysiloxane solution, washes with water then for several times, the method that the organic layer that obtains is concentrated with evaporator again.What is called is utilized TREATMENT OF ION EXCHANGE RESINS, is the method for instigating polysiloxane solution to contact with suitable ion exchange resin.
Photosensitive composite of the present invention contains (b) acryl resin.To not restriction especially of acryl resin, preferably enumerate the polymkeric substance of unsaturated carboxylic acid.As the example of unsaturated carboxylic acid, can enumerate acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid etc.These unsaturated carboxylic acids can use separately, but also can be used in combination with the alefinically unsaturated compounds of other copolymerization.But, can enumerate following compound as the example of the alefinically unsaturated compounds of copolymerization.That is methyl acrylate,, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, the acrylic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, the metering system tert-butyl acrylate, the acrylic acid n-pentyl ester, the methacrylic acid n-pentyl ester, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, glycidyl acrylate, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, p-methylstyrene, o-methyl styrene, between methyl styrene, α-Jia Jibenyixi, acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester etc.
In addition, to the restriction especially of the weight-average molecular weight (Mw) of acryl resin used in the present invention, preferably the polystyrene conversion weight-average molecular weight of measuring by GPC is 5000～50000, more preferably 8000～35000.If Mw is less than 5000, take place then that pattern caves in during heat curing and resolution reduces.On the other hand, if Mw greater than 50000, then polysiloxane and acryl resin are separated and cause the film gonorrhoea, thereby the transmissivity of cured film reduces.
In addition, acryl resin used in the present invention is preferably alkali-soluble.The acid number of acryl resin is preferably 50～150mgKOH/g, more preferably 70～130mgKOH/g.If resinous acid value is less than 50mgKOH/g, it is residual that dissolving takes place when then developing easily.On the other hand, if acid number greater than 150mgKOH/g, the film of unexposed portion impairment becomes big when then developing.
In addition, acryl resin used in the present invention is preferably the acryl resin that is connected with ethylenically unsaturated group at side chain.By connecting ethylenically unsaturated group at side chain, thereby it is crosslinked that acryl resin is taken place, and improves the chemical-resistant of cured film.The scope of preferred unsaturated equivalent is 500～1500.If unsaturated equivalent is less than 500, then the cross-linking density of acryl resin becomes too high during heat curing, cracks on cured film easily.In addition, if unsaturated equivalent greater than 1500, then acryl resin is crosslinked insufficient during heat curing.Therefore, the effect of the chemical-resistant of raising cured film is insufficient.As ethylenically unsaturated group, vinyl, allyl, acrylic, methacrylic acid group etc. are arranged.As the method that connects ethylenically unsaturated group at the side chain of acryl resin, can enumerate the compound that uses functional groups such as containing hydroxyl, amino, glycidyl and ethylenically unsaturated group, and make the method for the carbonyl reaction in this functional group and the acryl resin.As the so-called compound that contains functional groups such as hydroxyl, amino, glycidyl and ethylenically unsaturated group here, can enumerate 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, acrylic acid-2-amino ethyl ester, methacrylic acid-2-amino ethyl ester, glycidyl acrylate, glycidyl methacrylate etc.
Photosensitive composite of the present invention contains (c) quinone di-azido compound.The photosensitive composite that contains quinone di-azido compound forms exposed portion and is developed the eurymeric that liquid is removed.To the restriction especially of employed quinone di-azido compound, be preferably the compound that compound with phenolic hydroxyl group and naphthoquinones two nitrine sulfonic acid pass through the ester bond be combined into.The ortho position of the preferred phenolic hydroxyl group that uses this compound and contraposition are any the compound in the substituting group shown in hydrogen atom or the general formula (2) independently of one another.
Figure GPA00001029901900101
(in the formula, R 3, R 4, R 5Represent that independently of one another carbon number is any in 1～10 alkyl, carboxyl, phenyl, the substituted-phenyl.In addition, R 3, R 4, R 5Also can form ring.)
In the substituting group shown in the general formula (2), R 3, R 4, R 5Represent that independently of one another carbon number is any in 1～10 alkyl, carboxyl, phenyl, the substituted-phenyl.Alkyl can be any in no substituent, the substituent, can select according to the characteristic of composition.As the concrete example of alkyl, can enumerate following group.That is, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, n-heptyl, n-octyl, trifluoromethyl, 2-carboxyethyl etc.In addition, as the substituting group of substituted-phenyl, can enumerate hydroxyl.In addition, R 3, R 4, R 5Also ring can be formed,, cyclopentane ring, cyclohexane ring, diamantane ring, fluorenes ring can be enumerated as concrete example.
During for other groups except that above-mentioned group, for example methyl, owing to oxygenolysis takes place in heat curing, thereby cured film is painted, the water white transparency reduction in the ortho position of phenolic hydroxyl group and contraposition.In addition, compound that these quinone di-azido compounds can be by having phenolic hydroxyl group and naphthoquinones two nitrine sulfonic acid chlorides carry out known esterification and synthesize.
As the concrete example of compound, can enumerate following compound (being Honshu chemical industry (strain) manufacturing) with phenolic hydroxyl group.
Figure GPA00001029901900121
As naphthoquinones two nitrine sulfonic acid, can use 4-naphthoquinones two nitrine sulfonic acid or 5-naphthoquinones two nitrine sulfonic acid.Because 4-naphthoquinones two nitrine sulfonate compounds have absorption in i line (wavelength 365nm) zone, thereby suitable i line exposing.In addition, because there be absorptions in 5-naphthoquinones two nitrine sulfonate compounds in the wavelength region may of wide region, thereby the wavelength that is adapted at wide region time exposes.Preferably select 4-naphthoquinones two nitrine sulfonate compounds, 5-naphthoquinones two nitrine sulfonate compounds according to the wavelength difference of exposure.Can also mix and use 4-naphthoquinones two nitrine sulfonate compounds and 5-naphthoquinones two nitrine sulfonate compounds.
Addition to quinone di-azido compound does not limit especially, is 1～20 weight portion with respect to 100 parts by weight resin (polysiloxane+acryl resin) preferably, more preferably 2～15 weight portions.When the addition of quinone di-azido compound was lower than 1 weight portion, the dissolving contrast of exposed portion and unexposed portion was low excessively, did not have the photonasty of reality.In addition, in order to obtain better to dissolve contrast, the addition of preferred quinone di-azido compound is more than 2 weight portions.On the other hand, when the addition of quinone di-azido compound is higher than 20 weight portions, the water white transparency reduction of cured film.This is caused by following reason: the compatibility variation of polysiloxane and quinone di-azido compound and the albefaction that causes filming, and/or the quinone di-azido compound that takes place during heat curing decompose cause painted.In addition, in order to obtain the higher film of the transparency, the addition of preferred quinone di-azido compound is below 15 weight portions.
Photosensitive composite of the present invention contains (d) solvent.To the not restriction especially of employed solvent, the preferred ring compound that has the compound of alcoholic extract hydroxyl group and/or have carbonyl that uses.If use these solvents, then can the uniform dissolution polysiloxane, acryl resin and quinone di-azido compound, the film albefaction can not take place even composition is carried out coating film forming, thereby can realize high transparent yet.
To above-mentioned not restriction especially of compound with alcoholic extract hydroxyl group, preferred boiling point under atmospheric pressure is 110～250 ℃ a compound.If boiling point is higher than 250 ℃, then the remaining quantity of solvent in the film increases, and the film during curing shrinks and becomes big, can not obtain good flatness.On the other hand, if boiling point is lower than 110 ℃, dry too fast when then filming causes filming property variation such as film rough surface.
As the concrete example of compound, can enumerate following compound with alcoholic extract hydroxyl group.That is, acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxyl-2 pentanone, 4-hydroxy-4-methyl-2 pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, propylene glycol list tertbutyl ether, dipropylene glycol monomethyl ether, 3-methoxyl-1-butanols, 3-methyl-3-methoxyl-1-butanols, benzylalcohol etc.Wherein, more preferably use compound, especially preferably use diacetone alcohol with carbonyl.In addition, these compounds with alcoholic extract hydroxyl group can use separately, or are used in combination more than 2 kinds.
To the not restriction especially of ring compound with carbonyl, preferred boiling point under atmospheric pressure is 150～250 ℃ a compound.If boiling point is higher than 250 ℃, then the remaining quantity of solvent in the film increases, and the film during curing shrinks and increases, and can not obtain good flatness.On the other hand, if boiling point is lower than 150 ℃, dry too fast when then filming causes filming property variation such as film rough surface.
As the concrete example of ring compound, can enumerate following compound with carbonyl.That is, gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi, propylene carbonate, N-Methyl pyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone etc.Wherein, especially preferably use gamma-butyrolacton.In addition, these ring compounds with carbonyl can use separately, or are used in combination more than 2 kinds.
Above-mentioned compound with alcoholic extract hydroxyl group can use separately with the ring compound with carbonyl, or mixes respectively and use.When mix using, to the restriction especially of its weight rate, preferably have the compound of alcoholic extract hydroxyl group/have ring compound=99～50/1～50 of carbonyl, more preferably 97～60/3～40.If the compound with alcoholic extract hydroxyl group is more than 99 weight % (ring compound with carbonyl is less than 1 weight %), the compatibility variation of polysiloxane and quinone di-azido compound then, cured film albefaction and the transparency reduces.In addition, be less than 50 weight % (ring compound with carbonyl is more than 50 weight %), then cause the condensation reaction of the unreacted silicon silane alcohol base in the polysiloxane easily, the storage stability variation if having the compound of alcoholic extract hydroxyl group.
In addition, in the scope of not damaging effect of the present invention, photosensitive composite of the present invention can also contain other solvents.As other solvents, can enumerate following solvent.Promptly, ester classes such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxyl-1-butylacetic acid ester, 3-methyl-3-methoxyl-1-butylacetic acid ester, ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, diacetone, ethers such as ether, isopropyl ether, n-butyl ether, diphenyl ether, diglycol methyl ethyl ether etc.
To the not restriction especially of addition of solvent, be the scope of 100～1000 weight portions preferably with respect to 100 parts by weight resin (polysiloxane+acryl resin).
In addition, photosensitive composite of the present invention can also contain adjuvants such as silane coupling agent, crosslinking chemical, crosslinking accelerator, sensitizer, thermal free radical initiator, dissolution accelerator, dissolution inhibitor, surfactant, stabilizing agent, defoamer as required.
Photosensitive composite of the present invention can contain silane coupling agent.By containing silane coupling agent, can improve adhesiveness with substrate.
As the concrete example of silane coupling agent, can enumerate following compound.Promptly, methyltrimethoxy silane, methyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloyl-oxy propyl trimethoxy silicane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1,3-dimethyl butylidene) propylamine, N-phenyl-3-TSL 8330, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, ((3-ethyl-3-oxetanyl) methoxyl) propyl trimethoxy silicane, ((3-ethyl-3-oxetanyl) methoxyl) propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-urea groups propyl-triethoxysilicane, 3-isocyanate group propyl-triethoxysilicane, 3-trimethoxy-silylpropyl succinic acid, the N-tert-butyl group-3-(3-trimethoxy-silylpropyl) succinimide etc.
To the not restriction especially of addition of silane coupling agent, be the scope of 0.1～10 weight portion preferably with respect to 100 parts by weight resin (polysiloxane+acryl resin).If addition is less than 0.1 weight portion, it is insufficient then to improve adhering effect, if more than 10 weight portions, then condensation reaction takes place silane coupling agent each other in preservation, and the dissolving when causing developing is residual.
Photosensitive composite of the present invention can also contain crosslinking chemical.Crosslinking chemical is cross linking polysiloxane and/or an acryl resin and be incorporated into compound in the resin when heat curing, by containing the degree of crosslinking that crosslinking chemical can improve cured film.Thus, the chemical-resistant of cured film improves, and the cave in pattern resolution that causes of the pattern during heat curing reduces and is suppressed.
To not restriction especially of crosslinking chemical, preferably enumerate compound with following structure more than 2, described structure is selected from the group shown in the general formula (3), epoxy construction, the oxetanes structure.To the not restriction especially of combination of said structure, preferred selected structure is identical.
(R 6Expression hydrogen atom, carbon number are any in 1～10 the alkyl.Wherein, a plurality of R in the compound 6Can be the same or different respectively.)
In compound with the group shown in 2 above general formulas (3), R 6Expression hydrogen atom, carbon number are any in 1～10 the alkyl.In addition, a plurality of R in the compound 6Can be the same or different respectively.As the concrete example of alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl.
As the concrete example of compound with the group shown in 2 above general formulas (3), melamine derivative that can be listed below and/or urea derivative (trade name, three and ケ ミ カ Le (strain) make).
Figure GPA00001029901900171
As the concrete example of compound, can enumerate following compound with 2 above epoxy constructions.Promptly, エ Port ラ イ ト 40E, エ Port ラ イ ト 100E, エ Port ラ イ ト 200E, エ Port ラ イ ト 400E, エ Port ラ イ ト 70P, エ Port ラ イ ト 200P, エ Port ラ イ ト 400P, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 80MF, エ Port ラ イ ト 4000, (above be trade name to エ Port ラ イ ト 3002, common prosperity society chemical industry (strain) is made), デ Na コ one Le EX-212L, デ Na コ one Le EX-214L, デ Na コ one Le EX-216L, デ Na コ one Le EX-850L, (above be trade name to デ Na コ one Le EX-321L, Na ガ セ ケ system テ Star Network ス (strain) makes), GAN, GOT, EPPN502H, NC3000, (above be trade name to NC6000, Japan's chemical drug (strain) is made), エ ピ コ one ト 828, エ ピ コ one ト 1002, エ ピ コ one ト 1750, エ ピ コ one ト 1007, YX8100-BH30, E1256, E4250, (above be trade name to E4275, ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) is made), エ ピ Network ロ Application EXA-9583, エ ピ Network ロ Application HP4032, エ ピ Network ロ Application N695, (above be trade name to エ ピ Network ロ Application HP7200, big Japanese イ Application キ chemical industry (strain) is made), テ ピ Star Network S, テ ピ Star Network G, (above be trade name to テ ピ Star Network P, daily output chemical industry (strain) is made), エ Port ト one ト YH-434L (trade name, Dongdu changes into (strain) and makes), セ ロ キ サ イ De 2021P (trade name, ダ イ セ Le chemical industry (strain) is made), オ グ ソ one Le PG-100, オ グ ソ one Le EG-210 (above is trade name, and Osaka ガ ス ケ ミ カ Le (strain) is made) etc.
As the concrete example of compound, can enumerate following compound with 2 above oxetanes structures.Promptly, (above is trade name for OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX, East Asia synthetic (strain) manufacturing), エ タ Na コ one Le OXBP, エ タ Na コ one Le OXTP (above is trade name, and the emerging product of space portion (strain) is made) etc.
In addition, above-mentioned crosslinking chemical may be used alone, two or more kinds can also be used in combination.
To the not restriction especially of addition of crosslinking chemical, be the scope of 0.1～10 weight portion preferably with respect to 100 parts by weight resin (polysiloxane+acryl resin).If the addition of crosslinking chemical is less than 0.1 weight portion, the crosslinked insufficient and weak effect of resin then.On the other hand, if the addition of crosslinking chemical more than 10 weight portions, then the storage stability of the water white transparency reduction of cured film, composition reduces.
Photosensitive composite of the present invention can contain crosslinking accelerator.So-called crosslinking accelerator promotes the crosslinked compound of polysiloxane when being meant heat curing, acidic photoacid generator in the time of can using when heat curing acidic hot acid agent and/or the exposure of the bleaching before heat curing.In film, there is acid during by heat curing, can promotes the condensation reaction of the unreacted silicon silane alcohol base in the polysiloxane, improve the degree of crosslinking of cured film.Thus, can improve the chemical-resistant of cured film, and the pattern resolution that is caused of caving in of the pattern can suppress heat curing the time reduces.
Employed hot acid agent is an acidic compound when heat curing among the present invention, does not preferably produce acid during the preliminary drying behind coating composition or only produces the compound of small amount of acid.Therefore, be preferably at the temperature more than the preliminary drying temperature, acidic compound more than 100 ℃ for example.If produce acid under the temperature below the preliminary drying temperature, it is crosslinked and cause light sensitivity to reduce that polysiloxane then takes place during preliminary drying easily, and it is residual that dissolving takes place during development.
As the concrete example of the hot acid agent of preferred use, can enumerate following hot acid agent.Promptly, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above is trade name, and three new chemical industry (strain) are made), 4-hydroxy phenyl dimethyl trifluoromethayl sulfonic acid sulfonium, benzyl-4-hydroxy phenyl methyl trifluoro Loprazolam sulfonium, 2-methyl-benzyl-4-hydroxy phenyl methyl trifluoro Loprazolam sulfonium, 4-acetoxyl group phenyl dimethyl trifluoromethayl sulfonic acid sulfonium, 4-acetoxyl group phenyl benzyl methyl trifluoro Loprazolam sulfonium, 4-methoxycarbonyl group oxygen base phenyl dimethyl trifluoromethayl sulfonic acid sulfonium, benzyl-4-methoxycarbonyl group oxygen base phenyl methyl trifluoromethayl sulfonic acid sulfonium (more than be three new chemical industry (strain) make) etc.In addition, these compounds may be used alone, two or more kinds can also be used in combination.
Employed photoacid generator is an acidic compound when the bleaching exposure among the present invention, is to come acidic compound by exposure wavelength 365nm (i line), 405nm (h line), 436nm (g line) or the irradiation of their hybrid ray.Therefore, even in the pattern exposure that uses same light source, also may produce acid.But,, can not throw into question because pattern exposure is littler than the exposure of bleaching exposure, thereby only produces a spot of acid.In addition, the acid as producing is preferably strong acid such as perfluoro alkyl sulfonic acid, p-toluenesulfonic acid.In addition, the quinone di-azido compound that produces carboxylic acid does not have the function of said photoacid generator here, is different with crosslinking accelerator among the present invention.
As the concrete example of the photoacid generator of preferred use, can enumerate following photoacid generator.Promptly, SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, (above be trade name to PAI-1001, body ど ら chemistry (strain) is made), SP-077, (above be trade name to SP-082, (strain) ADEKA makes), (above be trade name to TPS-PFBS, Japan's compound probability (strain) is made), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, (above be trade name to WPAG-506, make with the pure pharmaceutical worker's industry of light (strain)), CGI-MDT, CGI-NIT (above is trade name, and チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) makes) etc.In addition, these compounds may be used alone, two or more kinds can also be used in combination.
In addition, as crosslinking accelerator, also can mix and use above-mentioned hot acid agent and photoacid generator.
To the not restriction especially of addition of crosslinking accelerator, be the scope of 0.01～5 weight portion preferably with respect to 100 parts by weight resin (polysiloxane+acryl resin).If addition is less than 0.01 weight portion, then effect is insufficient, if more than 5 weight portions, then polysiloxane takes place crosslinked when preliminary drying and/or during pattern exposure.
Photosensitive composite of the present invention can contain sensitizer.By containing sensitizer, can promote reaction and raising light sensitivity as naphthoquinones two triazo-compounds of emulsion.In addition, when containing photoacid generator as crosslinking accelerator, the solvent resistance and the pattern resolution of reaction in the time of can promoting to bleach exposure and raising cured film.
To restriction especially of employed sensitizer among the present invention, preferred use can be by thermal treatment gasification and/or the sensitizer that can fade by rayed.This sensitizer need have absorption to wavelength 365nm (i line), 405nm (h line), the 436nm (g line) of the light source in pattern exposure and/or the bleaching exposure.But, if it directly remains on the cured film, then exist to absorb in the visible region, so the water white transparency reduction.Therefore, the sensitizer that preferred use can be by thermal treatments such as heat curing gasification and/or the sensitizer that can fade by rayed such as bleaching exposures.
Can enumerate following sensitizer by the concrete example of thermal treatment gasification and/or the sensitizer that can fade by rayed as above-mentioned.Promptly, 3,3 '-carbonyl two cumarins such as (diethyl amino coumarins), 9, anthraquinones such as 10-anthraquinone, benzophenone, 4,4 '-dimethoxy-benzophenone, acetophenone, the 4-methoxyacetophenone, aromatic ketones such as benzaldehyde, biphenyl, 1, the 4-dimethylnaphthalene, the 9-Fluorenone, fluorenes, luxuriant and rich with fragrance, benzo [9,10] phenanthrene, pyrene, anthracene, the 9-phenylanthracene, 9-methoxyl anthracene, 9, the 10-diphenylanthrancene, 9,10-two (4-methoxyphenyl) anthracene, 9,10-two (triphenyl silicyl) anthracene, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 9,10-dibutoxy anthracene, 9,10-two amoxy anthracenes, the 2-tert-butyl group-9,10-dibutoxy anthracene, 9,10-two (trimethyl silyl ethinyl) anthracene etc. condenses aromatics etc.
In these sensitizers, preferably can distil, evaporate by thermal treatment, and the pyrolysate that thermal decomposition the produced sensitizer that can distil or evaporate.In addition, as the gasification temperature of sensitizer, be preferably 130 ℃～400 ℃, more preferably 150 ℃～250 ℃.If the gasification temperature of sensitizer is lower than 130 ℃, then sensitizer gasifies in preliminary drying and can not be present in the exposure process sometimes, thereby can not improve light sensitivity.In addition, in order to suppress the gasification in the preliminary drying as far as possible, the gasification temperature of sensitizer is preferably more than 150 ℃.On the other hand, if the gasification temperature of sensitizer is higher than 400 ℃, then sensitizer can not gasify when heat curing and remain in the cured film sometimes, thereby the water white transparency reduction.In addition, be gasified totally when the heat curing in order to make sensitizer, the gasification temperature of sensitizer is preferably below 250 ℃.
On the other hand, from the viewpoint of the transparency, can be preferably the sensitizer that the absorption in the visible region can be faded by rayed by the sensitizer that rayed is faded.In addition, the preferred compound that can fade by rayed is the compound that carries out dimerization by rayed.Because carry out dimerization by rayed, insoluble thereby molecular weight increases, so can obtain that chemical-resistant improves, thermotolerance improves, reduce such effect from the extract of transparent cured film.
In addition, from the viewpoint that realizes ISO, can carry out the viewpoint that dimerization fades by rayed, sensitizer is preferably the anthracene based compound.Because 9,10 be the anthracene based compound of hydrogen to thermally labile, so be preferably 9 especially, 10-two replaces the anthracene based compounds.In addition, from the dissolubility of raising sensitizer and reactive viewpoint of photodimerization reaction, be preferably 9 shown in the general formula (4), 10-dialkoxy anthracene based compound.
The R of general formula (4) 7～R 14Represent that independently of one another hydrogen atom, carbon number are that 1～20 alkyl, alkoxy, alkenyl, aryl, acyl group and they are substituted the organic group that gets.As the concrete example of alkyl, can enumerate methyl, ethyl, n-pro-pyl.As the concrete example of alkoxy, can enumerate methoxyl, ethoxy, propoxyl group, butoxy, amoxy.As the concrete example of alkenyl, can enumerate vinyl, acryloxy propyl group, methacryloxypropyl.As the concrete example of aryl, can enumerate phenyl, tolyl, naphthyl.As the concrete example of acyl group, can enumerate acetyl group.From the reactive viewpoint of gasification, photodimerizationization of compound, R 7～R 14Be preferably hydrogen atom or carbon number and be 1～6 organic group.More preferably R 7, R 10, R 11, R 14Be hydrogen atom.
The R of general formula (4) 15, R 16The expression carbon number is that 1～20 alkoxy and they are substituted the organic group that gets.As the concrete example of alkoxy, can enumerate methoxyl, ethoxy, propoxyl group, butoxy, amoxy.Viewpoint from the color fading reaction of the dissolubility of compound and photodimerization generation is preferably propoxyl group, butoxy especially.
To the not restriction especially of addition of sensitizer, preferably in the scope of 0.01～5 weight portion, add with respect to 100 parts by weight resin (polysiloxane+acryl resin).If break away from this scope, then transparency reduction, light sensitivity reduce.
Photosensitive composite of the present invention can contain thermal free radical initiator.Particularly during as acryl resin, preferably use thermal free radical initiator at the acryl resin that uses side chain to be connected with ethylenically unsaturated group.By containing thermal free radical initiator, thereby when heat curing, produce radical source.Consequently, the ethylenically unsaturated group in the acryl resin is each other by combined with radical and crosslinked, thereby improved the chemical-resistant of cured film.
As thermal free radical initiator, preferably enumerate the organic peroxide shown in the general formula (5).
R 17-O-O-R 18 (5)
The R of general formula (5) 17And R 18Can be the same or different, expression hydrogen atom, carbon number are that 1～30 alkyl, carbon number are that 6～30 aryl, carbon number are that 1～30 acyl group, carbon number are 2～30 ester group.The R of general formula (5) 17And R 18In cited alkyl, aryl, acyl group, ester group all can have substituting group.In addition, also can be not have substituent no substituent, can select according to the characteristic of composition.
As the concrete example of alkyl, can enumerate following group.That is, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, positive decyl, 1,1-dimethylbutyl etc.As the concrete example of aryl, can enumerate following group.That is, phenyl, tolyl, p-hydroxybenzene, 1-methyl isophthalic acid-phenylethyl, benzyl, 1-methyl isophthalic acid-3-(1-t-butylperoxy-1-Methylethyl)-phenylethyl etc.As the concrete example of acyl group, can enumerate following group.That is, acetyl group, 2,2-dimethyl propylene acyl group, 1-ethyl valeryl, benzoyl, 3-methyl benzoyl etc.As the concrete example of ester group, can enumerate following group.That is, carbomethoxy, ethoxycarbonyl, n-propyl base, isopropyl ester base, positive butyl ester base, tert-butyl ester base, Zhong Ding ester group, tert-butyl group hexamethylene ester group etc.Do not produce viewpoint, preferred alkyl or the aryl of gases such as carbon dioxide during wherein, from decomposition temperature height, curing.Under the situation of acyl group and/or ester group, decompose the further carbon dioxide that is produced that heats in back sometimes and remain in the film, thereby film becomes fragile.
As the concrete example of the organic peroxide shown in the general formula (5), can enumerate following compound.Promptly; 1; 1-two (t-butylperoxy) cyclohexane; 2; 2-two (4; 4-two (t-butylperoxy) cyclohexyl) propane; uncle's hexyl peroxidating isopropyl monocarbonate; the tert-butyl hydroperoxide maleate; tert-butyl hydroperoxide-3; 5; 5-tri-methyl hexanoic acid ester; the tert-butyl hydroperoxide laurate; tert-butyl hydroperoxide isopropyl monocarbonate; uncle's hexyl peroxide benzoate; 2; 5-dimethyl-2; 5-two (benzoyl peroxy) hexane; the tert-butyl hydroperoxide acetic acid esters; 2; 2-two (t-butylperoxy) butane; tert butyl peroxy benzoate; normal-butyl-4; 4-two (t-butylperoxy) valerate; two (uncle's 2-peroxidating isopropyl) benzene; the diisopropylbenzyl superoxide; two uncle's hexyl superoxide; 2; 5-dimethyl-2,5-two (t-butylperoxy) hexane; tert butyl isopropyl benzene peroxide; di-tert-butyl peroxide; right Alkane hydrogen peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3-diisopropyl benzene hydrogen peroxide, 1,1,3,3-tetramethyl butyl hydroperoxide, cumene hydroperoxide etc.
The formation method that regards to the cured film of having used photosensitive composite of the present invention down describes.By known method such as spin coating, slot coated photosensitive composite of the present invention is coated on the basal substrate, carries out preliminary drying with heating arrangements such as electric hot plate, baking ovens.Preliminary drying carried out in 50～150 ℃ temperature range 30 seconds～30 minutes, and pre-baked thickness is preferably 0.1～15 μ m.
After preliminary drying, use stepping exposure machine, mirror surface projection litho machine (MPA), parallel beam litho machine UV, visible light exposure machines such as (PLA), be situated between by required mask with 10～4000J/m 2About (being converted into the exposure of wavelength 365nm) carry out pattern exposure.
After exposure,, can obtain the eurymeric pattern by the dissolving exposed portion that develops.As developing method, preferably utilize methods such as spray, dipping, stirring in developer solution, to flood 5 seconds～10 minutes.As developer solution, can use known alkaline-based developer.As concrete example, can enumerate inorganic bases such as containing alkali-metal oxyhydroxide, carbonate, phosphate, silicate, borate, amines such as 2-DEAE diethylaminoethanol, monoethanolamine, diethanolamine, the aqueous solution etc. of compound more than a kind or 2 kinds in the quaternary ammonium salts such as Tetramethylammonium hydroxide, choline.In addition, preferably water carries out rinsing after developing, and can also dehydrate baking in 50～150 ℃ scope with heating arrangements such as electric hot plate, baking ovens in case of necessity.
Then, preferably bleach exposure.By bleaching exposure, remain in the unreacted quinone di-azido compound generation photodissociation in the film, the optical transparency of film further improves.As the method for bleaching exposure, use UV, visible light exposure machines such as PLA, with 100～20000J/m 2About (being converted into the exposure of wavelength 365nm) carry out blanket exposure.
Where necessary, in 50～150 ℃ scope, the film after bleaching exposure is carried out 30 seconds～30 minutes soft roasting with heating arrangements such as electric hot plate, baking ovens.Then, in 150～450 ℃ temperature range, solidified about 1 hour with heating arrangements such as electric hot plate, baking ovens, thereby form TFT in the display element with interlayer dielectric in planarization film, the semiconductor element or the core in the optical waveguide and/or coat cured film such as material.
Using the light transmission of cured film per 3 μ m thickness under wavelength 400nm of photosensitive composite making of the present invention is more than 90%, more preferably more than 92%.If light transmission is lower than 90%, then as the TFT substrate of liquid crystal display cells with under the situation of planarization film, backlight by the time change color takes place, white shows and has yellow.
Above-mentioned under wavelength 400nm the transmissivity of per 3 μ m thickness can try to achieve by the following method.Use spinner composition to be spin-coated on the TEMPAX glass plate, use electric hot plate 100 ℃ of following preliminary dryings 2 minutes with rotation number arbitrarily.Then, as the bleaching exposure, use PLA to use ultrahigh pressure mercury lamp with 3000J/m 2(being converted into the exposure of wavelength 365nm) exposes to whole face, and the use baking oven 220 ℃ of following heat curings 1 hour, is made the cured film of thickness 3 μ m in air." MultiSpec-1500 " that uses (strain) Shimadzu Seisakusho Ltd. to make measures the ultraviolet-visible absorption spectroscopy of resulting cured film, tries to achieve the transmissivity under wavelength 400nm.
This cured film is suitable for TFT planarization film, interlayer dielectric or the core in the optical waveguide in the semiconductor element in the display element and/or coats material etc.
Element among the present invention is meant aforesaid display element, semiconductor element or optical waveguide material with cured film of high-fire resistance, high transparent.Particularly can be used to have liquid crystal display cells and the organic EL display element of TFT effectively with planarization film.
Embodiment
The present invention will be described in more detail below to enumerate embodiment, but the present invention is not limited to these embodiment.In addition, in employed compound, as follows for the compound that uses abbreviation.
DAA: diacetone alcohol
PGMEA: propylene glycol methyl ether acetate
EAA: ethyl acetoacetate
GBL: gamma-butyrolacton
In addition, the acid number of the weight-average molecular weight of the solid component concentration of polysiloxane solution and acrylic resin soln, polysiloxane and acryl resin (Mw), acryl resin is following trying to achieve.
(1) solid component concentration
In the aluminium cup, take by weighing 1g polysiloxane (acryl resin) solution, use electric hot plate to heat 30 minutes evaporating liquid compositions down at 250 ℃.Remain in the solid constituent in the aluminium cup after the weighing heating, try to achieve the solid component concentration of polysiloxane (acryl resin) solution.
(2) weight-average molecular weight
Weight-average molecular weight is to utilize GPC (the 996 type detecting devices that Waters society makes, expansion solvent: tetrahydrofuran) try to achieve by polystyrene conversion.
(3) acid number
Take by weighing the resin solution that is equivalent to the 1g acryl resin, in this solution, drip potassium hydroxide (KOH) aqueous solution of 0.1N, try to achieve acid number according to the required KOH weight of neutralization.
Synthesizing of synthesis example 1 polysiloxane solution (a)
In the there-necked flask of 500ml, add 40.86g (0.3mol) methyltrimethoxy silane, 118.98g (0.6mol) phenyltrimethoxysila,e, 24.64g (0.1mol) 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 171.38g diacetone alcohol (being designated hereinafter simply as DAA), at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.092g phosphoric acid (is 0.05 weight % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, through 30 minutes oil bath is warming up to 115 ℃ then.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (a).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 120g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (a) is 40 weight %, and the weight-average molecular weight of polysiloxane is 6500.In addition, the phenyl containing ratio in the polysiloxane is 60 moles of % with respect to the Si atom.
Synthesizing of synthesis example 2 polysiloxane solutions (b)
In the there-necked flask of 500ml, add 23.84g (0.175mol) methyltrimethoxy silane; 99.15g (0.5mol) phenyltrimethoxysila,e; 12.32g (0.05mol) 2-(3; the 4-epoxycyclohexyl) ethyl trimethoxy silane; 66.09g (counting 0.275mol with the silane atom molal quantity) silicon dioxide granule DAA dispersion liquid Network オ one ト ロ Application PL-2L-DAA (make by Japan's chemical industry (strain); silicon dioxide granule concentration: 25 weight %); 63.04g DAA; at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.076g phosphoric acid (is 0.05 weight % with respect to the monomer that is added) in the 39.15g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, through 30 minutes oil bath is warming up to 115 ℃ then.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (b).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 85g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (b) is 46 weight %, and the weight-average molecular weight of polysiloxane is 8000.In addition, the phenyl containing ratio in the polysiloxane is 50 moles of % with respect to the Si atom.
Synthesizing of synthesis example 3 polysiloxane solutions (c)
In the there-necked flask of 500ml, add 88.53g (0.65mol) methyltrimethoxy silane, 49.58g (0.25mol) phenyltrimethoxysila,e, 24.64g (0.1mol) 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 144.83g DAA, at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.081g phosphoric acid (is 0.05 weight % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, then, oil bath is warming up to 115 ℃ through 30 minutes.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (c).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 120g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (c) is 40 weight %, and the weight-average molecular weight of polysiloxane is 9000.In addition, the phenyl containing ratio in the polysiloxane is 25 moles of % with respect to the Si atom.
Synthesizing of synthesis example 4 polysiloxane solutions (d)
In the there-necked flask of 500ml, add 20.43g (0.15mol) methyltrimethoxy silane, 158.64g (0.8mol) phenyltrimethoxysila,e, 12.32g (0.05mol) 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 179.54g DAA, at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.383g phosphoric acid (is 0.2 quality % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, then, oil bath is warming up to 115 ℃ through 30 minutes.Heating up after the beginning 1 hour, temperature reaches 100 ℃ in the solution, begins heated and stirred since then 3 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (d).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 120g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (d) is 40 weight %, and the weight-average molecular weight of polysiloxane is 7000.In addition, the phenyl containing ratio in the polysiloxane is 80 moles of % with respect to the Si atom.
Synthesizing of synthesis example 5 acrylic resin solns (a)
In the flask of 500ml, add 5g 2,2 '-azoisobutyronitrile, uncle's 5g dodecyl mercaptans, 150g propylene glycol methyl ether acetate (being designated hereinafter simply as PGMEA).Then, add 30g methacrylic acid, 35g benzyl methacrylate, 35g methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, at room temperature stir a moment, with the flask interior nitrogen replacement, then 70 ℃ of following heated and stirred 5 hours.Then, in the solution of gained, add 15g glycidyl methacrylate, 1g dimethyl benzylamine, 0.2g p methoxy phenol,, obtain acrylic resin soln (a) 90 ℃ of following heated and stirred 4 hours.
The solid component concentration of the acrylic resin soln of gained (a) is 43 weight %, and the weight-average molecular weight of acryl resin is 10600, and acid number is 118mgKOH/g, and unsaturated equivalent is 1090.
Synthesizing of synthesis example 6 acrylic resin solns (b)
In the flask of 500ml, add 5g 2,2 '-azoisobutyronitrile, 150g PGMEA.Then, add 27g methacrylic acid, 38g benzyl methacrylate, 35g methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, at room temperature stir a moment, with the flask interior nitrogen replacement, then 70 ℃ of following heated and stirred 5 hours.Then, in the solution of gained, add 15g glycidyl methacrylate, 1g dimethyl benzylamine, 0.2g p methoxy phenol,, obtain acrylic resin soln (b) 90 ℃ of following heated and stirred 4 hours.
The solid component concentration of the acrylic resin soln of gained (b) is 43 weight %, and the weight-average molecular weight of acryl resin is 31400, and acid number is 105mgKOH/g, and unsaturated equivalent is 1090.
Synthesizing of synthesis example 7 acrylic resin solns (c)
In the flask of 500ml, add 5g 2,2 '-azoisobutyronitrile, 150g PGMEA.Then, add 15g methacrylic acid, 45g methyl methacrylate, 40g styrene, at room temperature stir a moment,, 70 ℃ of following heated and stirred 5 hours, obtain acrylic resin soln (c) then the flask interior nitrogen replacement.
The solid component concentration of the acrylic resin soln of gained (c) is 43 weight %, and the weight-average molecular weight of acryl resin is 20000, and acid number is 97mgKOH/g, and unsaturated equivalent is 0.
Synthesizing of synthesis example 8 acrylic resin solns (d)
In the flask of 500ml, add 3g 2,2 '-azoisobutyronitrile, 50g PGMEA.Then, add 30g methacrylic acid, 35g benzyl methacrylate, 35g methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, at room temperature stir a moment, with the flask interior nitrogen replacement, then 70 ℃ of following heated and stirred 5 hours.Then, in the solution of gained, add 15g glycidyl methacrylate, 1g dimethyl benzylamine, 0.2g p methoxy phenol, 100g PGMEA, 90 ℃ of following heated and stirred 4 hours, obtain acrylic resin soln (d) then.
The solid component concentration of the acrylic resin soln of gained (d) is 43 weight %, and the weight-average molecular weight of acryl resin is 65000, and acid number is 118mgKOH/g, and unsaturated equivalent is 1090.
Synthesizing of synthesis example 9 acrylic resin solns (e)
In the flask of 500ml, add 5g 2,2 '-azoisobutyronitrile, uncle's 20g dodecyl mercaptans, 200gPGMEA.Then, add 30g methacrylic acid, 35g benzyl methacrylate, 35g methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, at room temperature stir a moment, with the flask interior nitrogen replacement, then 70 ℃ of following heated and stirred 5 hours.Then, in the solution of gained, add 15g glycidyl methacrylate, 1g dimethyl benzylamine, 0.2g p methoxy phenol,, obtain acrylic resin soln (e) 90 ℃ of following heated and stirred 4 hours.
The solid component concentration of the acrylic resin soln of gained (e) is 43 weight %, and the weight-average molecular weight of acryl resin is 4500, and acid number is 118mgKOH/g, and unsaturated equivalent is 1090.
Synthesizing of synthesis example 10 quinone di-azido compounds (a)
Flow down at drying nitrogen, make 21.23g (0.05mol) TrisP-PA (trade name, Honshu chemical industry (strain) is made) and 37.62g (0.14mol) 5-naphthoquinones two nitrine sulfonic acid chlorides be dissolved in 450g 1, in the 4-diox, be controlled at room temperature.Under not making the condition that is warmed up in the system more than 35 ℃, 50g 1, the triethylamine 15.58g (0.154mol) of 4-diox have been mixed to wherein dripping.Stirred 2 hours down at 30 ℃ after dripping.Filter triethylamine salt, filtrate is added to the water.Then, filter and collect the precipitation of being separated out.Should precipitate with vacuum drier is dry, obtain the quinone di-azido compound (a) of following structure.
Figure GPA00001029901900291
Synthesizing of synthesis example 11 quinone di-azido compounds (b)
Flow down at drying nitrogen, make 15.32g (0.05mol) TrisP-HAP (trade name, Honshu chemical industry (strain) is made) and 26.87g (0.1mol) 5-naphthoquinones two nitrine sulfonic acid chlorides be dissolved in 450g 1, in the 4-diox, be controlled at room temperature.Under not making the condition that is warmed up in the system more than 35 ℃, drip therein and mixed 50g 1, the triethylamine 11.13g (0.11mol) of 4-diox.Stirred 2 hours down at 30 ℃ after dripping.Filter triethylamine salt, filtrate is added to the water.Then, filter and collect the precipitation of being separated out.Should precipitate with vacuum drier is dry, obtain the quinone di-azido compound (b) of following structure.
Figure GPA00001029901900292
Synthesizing of synthesis example 12 polysiloxane solutions (e)
In the there-necked flask of 500ml, add 54.48g (0.4mol) methyltrimethoxy silane, 99.15g (0.5mol) phenyltrimethoxysila,e, 24.64g (0.1mol) 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 163.35g DAA, at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.535g phosphoric acid (is 0.3 weight % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, then, oil bath is warming up to 115 ℃ through 30 minutes.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (e).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 120g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (e) is 40 weight %, and the weight-average molecular weight of polysiloxane is 6000.In addition, the phenyl containing ratio in the polysiloxane is 50 moles of % with respect to the Si atom.
Synthesizing of synthesis example 13 polysiloxane solutions (f)
In the there-necked flask of 500ml, add 54.48g (0.4mol) methyltrimethoxy silane, 99.15g (0.5mol) phenyltrimethoxysila,e, 24.64g (0.1mol) 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 163.80g DAA, at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.089g phosphoric acid (is 0.05 weight % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, then, oil bath is warming up to 115 ℃ through 30 minutes.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (f).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 110g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (f) is 42 weight %, and the weight-average molecular weight of polysiloxane is 4000.In addition, the phenyl containing ratio in the polysiloxane is 50 moles of % with respect to the Si atom.
Synthesizing of synthesis example 14 polysiloxane solutions (g)
In the there-necked flask of 500ml, add 68.10g (0.5mol) methyltrimethoxy silane, 99.15g (0.5mol) phenyltrimethoxysila,e, 149.91g DAA, at room temperature stir on one side, on one side through being added on the phosphate aqueous solution that is dissolved with 0.502g phosphoric acid (is 0.3 weight % with respect to the monomer that is added) in the 54g water in 10 minutes.Then, stirred 30 minutes in the oil bath with 40 ℃ of flask immersions, then, oil bath is warming up to 115 ℃ through 30 minutes.Heating up, the interior temperature of solution reaches 100 ℃ after the beginning 1 hour, begins heated and stirred since then 2 hours (interior temperature is 100～110 ℃), obtains polysiloxane solution (g).In addition, in the heated and stirred process, with 0.05L (liter)/minute feeding nitrogen.Total distillates methyl alcohol, the water of 120g as the accessory substance in the reaction.
The solid component concentration of the polysiloxane solution of gained (g) is 40 weight %, and the weight-average molecular weight of polysiloxane is 6500.In addition, the phenyl containing ratio in the polysiloxane is 50 moles of % with respect to the Si atom.
Synthesizing of synthesis example 15 quinone di-azido compounds (c)
Flow down at drying nitrogen, make 15.32g (0.05mol) Ph-cc-AP-MF (trade name, Honshu chemical industry (strain) is made) and 37.62g (0.14mol) 5-naphthoquinones two nitrine sulfonic acid chlorides be dissolved in 450g 1, in the 4-diox, be controlled at room temperature.Under not making the condition that is warmed up in the system more than 35 ℃, drip and mixed 50g 1, the triethylamine 15.58g (0.154mol) of 4-diox.Stirred 2 hours down at 30 ℃ after dripping.Filter triethylamine salt, filtrate is added to the water.Then, filter and collect the precipitation of being separated out.Should precipitate with vacuum drier is dry, obtain the quinone di-azido compound (c) of following structure.
Figure GPA00001029901900311
Embodiment 1
Under yellow fluorescent lamp with the polysiloxane solution (a) of 19.62g synthesis example 1 gained, 7.82g the acrylic resin soln (b) of synthesis example 6 gained, 1.01g the quinone di-azido compound (a) of synthesis example 10 gained, 0.11g KBM202ss (dimethoxydiphenylsilane as silane coupling agent, trade name, SHIN-ETSU HANTOTAI's chemical industry (strain) is made), 0.11g (2-(3 for KBM303, the 4-epoxycyclohexyl) ethyl trimethoxy silane, trade name, SHIN-ETSU HANTOTAI's chemical industry (strain) is made), 0.06g the N-tert-butyl group-3-(3-trimethoxy propyl group) succinimide, 5.10g DAA as solvent, 16.17g PGMEA mixes, stir, make homogeneous solution, use the filtrator of 0.45 μ m to filter then, thus preparation composition 1.In addition, the mixture ratio of polysiloxane and acryl resin is polysiloxane/acryl resin=70/30.
At TEMPAX glass plate (rising sun テ Network ノ ガ ラ ス plate (strain) manufacturing), silicon chip and forming on the OA-10 glass plate (NEG (strain) manufacturing) on the substrate (hereinafter to be referred as the SiN substrate) that the silicon nitride film about 100nm forms, use spinner (1H-360S that ミ カ サ (strain) makes) with any rotation number spin coating composition 1, use electric hot plate (big Japanese ス Network リ one Application manufacturing (strain) make SCW-636) 100 ℃ of following preliminary dryings 2 minutes then, make the film of thickness 3 μ m.Use parallel beam litho machine (being designated hereinafter simply as PLA) (キ ヤ ノ Application (strain) is made PLA-501F), be situated between with ultrahigh pressure mercury lamp and with gray scale mask the film of making carried out pattern exposure by sensitometry, use automatic developing device (Long damp industry (strain) make AD-2000) then, with the tetramethylammonium hydroxide aqueous solution ELM-D (trade name of 2.38 weight %, the ガ ス of Mitsubishi chemistry (strain) is made) spray and developed 80 seconds, then use water rinse 30 seconds.Then, as the bleaching exposure, use PLA (キ ヤ ノ Application (strain) is made PLA-501F) to use ultrahigh pressure mercury lamp with 3000J/m 2(being converted into the exposure of wavelength 365nm) exposes to whole face.Then, use electric hot plate, then use baking oven (タ バ イ エ ス ペ Star Network (strain) is made IHPS-222) in air, to solidify 1 hour down, make cured film at 220 ℃ 110 ℃ soft down roasting (soft bake) 2 minutes.
Table 3 shows the evaluation result of sensitometric characteristic and cured film characteristic.In addition, the evaluation in the table is carried out by the following method.And the evaluation of following (4), (5), (6), (7), (11) is to use silicon wafer substrate to carry out, and the evaluation of (9) is to use the TEMPAX glass plate to carry out, and the evaluation of (10) is to use the SiN substrate to carry out.
(4) determining film thickness
Use ラ system ダ エ one ス STM-602 (trade name, big Japanese ス Network リ one Application manufacturing), under 1.50 refractive index, measure.
(5) calculating of residual film ratio
Residual film ratio calculates according to following formula.
The pre-baked thickness of unexposed portion thickness ÷ * 100 after residual film ratio (%)=development
(6) calculating of light sensitivity
Form the exposure (below be referred to as optimum exposure) of line and the gap pattern of 10 μ m as light sensitivity with exposure, after developing with 1 to 1 width.
(7) calculating of resolution
Minimum pattern size after will developing under optimum exposure is as the back resolution of developing, with the minimum pattern size after solidifying as solidifying back resolution.
(8) weight slip
The composition that in the aluminium alms bowl, adds about 100mg, use thermogravimetric amount determining device (TGA-50, (strain) Shimadzu Seisakusho Ltd. makes), in nitrogen atmosphere gas, be heated to 300 ℃ with 10 ℃/minute programming rates, directly be heating and curing 1 hour, and be warming up to 400 ℃, the gravimetry slip with 10 ℃/minute programming rate then.Weight when mensuration reaches 300 ℃, and then measure weight when reaching 400 ℃, the weight when obtaining itself and 300 ℃ poor, the weight percent of obtaining minimizing is as the weight slip.
(9) mensuration of light transmission
Use MultiSpec-1500 (trade name, (strain) Shimadzu Seisakusho Ltd.), at first only measure the TEMPAX glass plate, then with its ultraviolet-visible absorption spectroscopy as benchmark.Then on the TEMPAX glass plate, form the cured film (not carrying out pattern exposure) of composition, use single beam to measure this sample, try to achieve the light transmission of per 3 μ m thickness under wavelength 400nm, with the difference of itself and benchmark light transmission as cured film.
(10) adhering evaluation
On the SiN substrate, form the cured film (not carrying out pattern exposure) of composition, on this cured film, stand vertically the aluminum stud pin (manufacturing of QUAD GROUP society) that scribbles epoxy resin, use baking oven in air, to heat 30 minutes down, make stud pin and cured film bonding at 200 ℃.Then, use テ Application シ ロ Application RTM-100 (trade name, (strain) オ リ エ Application テ Star Network is made), with 5mm/ minute haulage speed, with respect to cured film trussed shore bolt pin vertically, the intensity when measuring cured film/substrate interface and peeling off.
(11) evaluation of chemical-resistant (estimating) by the film impairment amount that TOK-106 handles
On silicon chip, form the cured film of composition, this sample middle the immersion 10 minutes of TOK-106 (trade name, Tokyo are answered chemical industry (strain) manufacturing) that is heated to 70 ℃, was used water rinse 5 minutes then.Estimate chemical-resistant according to thickness reduction by this processing.
Embodiment 2～12, comparative example 1～4
According to table 1,2 compositions of being put down in writing, similarly prepare composition 2～16 with composition 1.In addition, リ Port キ シ SPCR-10X (trade name as the acrylic resin soln use, clear and macromolecule (strain) is made) be the glycidyl methacrylate adduct (weight-average molecular weight: 17300 of methacrylic acid/benzyl methacrylate/methacrylic acid three ring decyl ester multipolymers, acid number: 109mgKOH/g), リ Port キ シ SPCR-6X (trade name, clear and macromolecule (strain) is made) be methacrylic acid/benzyl methacrylate/methacrylic acid three ring decyl ester multipolymers the glycidyl methacrylate adduct (weight-average molecular weight: 10700, acid number: 127mgKOH/g).In addition, KBM403 (trade name as the silane coupling agent use, SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), the エ ピ コ one ト 828 (trade names of using as crosslinking chemical, ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) is made), ニ カ ラ Star Network MX-270, ニ カ ラ Star Network MW-30HM (trade name, three and ケ ミ カ Le (strain) make) be have following shown in the compound of structure.In addition, the MCOPDMS-TFMS (manufacturing of three new chemical industry (strain)) that uses as crosslinking accelerator is a 4-methoxycarbonyl group oxygen base phenyl dimethyl trifluoromethayl sulfonic acid sulfonium, WPAG-469 (trade name, make with the pure pharmaceutical worker's industry of light (strain)) be the 20%PGMEA solution of 4-aminomethyl phenyl diphenyl perfluorinated butane sulfonic acid sulfonium, DPA (trade name as the sensitizer use, Kawasaki changes into industry (strain) manufacturing) be 9,10-dipropoxy anthracene.
Figure GPA00001029901900361
Figure GPA00001029901900371
Use each composition of gained, estimate each composition similarly to Example 1.But in the evaluation of embodiment 2,3,5,8,9,11 and comparative example 3,4, development is to develop with 0.4 weight % tetramethylammonium hydroxide aqueous solution (with the ELM-D dilute with water and solution) spray to carry out in 80 seconds.
The results are shown in table 3.
Figure GPA00001029901900381
The industry utilizability
The present invention can be used as the interlayer dielectric of the planarization film such as thin film transistor (TFT) (TFT) substrate that is used to form liquid crystal display cells and/or organic EL display element, semiconductor element or the core of fiber waveguide and/or the material of coating material and uses.

Claims (6)

1. photosensitive composite, contain (a) polysiloxane, (b) acryl resin, (c) quinone di-azido compound, (d) solvent, wherein, (a) polysiloxane/(b) mixture ratio of acryl resin counts 80/20～20/80 with weight ratio, and (a) polysiloxane is to react synthetic polysiloxane by the organosilane shown in the general formula (1) more than a kind
Figure FPA00001029901800011
In the following formula, R 1Expression hydrogen atom, carbon number are that 1～10 alkyl, carbon number are that 2～10 alkenyl, carbon number are any in 6～15 the aryl, a plurality of R 1Can be the same or different respectively; R 2Expression hydrogen atom, carbon number are that 1～6 alkyl, carbon number are that 2～6 acyl group, carbon number are any in 6～15 the aryl, a plurality of R 2Can be the same or different respectively; N represents 0～3 integer.
2. photosensitive composite as claimed in claim 1, in (a) polysiloxane, the phenyl containing ratio in the polysiloxane is 30～70 moles of % with respect to the Si atom.
3. photosensitive composite as claimed in claim 1 or 2, (b) side chain of acryl resin has ethylenically unsaturated group.
4. as each described photosensitive composite of claim 1～3, (b) weight-average molecular weight of acryl resin is in 5000～50000 scope.
5. cured film is the cured film that each the described photosensitive composite by claim 1～4 forms, and the light transmission of per 3 μ m thickness is more than 90% under wavelength 400nm.
6. the element that has the described cured film of claim 5.
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CN111240157A (en) * 2018-11-29 2020-06-05 罗门哈斯电子材料韩国有限公司 Positive photosensitive resin composition and cured film prepared therefrom
CN113641081A (en) * 2021-07-15 2021-11-12 深圳迪道微电子科技有限公司 High-adhesion positive photoresist composition, synthesis method thereof and cured film

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CN101784958B (en) 2013-03-27
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JP5099140B2 (en) 2012-12-12
JPWO2009028360A1 (en) 2010-11-25

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