CN103443707A - Resin composition and semiconductor element substrate - Google Patents

Resin composition and semiconductor element substrate Download PDF

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Publication number
CN103443707A
CN103443707A CN2012800148101A CN201280014810A CN103443707A CN 103443707 A CN103443707 A CN 103443707A CN 2012800148101 A CN2012800148101 A CN 2012800148101A CN 201280014810 A CN201280014810 A CN 201280014810A CN 103443707 A CN103443707 A CN 103443707A
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group
resin
methyl
acid
silane
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田口和典
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Zeon Corp
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Nippon Zeon Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • 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
    • 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
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • 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
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a resin composition comprising a binder resin (A), a silane-modified resin (B), and a compound (C) having an acidic group or a thermally latent acidic group, the resin composition being characterized in that the proportion of the silane-modified resin (B) and the compound (C) having an acidic group or a thermally latent acidic group, when expressed as "silane-modified resin (B)/compound (C) having an acidic group or a thermally latent acidic group," ranges from 0.5 to 20.

Description

Resin combination and semiconductor element substrate
Technical field
The present invention relates to resin combination and the semiconductor element substrate that possesses the resin molding formed by this resin combination, in more detail, relate to and there is excellent storage stability, and can form developing pattern formative and the resin combination of the resin molding of transparency excellence and the semiconductor element substrate that possesses the resin molding formed by this resin combination.
Background technology
In the electronic units such as the various display elements such as organic EL or liquid crystal display cells, integrated circuit component, solid-state imager, color filter film, black matrix", as the diaphragm for preventing its deteriorated or damage, for the planarization film that makes element surface or distribution planarization, for the electrical insulating film that keeps electrical insulating property etc., be provided with various resin moldings.In addition, in organic EL in order to separate luminous body, be provided with the resin molding as the pixel separation film, in addition, in the elements such as the display element of using at the film transistor type liquid crystal or integrated circuit component, in order to make to insulate between the distribution with the stratiform configuration, be provided with the resin molding as interlayer dielectric.
In the past, as the resin material that is used to form these resin moldings, the heat-curing resin materials such as universal epoxy resin.In recent years, follow the densification of distribution and device, also require to develop the new resin material of the electrical specification excellences such as low-dielectric for these resin materials.
For corresponding these requirements, for example, disclose following radiation sensitive resin composition in patent documentation 1, it contains: resin (A), have epoxy radicals crosslinking chemical (B), there is triazine ring structure or glycoluril structure and there is crosslinking chemical (C) and the radiation-sensitive compound (D) of functional group more than a kind be selected from imino group, methylol and alkoxy butyl.Yet, the pattern formative that the utilization of the resin molding that uses the resin combination of this patent documentation 1 record to obtain is developed, particularly developing adaptation (adaptation of the developing pattern making that the developing pattern width attenuates, during high-precision refinement) may not be abundant, therefore, expectation improves the pattern formative of utilizing development.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2010-224533 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of resin combination, this resin combination has excellent storage stability, and can form pattern formative and the excellent resin molding of the transparency.In addition, the present invention also aims to provide the semiconductor element substrate that possesses the resin molding formed by such resin combination.
The method of dealing with problems
The inventor etc. are in order to address the above problem, through further investigation, found that: by adopting following resin combination, can realize above-mentioned purpose, thereby completed the present invention, described resin combination ratio with regulation in adhesive resin coordinates silane-modified resin and the compound with acidic-group or hot latency acidic-group to obtain.
; according to the present invention; a kind of resin combination is provided; it is characterized in that; this resin combination contains adhesive resin (A), silane-modified resin (B) and has acidic-group or the compound of hot latency acidic-group (C); wherein, the ratio of above-mentioned silane-modified resin (B) and the above-mentioned compound (C) with acidic-group or hot latency acidic-group is counted " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group "=0.5～20 with weight ratio.
Preferred above-mentioned silane-modified resin (B) is to be selected from that at least one macromolecular material in polyester, polyamide, polyimide, polyamic acid, epoxy resin, acryl resin, urethane resin and phenolics and silicon compound carry out chemical bonding and the compound that obtains.
The partial hydrolysis condensation product that preferred above-mentioned silicon compound is the silicon compound shown in the silicon compound shown in following formula and/or following formula.
(R 8) r-Si-(OR 9) 4-r
(in above-mentioned formula, the integer that r is 0～3, R 8for thering is alkyl, the aryl of carbon number 6～20 or the unsaturated aliphatic base of carbon number 2～10 with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 8when a plurality of, a plurality of R 8can be identical also can be different separately.R 9for hydrogen atom maybe can have the alkyl with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 9when a plurality of, a plurality of R 9can be identical also can be different separately.)
Preferred above-mentioned silane-modified resin (B) containing proportional with respect to above-mentioned adhesive resin (A) 100 weight portions, be 1～100 weight portion.
Preferred above-mentioned adhesive resin (A) is for having cyclic olefin polymer or the acryl resin of protic polar group.
Preferred resin combination of the present invention also contains radiation-sensitive compound (D).
Preferred resin combination of the present invention also contains crosslinking chemical (E).
In addition, according to the present invention, provide the semiconductor element substrate that possesses the resin molding formed by above-mentioned any resin combination.
The effect of invention
According to the present invention, can provide and there is excellent storage stability and can access the developing pattern formative and the resin combination of the resin molding that the transparency is excellent and the semiconductor element substrate that possesses the resin molding formed by such resin combination.
the embodiment of invention
Resin combination of the present invention contains adhesive resin (A), silane-modified resin (B) and has acidic-group or the compound of hot latency acidic-group (C), and silane-modified resin (B) is counted the scope of " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group "=0.5～20 with the ratio of the compound (C) with acidic-group or hot latency acidic-group with weight ratio.
(adhesive resin (A))
As the adhesive resin used in the present invention (A), be not particularly limited, the cyclic olefin polymer (A1), acryl resin (A2), Cardo resin (A3), polysiloxane (A4) or the polyimide (A5) that preferably there is the protic polar group, wherein, the cyclic olefin polymer (A1) that particularly preferably there is the protic polar group.
These adhesive resins (A) both can be used separately respectively or also can be used in combination two or more.
As the cyclic olefin polymer with protic polar group (A1) (below, referred to as " cyclic olefin polymer (A1) "), can enumerate 1 or the polymkeric substance of cyclic olefin monomers of more than two kinds or, 1 or cyclic olefin monomers of more than two kinds and the multipolymer that can form with the monomer of its copolymerization, but in the present invention, as the monomer that is used to form cyclic olefin polymer (A1), preferably at least use the cyclic olefin monomers (a) with protic polar group.
Wherein, the protic polar group refers to the hydrogen atom Direct Bonding on the atom that belongs to the periodic table of elements the 15th family or the 16th family and the group that forms.In the atom that belongs to the periodic table of elements the 15th family or the 16th family, preferably belong to the atom in the 1st or the 2nd cycle of the periodic table of elements the 15th family or the 16th family, more preferably oxygen atom, nitrogen-atoms or sulphur atom, particularly preferably oxygen atom.
As the concrete example of such protic polar group, can enumerate the polar group that hydroxyl, carboxyl (hydroxycarbonyl group), sulfonic group, phosphate etc. have oxygen atom; Primary amino radical, secondary amino group, primary amide base, secondary amide base (imide) etc. have the polar group of nitrogen-atoms; Sulfydryls etc. have the polar group of sulphur atom etc.Wherein, preferably there is the group of oxygen atom, more preferably carboxyl.
In the present invention, the number of the protic polar group combined with the cyclic olefin resin with protic polar group is not particularly limited, and can also comprise different types of protic polar group.
As the concrete example of the cyclic olefin monomers with protic polar group (a) (below, referred to as " monomer (a) "), can enumerate: 2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene, 2-carboxyl methyl-2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-methoxycarbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-ethoxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-propoxycarbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-butoxy carbonyl methyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-pentyloxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-hexyloxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-cyclohexyloxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-phenyloxycarbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-naphthoxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-biphenylyloxy carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-benzyloxycarbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-2-hydroxyl-oxethyl carbonyl methyl bicycle [2.2.1] heptan-5-alkene, 2,3-dihydroxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-methoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-ethoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-propoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-butoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-pentyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-hexyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-cyclohexyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-phenyloxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-naphthoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-biphenylyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-benzyloxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-hydroxyl-oxethyl carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group-3-hydroxycarbonyl group methyl bicycle [2.2.1] heptan-5-alkene, 3-methyl-2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene, 3-hydroxymethyl-2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene, 2-hydroxycarbonyl group three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3,8-diene, 4-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4,5-dihydroxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-carboxyl methyl-4-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, N-(hydroxycarbonyl group methyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(hydroxycarbonyl group ethyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(hydroxycarbonyl group amyl group) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(dihydroxy carbonyl ethyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(dihydroxy carbonyl propyl group) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(hydroxycarbonyl group phenethyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(2-(4-hydroxy phenyl)-1-(hydroxycarbonyl group) ethyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imide, N-(hydroxycarbonyl group phenyl) dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboxyl acid imides etc. are containing the carboxyl cyclic olefin, 2-(4-hydroxy phenyl) dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-(4-hydroxy phenyl) dicyclo [2.2.1] heptan-5-alkene, 4-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 2-hydroxyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxymethyl dicyclo [2.2.1] heptan-5-alkene, 2-hydroxyethyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-hydroxymethyl dicyclo [2.2.1] heptan-5-alkene, 2, 3-dihydroxy methyl bicycle [2.2.1] heptan-5-alkene, 2-(hydroxyl-oxethyl carbonyl) dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-(hydroxyl-oxethyl carbonyl) dicyclo [2.2.1] heptan-5-alkene, 2-(1-hydroxyl-1-trifluoromethyl-2, 2, the 2-trifluoroethyl) dicyclo [2.2.1] heptan-5-alkene, 2-(2-hydroxyl-2-trifluoromethyl-3, 3, the 3-trifluoro propyl) dicyclo [2.2.1] heptan-5-alkene, 3-hydroxyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-4,8-diene, 3-hydroxymethyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-4,8-diene, 4-hydroxyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-hydroxymethyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4,5-dihydroxy methyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-(hydroxyl-oxethyl carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-(hydroxyl-oxethyl carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, N-(hydroxyethyl) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(hydroxy phenyl) dicyclo [2.2.1] heptan-5-alkene-2, the hydroxyl cyclic olefins such as 3-dicarboxyl acid imide etc.Wherein, the viewpoint improved from the adaptation of resulting resin molding is considered, preferably containing carboxyl cyclic olefin, particularly preferably 4-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene.These monomers (a) both can have been distinguished use separately, also can combine two or more use.
In cyclic olefin polymer (A1), the unit of monomer (a) be preferably 10～90 % by mole with respect to whole monomeric units containing proportional.When the unit of monomer (a) containing proportional when very few, radiation-sensitive while in resin combination of the present invention, adding the radiation-sensitive compound is insufficient, likely produce dissolved residue during development, the unit of monomer (a) containing proportional when too much, the dissolubility of cyclic olefin polymer (A1) in polar solvent is likely insufficient.
In addition, the unit of monomer (a) is different and different according to the kind of the resin molding formed by resin combination of the present invention containing proportional preferred scope.Particularly; when this resin molding diaphragm that is active-matrix substrate or encapsulating film of organic EL substrate etc. utilize photoetching process to carry out the resin molding of patterning; the unit of monomer (a) containing proportional more preferably 40～70 % by mole, be particularly preferably 50～60 % by mole.On the other hand, when the pixel separation film of the gate insulating film that is active-matrix substrate at resin molding or organic EL substrate etc. does not utilize photoetching process to carry out the resin molding of patterning, the unit of monomer (a) containing proportional more preferably 20～80 % by mole, be particularly preferably 30～70 % by mole.
In addition, the cyclic olefin polymer used in the present invention (A1) can be the cyclic olefin monomers (a) with protic polar group and the multipolymer that can obtain with monomer (b) copolymerization of its copolymerization.As such monomer that can copolymerization, can enumerate: monomer (b3) in addition of cyclic olefin monomers (b1), the cyclic olefin monomers (b2) that does not there is polar group and the cyclic olefin with the polar group beyond the protic polar group (below, referred to as " monomer (b1) ", " monomer (b2) ", " monomer (b3) ").
As the cyclic olefin monomers (b1) with protic polar group polar group in addition, for example, can enumerate: the cyclic olefin with N-substituted imides base, ester group, cyano group, anhydride group or halogen atom.
As the cyclic olefin with N-substituted imides base, for example can enumerate the monomer shown in the monomer shown in following formula (1) or following formula (2).
[Chemical formula 1]
Figure BDA0000386244120000061
(in above-mentioned formula (1), R 1the alkyl or aryl that means hydrogen atom or carbon number 1～16.N means 1 or 2 integer.)
[Chemical formula 2]
Figure BDA0000386244120000062
(in above-mentioned formula (2), R 2the alkylidene that means carbon number 1～3, R 3mean the alkyl of carbon number 1～10 or the haloalkyl of carbon number 1～10.)
In above-mentioned formula (1), R 1alkyl or aryl for carbon number 1～16, the concrete example of alkyl, can enumerate: the straight chained alkyls such as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl; The cyclic alkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring undecyl, cyclo-dodecyl, norborneol alkyl, bornyl, isobornyl, decahydro naphthyl, three ring decyls, adamantyl; The branched alkyls such as 2-propyl group, 2-butyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl, 1-methyl butyl, 2-methyl butyl, 1-methyl amyl, 1-ethyl-butyl, 2-methyl hexyl, 2-ethylhexyl, 4-methylheptyl, 1-methyl nonyl, 1-methyl tridecyl, 1-methyl myristyl etc.In addition, as the concrete example of aryl, can enumerate benzyl etc.Wherein, from thermotolerance and the dissolubility polar solvent, consider aspect more excellent, preferably alkyl and the aryl of carbon number 6～14, the more preferably alkyl of carbon number 6～10 and aryl.When the carbon number of these groups is too small, the dissolubility in polar solvent is likely poor, when carbon number is excessive, and poor heat resistance, in addition, by the resin molding patterning time, likely Yin Re and melting disappear pattern.
As the concrete example of the monomer shown in above-mentioned formula (1), can enumerate: dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-phenyl-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-methyl bicycle [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-ethyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-propyl group dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-butyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-cyclohexyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-adamantyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl amyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl amyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl-butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethyl-butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-butyl amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-butyl amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-propyl group amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-propyl group amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-Methyl Octyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-Methyl Octyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-Methyl Octyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-Methyl Octyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(5-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl decyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl dodecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl undecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl dodecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl tridecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl myristyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl pentadecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-phenyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4,5-dicarboxyl acid imide, N-(2,4-Dimethoxyphenyl)-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4,5-dicarboxyl acid imide etc.Wherein, they can distinguish use separately, combine two or more use.
On the other hand, in above-mentioned formula (2), R 2for the alkylidene of carbon number 1～3, as the alkylidene of carbon number 1～3, can enumerate methylene, ethylidene, propylidene and isopropylidene.Wherein, because polymerization activity is good, so preferred methylene and ethylidene.
In addition, in above-mentioned formula (2), R 3for the alkyl of carbon number 1～10 or the haloalkyl of carbon number 1～10.As the alkyl of carbon number 1～10, such as enumerating methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, hexyl and cyclohexyl etc.Haloalkyl as carbon number 1～10, for example can enumerate: methyl fluoride, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentachloro-ethyl, heptachlor propyl group, perfluoro butyl and perfluor amyl group etc.Wherein, due to the dissolubility excellence in polar solvent, so R 3preferable methyl and ethyl.
In addition, the monomer shown in above-mentioned formula (1), (2) for example can be by corresponding amine and 5-norborene-2, and the 3-dicarboxylic anhydride carries out amidation process and obtains.In addition, resulting monomer can separate efficiently by the reactant liquor with known method separation, purifying amidation process.
As the cyclic olefin with ester group, for example can enumerate: 2-acetoxyl group dicyclo [2.2.1] heptan-5-alkene, 2-acetoxy-methyl dicyclo [2.2.1] heptan-5-alkene, 2-methoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-ethoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-propoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-butoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-cyclohexyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-methoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-ethoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-propoxycarbonyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-butoxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-cyclohexyloxy carbonyl dicyclo [2.2.1] heptan-5-alkene, 2-(2, 2, 2-trifluoro ethoxy carbonyl) dicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-(2, 2, 2-trifluoro ethoxy carbonyl) dicyclo [2.2.1] heptan-5-alkene, 2-methoxycarbonyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-alkene, 2-ethoxy carbonyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-alkene, 2-propoxycarbonyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-alkene, 4-acetoxyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-ethoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-propoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-butoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-methoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-ethoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-propoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-butoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene etc.
As the cyclic olefin with cyano group, for example can enumerate: 4-cyano group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-cyano group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4,5-dicyano Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 2-cyano-bicyclo [2.2.1] heptan-5-alkene, 2-methyl-2-cyano-bicyclo [2.2.1] heptan-5-alkene, 2,3-dicyano dicyclo [2.2.1] heptan-5-alkene etc.
As the cyclic olefin with anhydride group, for example, can enumerate: Fourth Ring [6.2.1.13,6.02,7] 12 carbon-9-alkene-4,5-dicarboxylic anhydride, dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, 2-carboxyl methyl-2-hydroxycarbonyl group dicyclo [2.2.1] heptan-5-alkene anhydride etc.
As the cyclic olefin with halogen atom, for example, can enumerate: 2-chlorine dicyclo [2.2.1] heptan-5-alkene, 2-chloromethyl dicyclo [2.2.1] heptan-5-alkene, 2-(chlorphenyl) dicyclo [2.2.1] heptan-5-alkene, 4-chlorine Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-methyl-4-chlorine Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene etc.
These monomers (b1) both can have been distinguished use separately, also can combine two or more use.
As the cyclic olefin monomers that does not there is polar group (b2), can enumerate: dicyclo [2.2.1] hept-2-ene" (also referred to as " norborene "), 5-ethyl-dicyclo [2.2.1] hept-2-ene", 5-butyl-dicyclo [2.2.1] hept-2-ene", 5-ethylidene-dicyclo [2.2.1] hept-2-ene", 5-methene-dicyclo [2.2.1] hept-2-ene", 5-vinyl-dicyclo [2.2.1] hept-2-ene", three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3, bicyclopentadiene), Fourth Ring [10.2.1.0 8-diene (trivial name: 2,11.0 4,9] 15 carbon-4,6,8,13-tetraene, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene (also referred to as " tetracyclododecane "), 9-methyl-Fourth Ring [6.2.1.1 3, 6.0 2, 7] 12 carbon-4-alkene, 9-ethyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methene-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethylidene-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-vinyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-propenyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, five rings [9.2.1.1 3,9.0 2,10.0 4,8] 15 carbon-5,12-diene, cyclobutane, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclo-octadiene, indenes, 3a, 5,6,7a-tetrahydrochysene-4,7-endo-methylene group-1H-indenes, 9-phenyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, Fourth Ring [9.2.1.0 2,10.0 3,8] 14 carbon-3,5,7,12-tetraene, five rings [9.2.1.1 3,9.0 2,10.0 4,8] 15 carbon-12-alkene etc.
These monomers (b2) can be distinguished use separately, also can combine two or more use.
As the concrete example of the monomer (b3) beyond cyclic olefin, can enumerate: ethene; Propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4, the alpha-olefin of the carbon numbers 2～20 such as 4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene; Isosorbide-5-Nitrae-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, the non-conjugated diene such as 7-octadiene and their derivant etc.Wherein, preferred alpha-olefin, particularly preferably ethene.
These monomers (b3) both can have been distinguished use separately, also can combine two or more use.
Among these monomers (b1)～(b3), from making the more significant viewpoint of effect of the present invention, consider, the cyclic olefin monomers (b1) that preferably has the polar group beyond the protic polar group, particularly preferably have the cyclic olefin of N-substituted imides base.
In cyclic olefin polymer (A1), the unit of monomer (b) that can copolymerization be preferably 10～90 % by mole containing proportional with respect to whole monomeric units.When the unit of monomer (b) that can copolymerization containing proportional when very few, the dissolubility of cyclic olefin polymer (A1) in polar solvent is likely insufficient, the unit of monomer (b) that can copolymerization containing proportional when too much, radiation-sensitive while in resin combination of the present invention, adding the radiation-sensitive compound is inadequate, likely when developing, produces dissolved residue.
The unit of monomer (b) that in addition, can copolymerization different and different according to the kind of the resin molding formed by resin combination of the present invention containing proportional more preferably scope.Particularly; when this resin molding diaphragm that is active-matrix substrate, encapsulating film of organic EL substrate etc. utilize photoetching process to carry out the resin molding of patterning; the unit of monomer (b) that can copolymerization containing proportional more preferably 30～60 % by mole, be particularly preferably 40～50 % by mole.On the other hand, when the pixel separation film of the gate insulating film that resin molding is active-matrix substrate, organic EL substrate etc. does not utilize photoetching process to carry out the resin molding of patterning, the unit of monomer (b) that can copolymerization containing proportional more preferably 20～80 % by mole, be particularly preferably 30～70 % by mole.
In addition, in the present invention, can utilize known modifier to import the protic polar group by not thering is the cyclic olefin based polymer of protic polar group, make cyclic olefin polymer (A1).
The polymkeric substance that does not have the protic polar group, can carry out polymerization with monomer (b3) combination in any as required by least one by above-mentioned monomer (b1) and (b2) and obtain.
As for importing the modifier of protic polar group, usually, use the compound that there is protic polar group and reactive carbon-to-carbon unsaturated bond in a molecule.
As the concrete example of such compound, can enumerate: the unsaturated carboxylic acids such as acrylic acid, methacrylic acid, angelic acid, the acid of cautious lattice, oleic acid, elaidic acid, erucic acid, anti-erucic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid; The unsaturated alcohol of allyl alcohol, methyl ethylene methyl alcohol, crotonyl alcohol, methallyl alcohol, 1-phenyl ethene-1-alcohol, 2-propylene-1-alcohol, 3-butene-1-ol, 3-butene-2-ol, 3-methyl-3-butene-1-alcohol, 3-M2BOL, 2-M3BOL, 2-methyl-3-butene-1-alcohol, 4-amylene-1-ol, 4-methyl-4-amylene-1-ol, 2-hexen-1-ol etc. etc.
Use the modified-reaction of the polymkeric substance of these modifier to get final product according to conventional methods, usually, carry out under the existence of free radical generating agent.
Wherein, the cyclic olefin polymer used in the present invention (A1) can be both the ring-opening polymerization polymer that above-mentioned monomer ring-opening polymerization is obtained, can be also perhaps the addition polymer that above-mentioned monomer addition polymerization is obtained, but, from the more significant viewpoint of effect of the present invention is considered, be preferably ring-opening polymerization polymer.
Ring-opening polymerization polymer can be by will there is the protic polar group under the existence at the metathesis reaction catalyzer cyclic olefin monomers (a) and use as required can copolymerization monomer (b) carry out ring-opening metathesis polymerization and manufacture.
The metathesis reaction catalyzer, so long as the periodic table of elements 3rd～11 group transition metal compounds and be that the catalyzer of cyclic olefin monomers (a) ring-opening metathesis polymerization that will have the protic polar group can be just any catalyzer.For example, as the metathesis reaction catalyzer, can use the catalyzer of record in Olefin Metathesis and Metathesis Polymerization (K.J.Ivinand J.C.Mol, Academic Press, San Diego1997).
As the metathesis reaction catalyzer, for example can enumerate the periodic table of elements 3rd～11 group 4 transition metals-carbene complex catalyzer.Wherein, preferably use the Ru carbene complex catalyzer.
As periodic table 3rd～11 group 4 transition metals-carbene complex catalyzer, can enumerate, such as, tungsten alkylidene radical complex compound catalyst, molybdenum alkylidene radical complex compound catalyst, rhenium alkylidene radical complex compound catalyst, Ru carbene complex catalyzer etc.
As the concrete example of above-mentioned tungsten alkylidene radical complex compound catalyst, can enumerate: W (N-2,6-Pr i 2c 6h 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2c 6h 3) (CHBu t) (OCMe 2cF 3) 2, W (N-2,6-Pr i 2c 6h 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (OBu t) 2, W (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (OCMe 2cF 3) 2, W (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (OCMe (CF 3) 2) 2deng.
As the concrete example of molybdenum alkylidene radical complex compound catalyst, can enumerate: Mo (N-2,6-Pr i 2c 6h 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHBu t) (OCMe 2(CF 3) 2) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHBut) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHC Me 2ph) (OBu t) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (OCMe 2cF 3) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (BIPHEN), Mo (N-2,6-Pr i 2c 6h 3) (CHCMe 2ph) (BINO) (THF) etc.
As the concrete example of rhenium alkylidene radical complex compound catalyst, can enumerate: Re (CBu t) (CHBu t) (O-2,6-Pr i 2c 6h 3) 2, Re (CBu t) (CHBu t) (O-2-Bu tc 6h 4) 2, Re (CBu t) (CHBu t) (OCMe 2cF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu t) (O-2,6-Me 2c 6h 3) 2deng.
In above-mentioned formula, Pr imean isopropyl, Bu tmean the tert-butyl group, Me means methyl, and Ph means phenyl, and BIPHEN means 5,5 ', 6, and 6 '-tetramethyl-3,3 '-di-t-butyl-1,1 '-xenyl-2,2 '-dioxy base, BINO means 1,1 '-dinaphthyl-2,2 '-dioxy base, THF means tetrahydrofuran.
In addition, as the concrete example of Ru carbene complex catalyzer, can enumerate the compound shown in following formula (3) or (4).
[chemical formula 3]
Figure BDA0000386244120000131
[chemical formula 4]
Figure BDA0000386244120000132
In above-mentioned formula (3) and (4) ,=CR 4r 5and=C=CR 4r 5carbene compound for the Cabbeen carbon that contains reaction center.R 4and R 5mean independently respectively hydrogen atom, maybe can contain alkyl, alkoxy, aryloxy group, acyloxy, amino, acyl amino, diacylamino group, alkylthio group, arylthio, sulfonyl, sulfinyl, phosphino-(ホ ス Off ィ ノ yl), the silicyl of the carbon number 1～20 of halogen atom, oxygen atom, nitrogen-atoms, sulphur atom, phosphorus atoms or silicon atom, these carbene compounds can contain heteroatoms.L 1mean to contain heteroatomic carbene compound, L 2mean neutral arbitrarily supplied for electronic compound.
Wherein, containing heteroatomic carbene compound refers to and contains Cabbeen carbon and heteroatomic compound.L 1and L 2both sides or L 1for containing heteroatomic carbene compound, in them on contained Cabbeen carbon Direct Bonding the ruthenium metallic atom is arranged, and bonding has containing heteroatomic group.
L 3and L 4independently mean respectively anionic property part arbitrarily.In addition, R 4, R 5, L 1, L 2, L 3and L 4in 2,3,4,5 or 6 also mutually bonding form multiple tooth cheland.In addition, as heteroatomic concrete example, can enumerate N, O, P, S, As, Se atom etc.Wherein, from the viewpoint that obtains stable carbene compound, consider, preferably N, O, P, S atom etc., particularly preferably N atom.
In above-mentioned formula (3) and (4), negative ion (negative ion) property ligand L 3, L 4during Shi Cong center metal separation, with the part of negative charge, can enumerate such as halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atoms; Diketo, alkoxy, aryloxy group or carboxyl etc. are containing the alkyl of aerobic; The ester ring type alkyl that chlorinated cyclopentadiene base etc. replace with halogen atom etc.Wherein, preferred halogen atom, more preferably chlorine atom.
L 2in the situation that contains heteroatomic carbene compound neutral supplied for electronic compound in addition, with regard to L 2, so long as there is the part of neutral charge during from the center metal separation, getting final product, any part can.As its concrete example, can enumerate: carbonyl class, amine, pyridines, ethers, nitrile, ester class, phosphine class, thioether class, aromatics, olefines, isocyanide class, thiocyanate (ester) class etc.Wherein, preferred phosphine class or pyridines, more preferably trialkyl phosphine.In addition, R 4and L 2or R 5and L 2when bonding forms multiple tooth cheland mutually, preferred pyridines, ethers.
As the ruthenium complex catalyst shown in above-mentioned formula (3), for example can enumerate: (1,3-bis-for dichlorin benzylidene
Figure BDA0000386244120000141
base imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro
Figure BDA0000386244120000142
base imidazoline-2-subunit) (3-methyl-2-butene-1-subunit) (three cyclopentyl phosphines) closes ruthenium, (1,3-bis-for dichloro ((2-(1-methyl ethoxy) phenyl) methylene)
Figure BDA0000386244120000143
base imidazoline-2-subunit) close ruthenium, (1,3-bis-for dichlorin benzylidene
Figure BDA0000386244120000144
base imidazoline-2-subunit) two (3-bromopyridines) close ruthenium, (1,3-bis-for dichloro (3-(2-pyridine radicals) propylidene base)
Figure BDA0000386244120000145
base imidazoline-2-subunit) close that ruthenium, dichlorin benzylidene (1,3-, bis-Lai Ji-octahydro benzimidazolyl-2 radicals-subunit) (tricyclohexyl phosphine) close ruthenium, (1,3-bis-for dichloro (3-phenylindan-1-subunit)
Figure BDA0000386244120000146
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (2-thienyl methene)
Figure BDA0000386244120000147
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (2-thienyl methene)
Figure BDA0000386244120000148
base-4,5-dimethyl-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, dichloro (2-thienyl methene) (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichlorin benzylidene
Figure BDA00003862441200001421
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichlorin benzylidene
Figure BDA0000386244120000149
base-2,3-dihydrobenzo imidazoles-2-subunit) (tricyclohexyl phosphine) closes ruthenium, dichlorin benzylidene (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-subunit) (tricyclohexyl phosphine) closes ruthenium, dichlorin benzylidene (4,5-bis-is chloro-1, and 3-bis-
Figure BDA00003862441200001410
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, dichlorin benzylidene (4,5-bis-is bromo-1, and 3-bis-
Figure BDA00003862441200001411
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (3-phenylindan-1-subunit) base imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (3-phenylindan-1-subunit)
Figure BDA00003862441200001413
base imidazoline-2-subunit) two (pyridines) close ruthenium, (1,3-bis-for dichloro ((2-(1-acetyl group ethoxy) phenyl) methylene) base imidazoline-2-subunit) close ruthenium, (1,3-bis-for dichloro (thiophenyl methylene)
Figure BDA00003862441200001415
base imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (thiophenyl methylene)
Figure BDA00003862441200001416
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro (ethylmercapto group methylene)
Figure BDA00003862441200001417
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (13-bis-for dichloro ((1-azo-2-oxocyclopentyl) methylene) base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro ((carbazole-9-yl) methylene)
Figure BDA00003862441200001419
base-4-imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichloro ((2-(1-methyl ethoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl) methylene)
Figure BDA00003862441200001420
base imidazoline-2-subunit) close ruthenium, dichloro ((2-(1-methyl ethoxy)-5-(trifluoroacetamido) phenyl) methylene) (1,3-two (2, the 6-diisopropyl phenyl) imidazoline-2-subunit) close ruthenium, dichlorin benzylidene [1,3-bis-(1-phenylethyl)-4-imidazoline-2-subunit] (tricyclohexyl phosphine) close ruthenium, dichloro (1,3-diisopropyl hexahydropyrimidine-2-subunit) (ethoxy methylene) (tricyclohexyl phosphine) closes ruthenium, (1,3-bis-for dichlorin benzylidene base hexahydropyrimidine-2-subunit) (tricyclohexyl phosphine) closes ruthenium etc. and contains the Ru carbene complex that heteroatomic carbene compound and neutral supplied for electronic compound bonding obtain; Dichlorin benzylidene two (1,3-dicyclohexyl-4-imidazoline-2-subunits) closes ruthenium, dichlorin benzylidene two (1,3-diisopropyl-4-imidazoline-2-subunit) and closes ruthenium etc. and contain Ru carbene complex that 2 heteroatomic carbene compound bondings obtain etc.
As the Ru carbene complex catalyzer shown in above-mentioned formula (4), for example can enumerate: (1,3-bis-for dichloro (phenyl ethenylidene)
Figure BDA0000386244120000152
base imidazoline-2-subunit) (tricyclohexyl phosphine) closes ruthenium, dichloro (tert-butyl group ethenylidene (1,3-diisopropyl-4-imidazoline-2-subunit) (three cyclopentyl phosphines) closes ruthenium, two (1,3-dicyclohexyl-4-imidazoline-2-subunit) the phenyl ethenylidenes of dichloro close ruthenium etc.
With regard to the consumption of metathesis reaction catalyzer, the monomer of take is catalyzer: monomer=1:100～1:2 with respect to the molar ratio computing of catalyzer, 000,000, and preferred 1:500～1:1,000,000, more preferably 1:1,000～1:500,000.When catalytic amount is more too much than above-mentioned mol ratio, sometimes be difficult to remove catalyzer, when catalytic amount is very few, sometimes can not obtain sufficient polymerization activity.
Use the ring-opening polymerization of metathesis reaction catalyzer to carry out in solvent or under solvent-free.After polyreaction finishes, the polymkeric substance generated do not separated and directly carried out in the situation of hydrogenation, preferably in solvent, being carried out polymerization.
For the solvent used, so long as the polymer dissolution of generation and the solvent that do not hinder polyreaction are got final product, be not particularly limited.As the solvent used, can enumerate such as aliphatic hydrocarbons such as n-pentane, normal hexane, normal heptanes; The clicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethyl cyclohexane, trimethyl-cyclohexane, ethyl cyclohexane, diethyl cyclohexane, decahydronaphthalenes, norbornane, tristane, hexahydro indenes, cyclooctane; The aromatic hydrocarbon such as benzene,toluene,xylene, sym-trimethyl benzene; The nitrogenous class hydrocarbon such as nitromethane, nitrobenzene, acetonitrile, propionitrile, cyanobenzene; The ethers such as ether, tetrahydrofuran, diox; The ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; The ester classes such as methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate; Chloroform, methylene chloride, 1, the halogenated hydrocarbons such as 2-ethylene dichloride, chlorobenzene, dichloro-benzenes, trichloro-benzenes etc.Wherein, preferably use aromatic hydrocarbon, clicyclic hydrocarbon, ethers, ketone or ester class.
The concentration of the monomer mixture in solvent is preferably 1～50 % by weight, more preferably 2～45 % by weight, more preferably 5～40 % by weight.When the concentration of monomer mixture during lower than 1 % by weight, the throughput rate variation of polymkeric substance sometimes, when it surpasses 50 % by weight, the viscosity after polymerization is too high sometimes, is difficult to carry out hydrogenation thereafter etc.
The metathesis reaction catalyzer both can be dissolved in solvent and be added in reaction system, also can not make its dissolving and directly interpolation.As the solvent of Kaolinite Preparation of Catalyst solution, can enumerate the solvent same with the solvent for above-mentioned polyreaction.
In addition, in polyreaction, for the molecular weight of telomerized polymer, can in reaction system, add molecular weight regulator.As molecular weight regulator, can use: the alpha-olefins such as 1-butylene, 1-amylene, 1-hexene, 1-octene; Isosorbide-5-Nitrae-pentadiene, 1,5-hexadiene, 1, the α such as 6-heptadiene, ω-diolefin; The phenylethylenes such as styrene, vinyltoluene, divinylbenzene; The ethers such as ethyl vinyl ether, IVE, allyl glycidyl ether; The Halogen vinyl compounds such as allyl chloride; The oxygen containing vinyl compounds such as allyl acetate, allyl alcohol, glycidyl methacrylate; The vinyl compound that vinyl cyanide, acrylamide etc. are nitrogenous etc.Monomer mixture with respect to comprising the cyclic olefin monomers (a) with protic polar group, used the molecular weight regulator of 0.05～50 % by mole, can access thus the polymkeric substance of the molecular weight with hope.
Polymerization temperature is not particularly limited, and is generally-100 ℃～+ 200 ℃, is preferably-50 ℃～+ 180 ℃, more preferably-30 ℃～+ 160 ℃, more preferably 0 ℃～+ 140 ℃.Polymerization time is generally 1 minute～and 100 hours, can suitably regulate according to the situation of carrying out of reaction.
On the other hand, addition polymer can be by the catalyzer that uses known addition polymerization catalyst for example to consist of titanium, zirconium or vfanadium compound and organo-aluminum compound, make to have the cyclic olefin monomers (a) of protic polar group and use as required can copolymerization monomer (b) carry out polymerization and obtain.These polymerization catalysts can be used separately respectively or combine two or more and use.With regard to the amount of polymerization catalyst, with the metallic compound in polymerization catalyst: the molar ratio computing of monomer is generally 1:100～1:2,000,000 scope.
In addition, when the cyclic olefin polymer used in the present invention (A1) is ring-opening polymerization polymer, preferably further carry out hydrogenation, make the hydride that the contained carbon-to-carbon double bond of main chain is hydrogenated.When cyclic olefin polymer (A1) is hydride, the ratio of the carbon-to-carbon double bond be hydrogenated (hydrogenation ratio) is generally more than 50%, from stable on heating viewpoint, considers, is preferably more than 70%, more preferably more than 90%, more preferably more than 95%.
For the hydrogenation ratio of hydride, for example, can be by ring-opening polymerization polymer relatively 1from the peak strength of carbon-to-carbon double bond and hydride in the H-NMR spectrogram 1peak strength from carbon-to-carbon double bond in the H-NMR spectrogram is obtained.
Hydrogenation for example can by under the existence of hydrogenation catalyst with hydrogen, the carbon-to-carbon double bond in the main chain of ring-opening polymerization polymer be converted into to saturated singly-bound carry out.
The hydrogenation catalyst used is without particular limitation of in homogeneous catalyst, heterogeneous catalysis etc., the catalyzer usually adopted in the time of can suitably using olefin(e) compound hydrogenation.
As homogeneous catalyst, can enumerate such as: by the Ziegler series catalysts constituted of the transistion metal compounds such as combination, four titanium butoxide acid esters and the dimethyl magnesium of combination, bis cyclopentadienyl zirconium dichloride and the s-butyl lithium of combination, cyclopentadienyl titanium dichloride and the n-BuLi of combination, nickel acetylacetonate and the triisobutyl aluminium of cobalt acetate and aluminium triethyl and alkali metal compound; The noble metal complexes catalyzer formed by ruthenium compound of record etc. in the Ru carbene complex catalyzer of recording and narrating in one of above-mentioned ring-opening metathesis catalysts, dichloro three (triphenylphosphine) rhodium, Japanese kokai publication hei 7-2929, Japanese kokai publication hei 7-149823, Japanese kokai publication hei 11-109460, Japanese kokai publication hei 11-158256, Japanese kokai publication hei 11-193323, Japanese kokai publication hei 11-109460 etc.
As heterogeneous catalysis, can enumerate such as metals such as making nickel, palladium, platinum, rhodium, ruthenium and support the hydrogenation catalyst formed on the carriers such as carbon, silicon dioxide, zeyssatite, aluminium oxide, titanium dioxide.More specifically, can use such as nickel/silicon dioxide, nickel/zeyssatite, nickel/aluminium oxide, palladium/carbon, palladium/silicon dioxide, palladium/zeyssatite, palladium/aluminium oxide etc.These hydrogenation catalysts can be used separately or combine two or more and use.
Wherein, from ring-opening polymerization polymer, the subsidiary reactions such as modification do not occur, the carbon-to-carbon double bond selective hydration aspect in this polymkeric substance can be considered in contained functional group, preferably use the palladiums such as the noble metal complexes catalyzer such as rhodium, ruthenium and palladium/carbon catalyst-loaded, more preferably use Ru carbene complex catalyzer or palladium catalyst-loaded.
Above-mentioned Ru carbene complex catalyzer can be used as ring-opening metathesis catalysts and hydrogenation catalyst.Now, can carry out continuously ring-opening metathesis reaction and hydrogenation.
In addition, use the Ru carbene complex catalyzer to carry out continuously in the situation of ring-opening metathesis reaction and hydrogenation, start the method for hydrogenation after also preferably adopting the catalyst modifiers such as vinyl compounds such as adding ethyl vinyl ether or alpha-olefin that this catalyzer is activated.And, also preferably adopt alkali such as adding triethylamine, DMA to put forward highly active method.
Hydrogenation carries out usually in organic solvent.As organic solvent, can suitably select according to the dissolubility of the hydride generated, can use the organic solvent same with above-mentioned polymer solvent.Therefore, also can add hydrogenation catalyst and make its reaction in reactant liquor or the filtrate obtained from this reactant liquor, removing by filter the metathesis reaction catalyzer, and need not after polyreaction, change solvent.
The condition of hydrogenation is suitably selected to get final product according to the kind of the hydrogenation catalyst used.For the consumption of hydrogenation catalyst, ring-opening polymerization polymer 100 weight portions, be generally 0.01～50 weight portion relatively, is preferably 0.05～20 weight portion, more preferably 0.1～10 weight portion.Temperature of reaction is generally-10 ℃～+ 250 ℃, is preferably 0 ℃～+ 240 ℃, more preferably 20 ℃～+ 230 ℃.At the temperature lower than this scope, reaction velocity is slack-off, on the contrary, at higher temperature, subsidiary reaction easily occurs.The pressure of hydrogen is generally 0.01～10.0MPa, is preferably 0.05～8.0MPa, more preferably 0.1～6.0MPa.
In order to control hydrogenation ratio, the time that suitably selective hydrogenation reacts.Reaction time is generally the scope of 0.1～50 hour, can in the carbon-to-carbon double bond on main polymer chain more than 50%, preferably more than 70%, more preferably more than 90%, most preferably carry out hydrogenation more than 95%.
In addition; the acryl resin used in the present invention (A2) is not particularly limited, and preferably take to be selected from the carboxylic acid with acryloyl group, the carboxylic acid anhydrides with acryloyl group or containing at least a kind in the acrylate compounds of the acrylate compounds of epoxy radicals and oxygen heterocycle butane group be essential component homopolymer or multipolymer.Wherein, " acryloyl group " can be also substituted acryl.
As the concrete example of the carboxylic acid with acryloyl group, can enumerate: (methyl) acrylic acid [meaning of acrylic acid and/or methacrylic acid.Below, (methyl) methyl acrylates etc. too], crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, phthalic acid list-(2-((methyl) acryloxy) ethyl), N-(carboxyl phenyl) maleimide, N-(carboxyl phenyl) (methyl) acrylamide etc.
As the concrete example of the carboxylic acid anhydrides with acryloyl group, can enumerate maleic anhydride, citraconic anhydride etc.
Concrete example as the acrylate compounds containing epoxy radicals, can enumerate: glycidyl acrylate, glycidyl methacrylate, the α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid-3, 4-epoxy radicals butyl ester, methacrylic acid-3, 4-epoxy radicals butyl ester, acrylic acid-6, 7-epoxy radicals heptyl ester, methacrylic acid-6, 7-epoxy radicals heptyl ester, α-ethylacrylate-6, 7-epoxy radicals heptyl ester, acrylic acid-3, 4-epoxy radicals cyclohexyl methyl esters, methacrylic acid-3, 4-epoxy radicals cyclohexyl methyl esters etc.
Concrete example as the acrylate compounds of oxygen heterocycle butane group, can enumerate: (methyl) acrylic acid (3-methyl oxetanes-3-yl) methyl esters, (methyl) acrylic acid (3-Ethyloxetane-3-yl) methyl esters, (methyl) acrylic acid (3-methyl oxetanes-3-yl) ethyl ester, (methyl) acrylic acid (3-Ethyloxetane-3-yl) ethyl ester, (methyl) acrylic acid (3-chloromethyl oxetanes-3-yl) methyl esters, (methyl) acrylic acid (oxetanes-2-yl) methyl esters, (methyl) acrylic acid (2-methyl oxetanes-2-yl) methyl esters, (methyl) acrylic acid (2-Ethyloxetane-2-yl) methyl esters, (1-methyl isophthalic acid-epoxy mix butane group-2-phenyl)-3-(methyl) acrylate, (1-methyl isophthalic acid-epoxy mix butane group)-2-trichloromethyl-3-(methyl) acrylate and (1-methyl isophthalic acid-epoxy mix butane group)-4-trichloromethyl-2-(methyl) acrylate etc.
Wherein, preferred (methyl) acrylic acid, maleic anhydride, (methyl) glycidyl acrylate, methacrylic acid-6,7-epoxy radicals heptyl ester etc.
Acryl resin (A2) can be selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and containing in the unsaturated compound of epoxy radicals one of at least with other acrylic ester monomers or acrylate beyond can copolymerization the multipolymer that forms of monomer.
As other acrylic ester monomers, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) acrylic acid isopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) alkyl acrylates such as the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid 2-hydroxyl-(methyl) acrylic acid phenoxyalkyl esters such as 3-phenoxy group propyl ester, (methyl) alkoxyalkyl acrylates such as (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-propoxyl group ethyl ester, (methyl) acrylic acid 2-butoxyethyl, (methyl) acrylic acid 2-methoxyl butyl ester, poly alkylene glycol (methyl) acrylate such as polyethyleneglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl polypropylene glycol (methyl) acrylate, ethoxy polypropylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid 4-butyl cyclohexyl, (methyl) acrylic acid 1-diamantane ester, (methyl) acrylic acid 2-methyl-2-diamantane ester, (methyl) acrylic acid 2-ethyl-2-diamantane ester, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6]-3-decene-8-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6(methyl) acrylic acid cycloalkyl esters such as]-3-decene-9-base ester, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) biphenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid tetrahydrofuran ester, (methyl) acrylic acid 5-tetrahydrofuran base oxo carbonyl pentyl ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid 2-(2-ethyleneoxy ethoxy) ethyl ester, 2-[tri-ring [5.2.1.0 2,6] decane-8-base oxygen base] ethyl (methyl) acrylate, 2-[tri-ring [5.2.1.0 2,6]-3-decene-8-base oxygen base] ethyl (methyl) acrylate, 2-[tri-ring [5.2.1.0 2,6]-3-decene-9-base oxygen base] ethyl (methyl) acrylate, gamma-butyrolacton (methyl) acrylate, maleimide, N-methyl maleimide, NEM, the N-butyl maleimide, the N-N-cyclohexylmaleimide, N-benzyl maleimide, N-phenylmaleimide, N-(2, 6-diethyl phenyl) maleimide, N-(4-acetylphenyl) maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-acetoxyl group phenyl) maleimide, N-(4-dimethylamino-3, the 5-dinitrophenyl) maleimide, N-(1-anilino-naphthyl-4) maleimide, N-[4-(2-benzo the azoles base) phenyl] maleimide, N-(9-acridinyl horse) carry out acid imide etc.
Wherein, preferably (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) benzyl acrylate, (methyl) acrylic acid three encircle [5.2.1.0 2,6] decane-8-base ester, N-phenylmaleimide and N-N-cyclohexylmaleimide etc.
As beyond acrylate can copolymerization monomer, so long as can with the above-mentioned carboxylic acid with acryloyl group, there is the carboxylic acid anhydrides of acryloyl group or get final product containing the compound that the acrylate compounds of epoxy radicals carries out copolymerization, be not particularly limited, for example can enumerate: the vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, vinyltoluene, indenes, vinyl naphthalene, vinyl biphenyl, chlorostyrene, bromostyrene, 1-chloro-4-methyl-benzene, to tert-butoxy styrene, 4-Vinyl phenol, to hydroxyl-alpha-methyl styrene, to acetoxy-styrene, to carboxyl styrene, 4-hydroxy phenyl vinyl ketone, vinyl cyanide, methacrylonitrile, (methyl) acrylamide, 1, 2-epoxy radicals-4-vinyl cyclohexane, isobutylene, norborene, butadiene, the free-radical polymerised compounds such as isoprene.
These compounds both can have been distinguished use separately, also can combine two or more use.
The polymerization of above-mentioned monomer gets final product according to conventional method, such as adopting suspension polymerization, emulsion polymerization method, solution polymerization process etc.
The Cardo resin (A3) used in the present invention has the Cardo structure, that is, and and the skeleton structure that forms forming that bonding on the quaternary carbon atom of ring texture has two ring texturees.The general structure of Cardo structure is that the fluorenes ring key closes the structure that phenyl ring forms.
As forming that bonding on the quaternary carbon atom of ring texture has two ring texturees, the concrete example of the skeleton structure that forms can be enumerated: fluorene skeleton, bisphenol fluorene skeleton, two aminophenyl fluorene skeleton, have epoxy radicals fluorene skeleton, there is the fluorene skeleton of acryloyl group etc.
The Cardo resin (A3) used in the present invention is to carry out polymerization by the skeleton with this Cardo structure by reacting between the functional group with its bonding etc. to form.Cardo resin (A3) has the structure (Cardo structure) that main chain is connected by an element with the large volume side chain, and has ring texture on the direction substantially vertical with respect to main chain.
As an example of Cardo structure, mean that in following formula (5) bonding has the example as the Cardo structure of the acryloyl group of functional group.
[chemical formula 5]
(in above-mentioned formula (5), the integer that n is 0～10.)
Monomer with Cardo structure, for example can enumerate: two (glycidoxy phenyl) fluorenes type epoxy resin; Bisphenol fluorene type epoxy resin and acrylic acid condensation product; Two (4-hydroxy phenyl) fluorenes, 9 of 9,9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc. are containing the bisphenols of Cardo structure; Two (cyano methyl) fluorenes of 9,9-etc. 9, two (cyano group alkyl) the fluorenes classes of 9-; Two (3-aminopropyl) fluorenes of 9,9-etc. 9, two (aminoalkyl) fluorenes classes of 9-etc.
Cardo resin (A3) is the polymkeric substance that the monomer polymerization that will have the Cardo structure obtains, but can be also with other can copolymerization the multipolymer that forms of monomer.
The kind of the polymerism functional group that the polymerization of above-mentioned monomer has according to monomer is selected to get final product, such as adopting ring-opening polymerization method or addition polymerization method etc.
As the polysiloxane used in the present invention (A4), be not particularly limited, preferably enumerate the polymkeric substance that its reaction is obtained by the one kind or two or more mixing in the organosilane by shown in following formula (6).
(R 6) m-Si-(OR 7) 4-m (6)
In above-mentioned formula (6), R 6for the alkyl of hydrogen atom, carbon number 1～10, the thiazolinyl of carbon number 2～10 or the aryl of carbon number 6～15, a plurality of R 6can distinguish identical also can be different.Wherein, any one can all have substituting group these alkyl, thiazolinyl, aryl, in addition also can be substituent without replacing body for having, can be selected according to the characteristic of composition.Concrete example as alkyl, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl, trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro propyl, 3-glycidoxy propyl group, 2-(3,4-epoxy radicals cyclohexyl) ethyl, 3-aminopropyl, 3-mercapto propyl group, 3-isocyanates propyl group.As the concrete example of thiazolinyl, can enumerate: vinyl, 3-acryloxy propyl group, 3-methacryloxypropyl.As the concrete example of aryl, can enumerate phenyl, tolyl, p-hydroxybenzene, 1-(p-hydroxybenzene) ethyl, 2-(p-hydroxybenzene) ethyl, 4-hydroxyl-5-(p-hydroxybenzene carbonyl oxygen base) amyl group, naphthyl.
In addition, in above-mentioned formula (6), R 7for the alkyl of hydrogen atom, carbon number 1～6, the acyl group of carbon number 1～6 or the aryl of carbon number 6～15, a plurality of R 7can distinguish identical also can be different.Wherein, these alkyl, acyl group all can have substituting group, also can be substituent without replacing body for not having, 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.Concrete example as aryl can be enumerated phenyl.
In addition, in above-mentioned formula (6), the integer that m is 0～3, mean 4 functional silanes during m=0, mean 3 functional silanes during m=1, means 2 functional silanes during m=2, means 1 functional silanes during m=3.
As the concrete example of the organosilane shown in above-mentioned formula (6), can enumerate: 4 functional silanes such as tetramethoxy-silicane, tetraethoxysilane, tetrem acyloxy silane, 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-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy 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 carbonyl oxygen base) amyltrimethoxysilane, the trifluoromethyl trimethoxy silane, the trifluoromethyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, the 3-TSL 8330, APTES, the 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3 functional silanes such as 3-sulfydryl propyl trimethoxy silicane, 2 functional silanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diacetoxy silane, di-n-butyl dimethoxy silane, dimethoxydiphenylsilane, 1 functional silanes such as trimethyl methoxy silane, three normal-butyl Ethoxysilanes.
In these organosilanes, from the resistance to cracking of resulting resin molding and the viewpoint of hardness, consider, preferably use 3 functional silanes.These organosilanes both can be used separately, also can combine two or more use.
The polysiloxane used in the present invention (A4) is by obtaining above-mentioned organosilane hydrolysis and part condensation.Hydrolysis and part condensation can be used general method.For example, add solvent, water in potpourri, add as required catalyzer, added thermal agitation.In stirring, can utilize as required distillation that hydrolysising by-product alcohol such as () methyl alcohol and condensation by-product (water) are distilled and removed.
The polyimide used in the present invention (A5) can be heat-treated and obtain by the polyimide precursor that tetracarboxylic dianhydride and diamine reactant are obtained.As for obtaining the precursor of polyimide, can enumerate polyamic acid, poly amic acid ester, polyisoimide, polyamic acid sulfonamide etc.
Can, as the acid dianhydride of the raw material that obtains polyimide (A5), particularly, can enumerate pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2,2-, 2,2-pair [3-[(3,4-dicarboxyl benzoyl) amino]-the 4-hydroxy phenyl] hexafluoropropane dianhydride, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (3,4-dicarboxyl phenyl) methane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydrides or 1,2,3 such as two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, 4-butane tetracarboxylic acid dianhydride, the aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentane tetracarboxylic dianhydride etc.Two or more use alone or in combination of these acid dianhydrides.
Can be used as the object lesson of the diamines of the raw material that obtains polyimide (A5), can enumerate: 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl thioether, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, m-phenylene diamine, p-phenylenediamine (PPD), 1,5-naphthylenediamine, 2,6-naphthylenediamine, two (4-amino-benzene oxygen phenyl) sulfone, two (3-amino-benzene oxygen phenyl) sulfone, two (4-amino-benzene oxygen) biphenyl, two { 4-(4-amino-benzene oxygen) phenyl } ether, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-diethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-diethyl-4,4 '-benzidine, 2,2 ', 3,3 '-tetramethyl-4,4 '-benzidine, 3,3 ', 4,4 '-tetramethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, the compound that has perhaps replaced alkyl or halogen atom on the aromatic ring of these compounds and obtained, aliphatic cyclohexyl diamines, di-2-ethylhexylphosphine oxide cyclo-hexylamine, two [(3-aminopropyl) dimetylsilyl] ether, 2, the 4-diaminobenzoic acid, 2, the 5-diaminobenzoic acid, 3, the 5-diaminobenzoic acid, 4, the 6-diaminostilbene, the 3-benzene dicarboxylic acid, 2, the 5-diaminostilbene, the 4-benzene dicarboxylic acid, two (4-amino-3-carboxyl phenyl) ether, it is two that (4-amino-3, 5-dicarboxyl phenyl) ether, two (4-amino-3-carboxyl phenyl) sulfone, it is two that (4-amino-3, 5-dicarboxyl phenyl) sulfone, 4, 4 '-diamido-3, 3 '-dicarboxylate biphenyl, 4, 4 '-diamido-3, 3 '-dicarboxyl-5, 5 '-dimethyl diphenyl, 4, 4 '-diamido-3, 3 '-dicarboxyl-5, 5 '-dimethoxy-biphenyl, 1, two (4-amino-3-carboxyphenoxy) benzene of 4-, 1, two (4-amino-3-carboxyphenoxy) benzene of 3-, two [4-(4-amino-3-carboxyphenoxy) phenyl] sulfone, two [4-(4-amino-3-carboxyphenoxy) phenyl] propane, 2, two [4-(4-amino-3-carboxyphenoxy) phenyl] HFC-236fa etc. of 2-have the diamine compound of carboxyl, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diamido quinhydrones, two (3-amino-4-hydroxylphenyl) ether, two (4-amino-3-hydroxy base) ether, two (4-amino-3,5-dihydroxy phenyl) ether, two (3-amino-4-hydroxylphenyl) methane, two (4-amino-3-hydroxy base) methane, two (4-amino-3,5-dihydroxy phenyl) methane, two (3-amino-4-hydroxylphenyl) sulfone, two (4-amino-3-hydroxy base) sulfone, two (4-amino-3,5-dihydroxy phenyl) sulfone, m-phthalic acid two (2-hydroxyl-5-amino aniline), 2-(4-amino benzoyl amino)-PAP, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-, two (the 4-amino-3-hydroxy base) HFC-236fa of 2,2-, 2,2-two (4-amino-3,5-dihydroxy phenyl) HFC-236fa, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxy-5,5 '-dimethyl diphenyl, 4,4 '-diamido-3,3 '-dihydroxy-5,5 '-dimethoxy-biphenyl base, Isosorbide-5-Nitrae-bis-(3-amino-4-hydroxy phenoxy group) benzene, two (the 3-amino-4-hydroxy phenoxy group) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-3-hydroxy oxygen base) benzene, two (the 4-amino-3-hydroxy oxygen base) benzene of 1,3-, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] sulfone, two [4-(3-amino-4-hydroxy phenoxy group) phenyl] propane, two [4-(the 3-amino-4-hydroxy phenoxy group) phenyl] HFC-236fa of 2,2-, two [N-(2-hydroxyl-5-aminophenyl) benzamide-4-yl] HFC-236fa of 2,2-, 2,2-pair [the 3-[(3-amino benzoyl) amino]-the 4-hydroxy phenyl] HFC-236fa, 2,2-two [3-[(4-amino benzoyls) amino]-4-hydroxy phenyl] HFC-236fa etc. has the diamine compound of phenol hydroxyl, 1,3-diamido-4-sulfenyl benzene, 1,3-diamido-5-sulfenyl benzene, Isosorbide-5-Nitrae-diamido-2-sulfenyl benzene, two (4-amino-3-sulfenyl phenyl) ether, 2, two (3-amino-4-sulfenyl phenyl) HFC-236fa etc. of 2-have the diamine compound of thiophenol base, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, two (4-aminobenzene-3-sulfonic acid) ether, 4,4 '-benzidine base) 3,3 '-disulfonic acid, 4,4 '-diamido-3,3 '-dimethyl diphenyl base-6,6 '-disulfonic acid etc. have sulfonic diamine compound etc.Two or more use alone or in combination of these diamines.
The polyimide used in the present invention (A5) can be synthetic by known method.; optionally combine tetracarboxylic dianhydride and diamines; make them the known method such as react in the inferior phosphoric triamide of METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO), hexamethyl, gamma-butyrolacton, cyclopentanone isopolarity solvent synthetic.
When excessively using diamines to carry out polymerization, the terminal amino group of generated polyimide (A5) is reacted with carboxylic acid anhydrides, can protect terminal amino group.In addition, when excessively using tetracarboxylic anhydride to carry out polymerization, the end anhydride group of generated polyimide (A5) is reacted with amines, also can protect the end anhydride group.
Example as such carboxylic acid anhydrides, can enumerate: phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenation phthalic anhydride, methyl-5-norborene-2,3-dicarboxylic anhydride, itaconic anhydride, tetrabydrophthalic anhydride etc., as the example of amines, can enumerate: aniline, 2-hydroxyanilines, 3-hydroxyanilines, 4-hydroxyanilines, 2-acetylenylaniline, 3-acetylenylaniline, 4-acetylenylaniline etc.
The weight-average molecular weight (Mw) of the adhesive resin used in the present invention (A) is generally 1,000～1,000,000, is preferably 1,500～100,000, more preferably 2,000～10,000 scope.
In addition, the molecular weight distribution of adhesive resin (A), in weight-average molecular weight/number-average molecular weight (Mw/Mn) ratio, be generally below 4, is preferably below 3, more preferably below 2.5.
The weight-average molecular weight (Mw) of adhesive resin (A) and molecular weight distribution (Mw/Mn) are the gel permeation chromatographies (GPC) utilized the tetrahydrofuran equal solvent as eluent, the value of obtaining with the polystyrene conversion value.
(silane-modified resin (B))
The silane-modified resin used in the present invention (B) has resin portion and silane compound section, and the two state that is mutual chemical bonding.
Material as the resin portion that forms silane-modified resin (B), be not particularly limited, preferably have can with the silane compound section macromolecular material of the functional group of bonding chemically.Macromolecular material as such, be not particularly limited, and can enumerate such as polyester, polyamide, polyimide, polyamic acid, epoxy resin, acrylic resin, urethane resin, phenolics etc.Wherein, consider preferred polyamide acid, epoxy resin, acryl resin and phenolics from the more significant viewpoint of effect of the present invention.In addition, as can with the functional group of silane compound section bonding, be not particularly limited, but can enumerate such as hydroxyl, amino, sulfydryl, carboxylic acid group, anhydride group, epoxy radicals, amide group, imide etc., from the reactive viewpoint with silane compound, consider, preferably hydroxyl, carboxylic acid group or anhydride group.
Silicon compound as the silane compound section that forms silane-modified resin (B), be not particularly limited, for example can enumerate: the partial hydrolysis condensation product of the silicon compound shown in the silicon compound shown in following formula (7) and/or following formula (7), the more significant viewpoint of effect of the present invention is considered, the silicon compound shown in the following formula (8) that particularly preferably the silicon compound partial hydrolysis shown in formula (7) can be obtained.
(R 8) r-Si(OR 9) 4-r (7)
[chemical formula 6]
In above-mentioned formula (7), the integer that r is 0～3.R 8alkyl, the aryl of carbon number 6～20 or the unsaturated aliphatic base of carbon number 2～10 that can have with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 8when a plurality of, a plurality of R 8can distinguish identical also can be different.In addition, R 9be hydrogen atom, maybe can there is the alkyl with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 9when a plurality of, a plurality of R 9can distinguish identical also can be different.In addition, as forming R 8, R 9with the functional group of carbon atom Direct Bonding, can enumerate: hydroxyl, epoxy radicals, halogen, sulfydryl, carboxyl, methacryloxy.
In addition, in above-mentioned formula (8), p is 0 or 1.The integer that q is 2～10.
As forming R 8, R 9can there is the concrete example with the alkyl of the carbon number 1～10 of the functional group of carbon atom Direct Bonding, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl, isohesyl, Sec-Hexyl, cyclopentyl, cyclohexyl, suberyl, 3-chloropropyl, 3-glycidoxy propyl group, epoxypropyl, 3-methacryloxypropyl, 3-mercapto propyl group, 3,3,3-trifluoro propyl etc.
As forming R 8can there is the concrete example with the aryl of the carbon number 6～20 of the functional group of carbon atom Direct Bonding, can enumerate: phenyl, toluyl, p-hydroxybenzene, 1-(p-hydroxybenzene) ethyl, 2-(p-hydroxybenzene) ethyl, 4-hydroxyl-5-(p-hydroxybenzene carbonyl oxygen base) amyl group, naphthyl etc.
In addition, as forming R 8can there is the concrete example with the unsaturated aliphatic base of the carbon number 1～10 of the functional group of carbon atom Direct Bonding, can enumerate vinyl, 3-acryloxy propyl group, 3-methacryloxypropyl etc.
As the concrete example of such silicon compound, can enumerate: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane, methyltrimethoxy silane, ethyl trimethoxy silane, the n-pro-pyl trimethoxy silane, the isopropyl trimethoxy silane, the 3-r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, methyl triethoxysilane, ethyl triethoxysilane, the n-pro-pyl triethoxysilane, the isopropyl triethoxysilane, the 3-chloropropyl triethoxysilane, vinyltriethoxysilane, phenyl triethoxysilane, methyl three isopropoxy silane, ethyl three isopropoxy silane, n-pro-pyl three isopropoxy silane, isopropyl three isopropoxy silane, 3-chloropropyl three isopropoxy silane, vinyl silane triisopropoxide, phenyl three isopropoxy silane, methyl three butoxy silanes, ethyl three butoxy silanes, n-pro-pyl three butoxy silanes, isopropyl three butoxy silanes, 3-chloropropyl three butoxy silanes, vinyl three butoxy silanes, phenyl three butoxy silanes, 3,3,3-trimethylsilyl trifluoroacetamide TMOS, the 3-methacryloxypropyl trimethoxy silane, methyl three glycidoxy silane, the 3-glycidoxypropyltrime,hoxysilane, the 3-mercaptopropyl trimethoxysilane, 3,4-epoxy radicals cyclohexyl trimethoxy silane, 3,3,3-trifluoro triethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-glycidoxy propyl-triethoxysilicane, the 3-mercaptopropyltriethoxysilane, 3,4-epoxy radicals cyclohexyltriethyloxysilane, 3,3,3-trifluoro, three isopropoxy silane, 3-methacryloxypropyl three isopropoxy silane, 3-glycidoxy propyl group three isopropoxy silane, 3-mercapto propyl group three isopropoxy silane, 3,4-epoxy radicals cyclohexyl, three isopropoxy silane, 3,3,3-trifluoro, three butoxy silanes, 3-methacryloxypropyl three butoxy silanes, 3-glycidoxy propyl group three butoxy silanes, 3-mercapto propyl group three butoxy silanes, 3,4-epoxy radicals cyclohexyl, three butoxy silanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silanes etc., they preferably use as the partial hydrolysis condensation product.They can use separately a kind or be used in combination two or more.
In addition, during partial hydrolysis condensation product that silane compound section is silicon compound, can directly use above-mentioned silicon compound is carried out to the partial condensate that partial hydrolysis obtains, thereby or use the alcohol with functional groups such as epoxy radicals, halogen, sulfydryl, carboxyl or methacryloxies to carry out that dealcoholization is replaced the part of resulting partial condensate and the product that obtains.By using such alcohol with functional group to be replaced the above-mentioned silicon compound partial condensate obtained that partly is hydrolyzed, can obtain easily such partial hydrolysis condensation product with functional group.
Obtain the method for silane-modified resin (B) as making above-mentioned resin portion and silane compound section carry out chemical bonding, be not particularly limited, for example can enumerate: resin portion is used the macromolecular material with hydroxyl, make the alkoxy of itself and silane compound section carry out dealcoholization, thereby make resin portion and silane compound section carry out the method for chemical bonding.Perhaps, can enumerate: resin portion is used the macromolecular material with carboxylic acid group or anhydride group, silane compound is used the compound with glycidoxypropyl, makes them carry out the method for addition reaction or makes the open loop of oxirane ring cause the method etc. of esterification by ring opening reaction.Also can after making resin portion and silane compound section carry out chemical bonding, make the resin portion polymerization in addition, thus the resin portion macromolecule be quantized.In addition, now, also can adopt following method: as the material with silane compound section chemical bonding, use low molecule organic material, after making low molecule organic material and silane compound section chemical bonding, will hang down the polymerization of molecule organic material and carry out the macromolecule quantification.
For example, among said method, according to dealcoholization, pack into the material that forms resin portion and the material that forms silane compound section, heated, and limit is carried out ester exchange reaction by the distillation of the alcohol of generation except trimming, obtains thus silane-modified resin (B).Temperature of reaction is generally 70～150 ℃, is preferably 80～130 ℃, and total reaction time is generally 2～15 hours.If temperature of reaction is too low, can not effectively the alcohol distillation be removed, in addition, if temperature of reaction is too high, the material that sometimes forms silane compound section starts to solidify condensation.
In addition, when above-mentioned dealcoholization, in order to promote reaction, can use the ester exchange catalyst of existing known ester and hydroxyl.As ester exchange catalyst, can enumerate such as: the metal such as the organic acid such as acetic acid, p-methyl benzenesulfonic acid, benzoic acid, propionic acid or lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, barium, strontium, zinc, aluminium, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, their oxide, acylate, halogenide, alkoxide etc.Wherein, preferably use the acylate of metal and organic acid, particularly preferably organotin, organic acid tin.Particularly, preferred acetic acid, tin octoate, dibutyl tin dilaurate.
In addition, dealcoholization both can carry out also can solvent-freely carrying out in organic solvent.As organic solvent, so long as the organic solvent of the material of the material of dissolving formation resin portion and formation silane compound section just is not particularly limited, for example, preferably using the boiling points such as dimethyl formamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, diethylene glycol methyl ethyl ether is the non-proton property polar solvent more than 75 ℃.
Perhaps, in said method, according to the esterification by ring opening reaction, pack into the material that forms resin portion and the material that forms silane compound section, heated, thereby caused the esterification by ring opening reaction, can access thus silane-modified resin (B).Temperature of reaction is generally 40～130 ℃, is preferably 70～110 ℃, and total reaction time is generally 1～7 hour.If temperature of reaction is too low, the reaction time extends, and in addition, if temperature of reaction is too high, the material that sometimes forms silane compound section starts to solidify condensation.
In the esterification by ring opening reaction, can use for promoting the catalyzer of reaction.As catalyzer, can enumerate, for example: the tertiary amines such as 1,8-diaza-dicyclo [5.4.0]-7-laurene, triethylenediamine, benzyl dimethyl amine, triethanolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol; The imidazoles such as glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazoles, benzimidazole; The organic phosphine classes such as tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine; The tetraphenyl borate salts such as tetraphenylphosphoniphenolate tetraphenyl borate salts, 2-ethyl-4-methylimidazole tetraphenyl borate salts, N-methylmorpholine tetraphenyl borate salts etc.
In addition, the esterification by ring opening reaction is preferably carried out under organic solvent exists, as organic solvent, so long as the organic solvent of the material of the material of dissolving formation resin portion and formation silane compound section just is not particularly limited, for example, can use METHYLPYRROLIDONE, dimethyl formamide, dimethyl acetamide, cyclohexanone etc.
The resin portion of the silane-modified resin used in the present invention (B) and the ratio of silane compound section, the weight ratio in " resin portion: silane compound section ", be preferably 1:50～50:1, more preferably 1:10～10:1.Be located at above-mentioned scope by the ratio by resin portion and silane compound section, it is more remarkable that effect of the present invention can become, so preferably.
The content of the silane-modified resin in resin combination of the present invention (B) determines to get final product according to the relation of the content with the compound (C) with acidic-group or hot latency acidic-group described later, with respect to adhesive resin (A) 100 weight portions, be preferably 1～100 weight portion, more preferably 2～50 weight portions, be more preferably 5～40 weight portions.If the content of silane-modified resin (B) is very few, utilize the pattern formative of developing to reduce, the adaptation of special developing pattern when the developing pattern width is attenuated likely reduces.On the other hand, if too much, utilize the pattern formative of developing, the void shape while particularly firing likely to worsen.
(compound (C) with acidic-group or hot latency acidic-group)
The compound (C) with acidic-group or hot latency acidic-group used in the present invention so long as the compound that there is acidic-group or produced the hot latency acidic-group of acidic-group by heating get final product, be not particularly limited, be preferably fatty compound, aromatics, heterogeneous ring compound, more preferably aromatics, heterogeneous ring compound.
These compounds (C) with acidic-group or hot latency acidic-group both can be used separately respectively or also can combine two or more use.
There is the acidic-group of compound (C) of acidic-group or hot latency acidic-group and the quantity of hot latency acidic-group and be not particularly limited, preferably add up to and there is acidic-group and/or the hot latency acidic-group more than 2.Acidic-group was both can be mutually identical also can be different.
As acidic-group, so long as acid functional group gets final product, as its concrete example, can enumerate the strong acid groups such as sulfonic group, phosphate; The faintly acid groups such as carboxyl, sulfydryl and carboxyl methylene sulfenyl.Wherein, preferred carboxyl, sulfydryl or carboxyl methylene sulfenyl, particularly preferably carboxyl.In addition, among these acidic-groups, preferred acid dissociation constant pKa is at the group of the scope below 5.0 more than 3.5.Wherein, at acidic-group, be 2 when above, using the first dissociation constant pKa1 as acid ionization constant, preferably the first dissociation constant pKa1 is at the group of above-mentioned scope.In addition, pKa, by under thin aqueous conditions, measures acid ionization constant Ka=[H 3o +] [B -]/[BH], according to pKa=-logKa, try to achieve.Here BH means organic acid, and B-means the organic acid conjugate base.
In addition, the assay method of pKa, for example can be used pH meter to measure pH, from concentration and the pH of this material, calculates.
In addition, as hot latency acidic-group, so long as the group that produces acid functional group by heating gets final product, as its concrete example, can enumerate: sulfonium salt base, benzothiazole alkali, ammonium salt base, phosphonium salt base, end-blocking carboxylic acid group etc.Wherein, preferred end-blocking carboxylic acid group.In addition, the end-blocking agent of the carboxyl used in order to obtain the end-blocking carboxylic acid group is not particularly limited, and is preferably vinyl ether compound.
In addition, the compound (C) that has acidic-group or a hot latency acidic-group can have the substituting group beyond acidic-group and hot latency acidic-group.
As such substituting group, except the alkyl such as alkyl, aryl, also can enumerate: halogen atom; Alkoxy, aryloxy group, acyloxy, heterocycle-oxo base; By amino, acyl amino, urea groups, sulfamoyl amino, alkoxycarbonyl amino, the aryloxy carbonyl amino that alkyl or aryl or heterocyclic radical replaced; Alkylthio group, arylthio, heterocycle sulfenyl etc. do not have alkyl that the polar group of proton, the polar group that do not have proton by these replace etc.
In such compound (C) with acidic-group or hot latency acidic-group, concrete example as the compound with acidic-group, can enumerate: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, two alkyd, glyceric acid, ethane diacid (also referred to as " oxalic acid "), malonic acid (also referred to as " beet acid "), succinic acid (also referred to as " succinic acid "), glutaric acid, hexane diacid (also referred to as " adipic acid "), 1, the 2-cyclohexane cyclohexanedimethanodibasic, 2 hydroxy propanoic acid, the 2-hydroxysuccinic acid, 2-hydroxy propane tricarboxylic acid, mercapto succinic acid, dimercaptosuccinic acid, 2, 3-dimercapto-1-propyl alcohol, 1, 2, 3-tri-thiol propane, 2, 3, 4-tri-thiol-n-butyl alcohol, 2, 4-dimercapto-1, the 3-butylene glycol, 1, 3, 4-tri-thiol-2-butanols, 3, 4-dimercapto-1, the 2-butylene glycol, 1, 5-dimercapto-fatty compounds such as 3-thia pentane,
Benzoic acid, P-hydroxybenzoic acid, septichen, the 2-naphthoic acid, methyl benzoic acid, mesitylenic acid, trimethylbenzoic acid, the 3-phenylpropionic acid, dihydroxy-benzoic acid, dimethoxybenzoic acid, benzene-1,2-dioctyl phthalate (also referred to as " phthalic acid "), benzene-1,3-dioctyl phthalate (also referred to as " m-phthalic acid "), benzene-Isosorbide-5-Nitrae-dioctyl phthalate (also referred to as " terephthalic acid (TPA) "), benzene-1,2, the 3-tricarboxylic acid, benzene-1,2, the 4-tricarboxylic acid, benzene-1,3, the 5-tricarboxylic acid, mellitic acid, xenyl-2,2 '-dioctyl phthalate, 2-(carboxyl methyl) benzoic acid, 3-(carboxyl methyl) benzoic acid, 4-(carboxyl methyl) benzoic acid, 2-(carboxyl carbonyl) benzoic acid, 3-(carboxyl carbonyl) benzoic acid, 4-(carboxyl carbonyl) benzoic acid, the 2-mercaptobenzoic acid, the 4-mercaptobenzoic acid, 2-sulfydryl-6-naphthoic acid, 2-sulfydryl-7-naphthoic acid, 1,2-thioresorcin, 1,3-thioresorcin, Isosorbide-5-Nitrae-thioresorcin, Isosorbide-5-Nitrae-naphthyl disulfide alcohol, 1,5-naphthyl disulfide alcohol, 2,6-naphthyl disulfide alcohol, 2,7-naphthyl disulfide alcohol, 1,2,3-tri-thiol benzene, 1,2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1,2,3-tri-(mercapto methyl) benzene, 1,2,4-tri-(mercapto methyl) benzene, 1,3,5-tri-(mercapto methyl) benzene, 1,2,3-tri-(mercaptoethyl) benzene, 1,2,4-tri-(mercaptoethyl) benzene, the aromatics such as 1,3,5-tri-(mercaptoethyl) benzene,
Nicotinic acid, isonicotinic acid, 2-furancarboxylic acid, pyrroles-2,3-dioctyl phthalate, pyrroles-2,4-dioctyl phthalate, pyrroles-2,5-dioctyl phthalate, pyrroles-3,4-dioctyl phthalate, imidazoles-2,4-dioctyl phthalate, imidazoles-2,5-dioctyl phthalate, imidazoles-4,5-dioctyl phthalate, pyrazoles-3,4-dioctyl phthalate, pyrazoles-3, the five member ring heterocyclic compound that 5-dioctyl phthalate etc. contains nitrogen-atoms, thiophene-2, the 3-dioctyl phthalate, thiophene-2, the 4-dioctyl phthalate, thiophene-2, the 5-dioctyl phthalate, thiophene-3, the 4-dioctyl phthalate, thiazole-2, the 4-dioctyl phthalate, thiazole-2, the 5-dioctyl phthalate, thiazole-4, the 5-dioctyl phthalate, isothiazole-3, the 4-dioctyl phthalate, isothiazole-3, the 5-dioctyl phthalate, 1,2,4-thiadiazoles-2, the 5-dioctyl phthalate, 1,3,4-thiadiazoles-2, the 5-dioctyl phthalate, 3-amino-5-sulfydryl-1,2, the 4-thiadiazoles, 2-amino-5-sulfydryl-1,3, the 4-thiadiazoles, 3,5-dimercapto-1,2, the 4-thiadiazoles, 2,5-dimercapto-1,3,4-thiadiazole, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base is to the phenalgin sulfonyl) succinic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base is to the phenalgin sulfonyl) succinic acid, (5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) acetic acid, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfenyl) acetic acid, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) propionic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfenyl) propionic acid, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) succinic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfenyl) succinic acid, 4-(3-sulfydryl-1,2,4-thiadiazoles-5-yl) sulfo-butane sulfonic acid, the five member ring heterocyclic compound that 4-(2-sulfydryl-1,3,4-thiadiazoles-5-yl) sulfo-butane sulfonic acid etc. contains nitrogen-atoms and sulphur atom,
Pyridine-2, the 3-dioctyl phthalate, pyridine-2, the 4-dioctyl phthalate, pyridine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, pyridine-3, the 4-dioctyl phthalate, pyridine-3, the 5-dioctyl phthalate, pyridazine-3, the 4-dioctyl phthalate, pyridazine-3, the 5-dioctyl phthalate, pyridazine-3, the 6-dioctyl phthalate, pyridazine-4, the 5-dioctyl phthalate, pyrimidine-2, the 4-dioctyl phthalate, pyrimidine-2, the 5-dioctyl phthalate, pyrimidine-4, the 5-dioctyl phthalate, pyrimidine-4, the 6-dioctyl phthalate, pyrazine-2, the 3-dioctyl phthalate, pyrazine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, triazine-2, the 4-dioctyl phthalate, 2-diethylamino-4, 6-dimercapto s-triazine, 2-dipropyl amino-4, 6-dimercapto s-triazine, 2-dibutylamino-4, 6-dimercapto s-triazine, 2-anilino--4, 6-dimercapto s-triazine, 2, 4, the 6-membered heterocyclic compound that 6-tri-thiol s-triazine etc. contains nitrogen-atoms.
Wherein, the viewpoint further improved from the adaptation that can make resulting resin molding considers, the quantity with the acidic-group in the compound of acidic-group is preferably more than 2, is particularly preferably 3.
In addition, in the compound (C) with acidic-group or hot latency acidic-group, concrete example with compound of hot latency acidic-group, can enumerate the compound that the above-mentioned acidic-group with compound of acidic-group is converted to hot latency acidic-group.For example, 1,2,4-benzene tricarbonic acid's carboxyl is converted to the end-blocking carboxylic acid group and obtain 1,2, the compound that the conducts such as 4-benzene tricarbonic acid three (1-propoxyl group ethyl ester) have hot latency acidic-group is used.The viewpoint further improved from the adaptation that makes resulting resin molding considers, the quantity with the hot latency acidic-group in the compound of hot latency acidic-group is preferably more than 2, is particularly preferably 3.
In resin combination of the present invention, silane-modified resin (B) and there is acidic-group or the ratio of the compound of hot latency acidic-group (C), weight ratio with " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group " counts 0.5～20, be preferably 0.7～18, more preferably 1～15.In the present invention, coordinate silane-modified resin (B) and there is acidic-group or the compound of hot latency acidic-group (C) in resin combination, and their ratio is located to above-mentioned scope, thereby can make the excellent storage stability of resin combination, and can make pattern formative and the transparency excellence of resulting resin molding.If containing of silane-modified resin (B) is proportional very few, the pattern formative reduces, and particularly when developing, is easy to produce residue, or the storage stability of resin combination reduces.On the other hand, if having acidic-group or hot latency acidic-group compound (C) containing proportional very few, pattern formative, the void shape while particularly firing likely worsen.
In addition, the content of the compound (C) with acidic-group or hot latency acidic-group in resin combination of the present invention determines to get final product according to the relation with silane-modified resin (B) as mentioned above, but with respect to adhesive resin (A), be preferably 0.05～200 weight portion, more preferably 0.1～75 weight portion, be more preferably 0.3～40 weight portion.If it is very few to have the content of compound (C) of acidic-group or hot latency acidic-group, the pattern formative reduces, and the adaptation of the pattern while particularly making pattern width attenuate, the void shape while firing likely worsen.On the other hand, if it is too much to have the content of compound (C) of acidic-group or hot latency acidic-group, the pattern formative reduces, and particularly when pattern forms, is easy to produce residue, or the reduction of the storage stability of resin combination.
(radiation-sensitive compound (D))
In addition, resin combination of the present invention contain adhesive resin (A), silane-modified resin (B) and there is acidic-group or the basis of the compound of hot latency acidic-group (C) on, can also contain radiation-sensitive compound (D).Radiation-sensitive compound (D) is by irradiation ultraviolet radiation or electron beam isoradial and can cause the compound of chemical reaction.In the present invention, radiation-sensitive compound (D) preferably can be controlled the alkali dissolubility from the formed resin molding of resin combination, particularly preferably uses photoacid generator.
As such radiation-sensitive compound (D), can enumerate such as the triazo-compounds such as acetophenone compound, triarylsulfonium salt, quinone di-azido compound etc., preferably triazo-compound, be particularly preferably quinone di-azido compound.
As quinone di-azido compound, can use quinone two nitrine sulfonic acid halides for example and there is the ester compounds that the compound of phenol hydroxyl forms.As the concrete example of quinone two nitrine sulfonic acid halides, can enumerate: 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride, 1,2-naphthoquinones two nitrine-4-sulfonic acid chloride, 1,2-benzoquinones two nitrine-5-sulfonic acid chloride etc.As the typical example of the compound with phenol hydroxyl, can enumerate: 1,1,3-tri-(2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol etc.As the compound with phenol hydroxyl beyond these, can enumerate: 2,3,4-trihydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, two (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) methane, 1 of 2-, 1,1-tri-(4-hydroxy-3-methyl phenyl) ethane, 1,1,2,2-tetra-(4-hydroxy phenyl) ethane, the oligomer of novolac resin, the compound that will have 1 above phenol hydroxyl and dicyclopentadiene carry out copolymerization and oligomer of obtaining etc.
In addition; as photoacid generator; except quinone di-azido compound; can use salt, halogenated organic compounds, α, the known compounds such as α '-bis-(sulfonyl) two azomethane compounds, alpha-carbonyl-α '-sulfonyl two azomethane compounds, sulphones, organic acid esters compound, organic amide compound, organic imide compound.
These radiation-sensitive compounds can be used separately respectively or combine two or more and use.
With regard to the content of the radiation-sensitive compound (D) in resin combination of the present invention, with respect to adhesive resin (A) 100 weight portions, preferably 10～100 weight portions, more preferably 15～70 weight portions, be more preferably the scope of 20～50 weight portions.If the content of radiation-sensitive compound (D) is in this scope, when the resin molding that will consist of resin combination carries out patterning, radiation exposure section and the radioactive ray not poor solubility of irradiation section in developer solution become large, radioactive ray sensitivity also uprises, utilize the formation pattern that develops easy, therefore preferably.
(crosslinking chemical (E))
In addition, resin combination of the present invention can also contain crosslinking chemical (E).The crosslinking chemical used in the present invention (E) is at the crosslinking chemical that forms cross-linked structure between cross-linker molecules or react with adhesive resin (A) and the crosslinking chemical of formation cross-linked structure between molecular resin by heating, particularly, can enumerate the compound with the reactive group more than 2.As such reactive group, for example can enumerate: amino, carboxyl, hydroxyl, epoxy radicals, isocyanate group, more preferably amino, epoxy radicals and isocyanate group, particularly preferably amino and epoxy radicals.
The molecular weight of crosslinking chemical (E) is not particularly limited, and is generally 100～100,000, is preferably 300～50,000, and more preferably 500～10,000.Crosslinking chemical both can be used separately respectively or also can combine two or more use.
As the concrete example of crosslinking chemical (E), can enumerate: the aliphatic polyamine classes such as hexamethylene diamine; 4, the aromatic polyamine classes such as 4 '-diamino-diphenyl ether, diamino diphenyl sulfone; Two (the 4 '-nitrine benzal) cyclohexanone, 4 of 2,6-, the nitrine classes such as 4 '-bis-nitrine diphenyl sulfones; Between nylon, polyhexamethylene diamines terephthalamide, polyhexamethylene, benzenedicarboxamide etc. is polyamide-based; N, N, N ', N ', N ' ', N ' '-(six alkoxyalkyls) melamine etc. can have the melamine class (the CYMEL series such as trade name " CYMEL303, CYMEL325, CYMEL370, CYMEL232, CYMEL235, CYMEL272, CYMEL212, MYCOAT506 " { above by cyanogen secret service industry company manufacture }, MYCOAT serial) of methylol or imino group etc.; N, N ', N ' ', N ' ' '-(four alkoxyalkyls) glycoluril etc. can have the glycoluril class (the CYMEL series such as trade name " CYMEL1170 " { above by cyanogen secret service industry company system }) of methylol or imino group etc.; The acrylate compounds such as ethylene glycol bisthioglycolate (methyl) acrylate; Hexamethylene diisocyanate is that polyisocyanates, isophorone diisocyanate are that polyisocyanates, toluene diisocyanate are the isocyanates based compounds such as polyisocyanates, hydrogenated diphenyl methane diisocyanate; Isosorbide-5-Nitrae-bis-(hydroxymethyl) cyclohexane, Isosorbide-5-Nitrae-bis-(hydroxymethyl) norbornane; 1,3,4-trihydroxy cyclohexane; The epoxy compounds such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, polynary phenol-type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylic ester polymer.
As the concrete example of epoxy compounds, can enumerate: the epoxy compound of 3 functionalities that the dicyclopentadiene of take is skeleton (trade name " XD-1000 ", Japan chemical drug company system), 1 of two (hydroxymethyl) n-butyl alcohols of 2,2-, 2-epoxy radicals-4-(2-Oxyranyle) cyclohexane addition product (alicyclic epoxy resin with 15 functionalities of cyclohexane skeleton and terminal epoxy groups, trade name " EHPE3150 ", Daicel chemical industrial company system), epoxidation 3-cyclohexene-1,2-dioctyl phthalate two (3-cyclohexenyl group methyl) is modified the 6-caprolactone (epoxy resin of aliphatics ring-type 3 functionalities, trade name " EPL GT301 ", Daicel chemical industrial company system), epoxidation ethylene-dimalonic acid four (3-cyclohexenyl group methyl) is modified the 6-caprolactone (epoxy resin of aliphatics ring-type 4 functionalities, trade name " EPL GT401 ", Daicel chemical industrial company system), 3,4-epoxy radicals cyclohexenyl group methyl-3 ', 4 '-epoxy radicals cyclohexene carboxylate ester (trade name " Celloxide2021 ", Daicel chemical industrial company system), 1,2:8,9-bicyclic oxygen citrene (trade name " Celloxide3000 ", Daicel chemical industrial company system), 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (trade name " Z-6043 ", Dong Li Dow Corning Corporation system) etc. the epoxy compounds that there is alicyclic structure,
Aromatic amine type multi-functional epoxy based compound (trade name " H-434 ", Dongdu changes into industrial group's system), isocyanuric acid three (2,3-epoxypropyl) ester (the multi-functional epoxy's based compound with triazine skeleton, trade name " TEPIC ", daily output chemical industrial company system), cresols phenolic varnish type multi-functional epoxy based compound (trade name " EOCN-1020 ", Japan chemical drug company system), phenol phenolic varnish type multi-functional epoxy based compound (EPIKOTE152, 154, japan epoxy resin company system), multi-functional epoxy's based compound (trade name EXA-4700 with naphthalene skeleton, Dainippon Ink Chemicals's system), chain-like alkyl multi-functional epoxy based compound (trade name " SR-TMP ", this pharmaceutical industries of slope Co., Ltd. system), multi-functional epoxy's polybutadiene (trade name " EPL PB3600 ", Daicel chemical industrial company system), the glycidyl polyethers compound of glycerine (trade name " SR-GLG ", this pharmaceutical industries of slope Co., Ltd. system), two glycerine poly epihydric alcohol ether compound (trade names " SR-DGE ", this pharmaceutical industries of slope Co., Ltd. system, polyglycereol poly epihydric alcohol ether compound (trade name " SR-4GL ", this pharmaceutical industries of slope Co., Ltd. system), glycidoxy oxypropyl trimethyl silane (trade name " Z-6040 ", Dong Li Dow Corning Corporation system) etc. the epoxy compounds that does not there is alicyclic structure.
The content of the crosslinking chemical in resin combination of the present invention (E) is not particularly limited, consider the desired thermotolerance degree of resin molding of using resin combination of the present invention to obtain, set and get final product arbitrarily, with respect to adhesive resin (A) 100 weight portions, be generally 5～80 weight portions, be preferably 7～75 weight portions, more preferably 10～70 weight portions.No matter crosslinking chemical (E) is too much still very few, all may make thermotolerance reduce.
(other compounding ingredients)
Can also contain solvent in resin combination of the present invention.As solvent, be not particularly limited, can enumerate as the solvent of resin combination and known solvent straight chain ketones such as acetone, methyl ethyl ketone, cyclopentanone, methyl-n-butyl ketone, 3-hexanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, methyln-hexyl ketone, 3-octanone, 4-octanone; The alcohols such as n-propanol, isopropyl alcohol, normal butyl alcohol, cyclohexanol; The ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, diox; The pure ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether; The ester classes such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate; The cellosolve ester classes such as cellosolve acetic acid esters, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic acid esters, butyl cellosolve acetate; The propandiolses such as propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; The diglycol classes such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol methyl ethyl ether; The saturated gamma lactone classes such as gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, γ-octalactone; The halogenated hydrocarbons such as triclene; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Dimethyl acetamide, dimethyl formamide, N-methylacetamide isopolarity solvent etc.These solvents both can be used separately also and can combine two or more use.The content of solvent is with respect to adhesive resin (A) 100 weight portions, preferably 10～10000 weight portions, more preferably 50～5000 weight portions, be more preferably the scope of 100～1000 weight portions.In addition, in the situation that contain solvent in resin combination, solvent is removed usually after forming resin molding.
In addition, resin combination of the present invention so long as do not hinder the scope of effect of the present invention, just can contain other compounding ingredients such as surfactant, acid compound, coupling agent or derivatives thereof, sensitizer, latency acid-producing agent, antioxidant, light stabilizer, defoamer, pigment, dyestuff, filler etc. as required.
Surfactant is used in order to prevent striped (coating striped), raising developability etc.As the concrete example of surfactant, can enumerate: the polyethylene oxide alkyl ethers classes such as polyethylene oxide bay ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; The polyethylene oxide aryl ethers such as polyethylene oxide octyl phenyl ether, polyethylene oxide nonylplenyl ether; The nonionics such as polyethylene oxide dialkyl esters such as polyethylene oxide dilaurate, polyethylene oxide distearate are surfactant; Fluorine class surfactant; Organosilicone surfactants; Methacrylic acid copolymer class surfactant; Acrylic copolymer class surfactant etc.
The coupling agent or derivatives thereof has the effect of the resin molding that further raising consists of resin combination and the adaptation of each layer that comprises the semiconductor layer that forms the semiconductor element substrate.As the coupling agent or derivatives thereof, can use and there is 1 atom be selected from silicon atom, titanium atom, aluminium atom, zirconium atom, and there is the oxyl (ヒ De ロ カ Le PVC Le オ キ シ, hydrocarbyloxy) that is bonded to this atom or compound of hydroxyl etc.
As the coupling agent or derivatives thereof, for example can enumerate:
The tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane;
Methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the isopropyl trimethoxy silane, the isopropyl triethoxysilane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, the n-pentyl trimethoxy silane, the n-hexyl trimethoxy silane, the n-heptyl trimethoxy silane, the n-octyl trimethoxy silane, positive decyl trimethoxy silane, to the styryl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-chloropropyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, 3,3,3-trifluoro propyl triethoxysilane, the 3-TSL 8330, APTES, N-2-(amino-ethyl)-3-TSL 8330, N-phenyl-3-TSL 8330, 2-hydroxyethyl trimethoxy silane, 2-hydroxyethyl triethoxysilane, 2-hydroxypropyl trimethoxy silane, 2-hydroxypropyl triethoxysilane, 3-hydroxypropyl trimethoxy silane, 3-hydroxypropyl triethoxysilane, the 3-mercaptopropyl trimethoxysilane, the 3-mercaptopropyltriethoxysilane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy radicals cyclohexyl) ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 3-ethyl (trimethoxy silane base propoxyl group methyl) oxetanes, 3-ethyl (triethoxysilicane alkyl propoxyl group methyl) oxetanes, 3-triethoxysilyl-N-(1,3-dimethyl-Ding fork) propyl group amine, the trialkoxysilanes such as two (tri-ethoxy silylpropyl) four thioethers,
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, diη-propyl dimethoxy silane, the diη-propyl diethoxy silane, diisopropyl dimethoxy silane, the diisopropyl diethoxy silane, di-n-butyl dimethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, the di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, the di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, the diphenyl diethoxy silane, 3-glycidoxy propyl group methyldiethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, N-2-(amino-ethyl)-dialkoxy silicane classes such as 3-aminopropyl methyl dimethoxysilane,
In addition, can enumerate: the silicon atoms compounds such as methyl triacetyl TMOS, dimethyl diacetyl TMOS;
(tetraisopropoxy titanium, four titanium n-butoxide, four (2-ethyl hexyl oxy) titanium, titanium-isopropoxy ethohexadiol salt, diisopropoxy two (diacetone) close titanium, propane dioxy base titanium two (ethyl acetoacetate), three titanium n-butoxide Monostearates, diisopropoxy titanium distearate, stearic acid titanium, diisopropoxy titanium diisostearate, (2-n-butoxy carbonyl benzoyl oxygen base) three titanium butoxide, two (the triethanolamine root closes) titaniums of two n-butoxies, in addition, also have Preneact series (Ajinimoto Fine Techno Co. Inc.'s system)) etc. the titaniferous atomic compound;
(acetyl aluminum alkoxide diisopropyl hydrochlorate) etc. is containing the aluminium atomic compound;
(four n-propoxyzirconium, four n-butoxy zirconiums, four acetyl acetone zirconiums, three butoxy acetyl acetone zirconiums, only son's oxygen ethylacetoacetone two (oacetic acid) are closed zirconium, dibutoxy two (oacetic acid) closes zirconium, tetrem acyl acetone zirconium, three butoxy zirconium stearates) etc. is containing the zirconium atom compound.
Concrete example as sensitizer, can enumerate: 2H-pyrido-(3,2-b)-1,4-oxazine-3 (4H)-one class, 10H-pyrido-(3,2-b)-Isosorbide-5-Nitrae-benzo thiazides, urazole class, hydantoins Hydantoins, barbital acids, glycine anhydride class, I-hydroxybenzotriazole class, alloxan class, maleimide etc.
As antioxidant, can use the phenol antioxidant used in common polymkeric substance, Phosphorus antioxidant, sulphur class antioxidant, lactone antioxidant etc.For example, as phenol antioxidant, can enumerate: 2, the 6-di-tert-butyl-4-methy phenol, p methoxy phenol, styrenated phenol, positive octadecyl-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 2, 2 '-methylene-bis-(4-methyl-6-tert-butylphenol), the 2-tert-butyl group-6-(3 '-tert-butyl group-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 4, 4 '-Ding pitches base-bis--(3 methy 6 tert butyl phenol), 4, 4 '-sulfo--bis-(3 methy 6 tert butyl phenol), [3-(3 for pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], alkylation bis-phenol etc.As Phosphorus antioxidant, can enumerate: triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester etc.As sulphur class antioxidant, can enumerate dilauryl thiodipropionate etc.
As light stabilizer, any of the material of the free radical that can utilize light to produce for seizure such as the ultraviolet light absorbers such as benzophenone, salicylate class, benzotriazole, cyanoacrylate, metallic complex salt system, hindered aminess (HALS) etc.Wherein, HALS is the compound with piperidine structure, to the less painted of resin combination and have good stability, therefore preferably.As concrete compound, can enumerate: two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl/tridecyl 1,2,3,4-butane tetracarboxylic acid esters, two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.
The preparation method of resin combination of the present invention is not particularly limited, and each composition that utilizes known method will form resin combination mixes and gets final product.
The method of mixing is not particularly limited, and preferably each composition that will form resin combination is dissolved or dispersed in to solvent and the solution or the dispersion liquid that obtain are mixed.Thus, can solution or the form of dispersion liquid obtain resin combination.
Be dissolved or dispersed in the method for solvent for each composition that will form resin combination, get final product according to conventional method.Particularly, can enumerate the method for using stirrer and magnetic stirring apparatus to be stirred or the method for using high-shear homogenizer, decollator, planetary mixer, biaxial rneader, bowl mill, three-roll grinder etc. etc.In addition, after each composition is dissolved or dispersed in to solvent, the filtrator that can to use such as aperture be 0.5 about μ m etc. is filtered.
The solid component concentration of resin combination of the present invention is generally 1～70 % by weight, is preferably 5～60 % by weight, more preferably 10～50 % by weight.As long as solid component concentration is in this scope, the film thickness uniformity of the resin molding of balance steady dissolution, coating or formation that just can be highly, flatness etc.
(semiconductor element substrate)
Then, for semiconductor element substrate of the present invention, describe.Semiconductor element substrate of the present invention has the resin molding that the resin combination by the invention described above forms.
As semiconductor element substrate of the present invention, so long as there is the substrate of the structure that semiconductor element is installed on substrate, get final product, be not particularly limited, can enumerate: active-matrix substrate, organic EL substrate, integrated circuit component substrate and solid-state imager substrate etc., the viewpoint that the resin molding formed from the resin combination by forming by the invention described above makes characteristic improve particular significant effect considers, preferably active-matrix substrate and organic EL substrate.
Active-matrix substrate as an example of semiconductor element substrate of the present invention, be not particularly limited, but illustration has the active-matrix substrate of following structure: the on-off elements such as thin film transistor (TFT) (TFT) are configured on substrate with rectangular, and supply with the signal line of the signal for driving this on-off element and arrange in the mode crossed one another for the source signal line of supplying with display to this on-off element.In addition, as the thin film transistor (TFT) of an example of on-off element, can be illustrated on substrate there is gate electrode, the formation of gate insulator, semiconductor layer, source electrode and drain electrode etc.
In addition, as the organic EL substrate of an example of semiconductor element substrate of the present invention, such as the organic EL substrate that can illustration there is following structure: there is the luminous body that formed by anode, hole injection/transport layer, organic luminous layer, electron injecting layer and negative electrode etc. as semiconductor layer and for separating of the pixel separation film of this luminous body on substrate.
And, as the resin molding that forms semiconductor element substrate of the present invention, preferably by above-mentioned resin combination, formed, and the semiconductor layer comprised with the semiconductor component surfaces that is arranged on the semiconductor element substrate or semiconductor element contacts and the resin molding that forms, be not particularly limited, when semiconductor element substrate of the present invention is active-matrix substrate or organic EL substrate, can adopt following structure.; for example; when semiconductor element substrate of the present invention is active-matrix substrate; the resin molding consisted of the resin combination of the invention described above can be made as at the formed diaphragm in the surface of active-matrix substrate or the gate insulating film that for example, forms with semiconductor layer (, the amorphous silicon layer) contact of the thin film transistor (TFT) that forms active-matrix substrate.Perhaps, when semiconductor element substrate of the present invention is the organic EL substrate, can adopt at the formed encapsulating film in the surface of organic EL substrate or for separating the pixel separation film of the luminous body that the organic EL substrate comprises (usually being formed by anode, hole injection/transport layer, organic luminous layer, electron injecting layer and negative electrode as semiconductor layer).
In semiconductor element substrate of the present invention, the method as forming resin molding, be not particularly limited, such as using the methods such as rubbing method, membrane laminating process.
Rubbing method is for example for carrying out the method that heat drying removes desolventizing after the coating resin composition.As the method for coating resin composition, can adopt such as spray-on process, spin-coating method, rolling method, mould and be coated with method, scrape the whole bag of tricks such as the skill in using a kitchen knife in cookery, whirl coating, excellent painting method, silk screen print method.The heat drying condition because of the kind of each composition or mixing ratio different, usually 30～150 ℃, preferably at 60～120 ℃, usually with 0.5～90 minute, preferably with 1～60 minute, more preferably with 1～30 minute, get final product.
Membrane laminating process comprises, resin combination is coated to the B level films such as resin molding or metal film and is formed with on matrix material, then, removes desolventizing by heat drying and obtains B level film, then by this B level film lamination.The heat drying condition can suitably be selected according to kind, the mixing ratio of each composition, and heating-up temperature is generally 30～150 ℃, is generally 0.5～90 minute heat time heating time.Can use the press-connection machines such as the stacked machine of pressurization, pressing machine, vacuum laminated machine, vacuum press, the stacked machine of roller to carry out film lamination.
Thickness as resin molding; be not particularly limited; suitably set and get final product according to purposes; resin molding be the diaphragm used of active-matrix substrate or organic EL substrate use encapsulating film the time; the thickness of resin molding is preferably 0.1～100 μ m; more preferably 0.5～50 μ m, be more preferably 0.5～30 μ m.
In addition, in the situation that resin combination of the present invention comprises crosslinking chemical (E), can carry out cross-linking reaction to the resin molding formed by above-mentioned rubbing method or membrane laminating process.The crosslinked kind according to crosslinking chemical (E) like this selects proper method to get final product, and usually by heating, is undertaken.With regard to heating means, can use such as electric hot plate, baking oven etc. and carry out.Heating-up temperature is generally 180～250 ℃, can suitably select heat time heating time according to size or thickness, the use equipment etc. of resin molding, for example uses in the situation of electric hot plate, is generally the scope of 5～60 minutes, use in the situation of baking oven, be generally the scope of 30～90 minutes.Heating can be carried out as required under the non-active gas atmosphere.As non-active gas, only otherwise contain oxygen and do not make the resin molding oxidation get final product, can enumerate such as nitrogen, argon, helium, neon, xenon, krypton etc.Wherein, preferred nitrogen, argon, particularly preferably nitrogen.Especially preferably oxygen content is that 0.1 volume % is following, preferred following non-active gas, the particularly nitrogen of 0.01 volume %.These inert gases can be used separately respectively or combine two or more and use.
In addition, the resin molding consisted of above-mentioned resin combination, also can patterning for for the diaphragm of active-matrix substrate or the film that forms with the pattern of regulation for the encapsulating film of organic EL substrate etc. the time.As resin molding being carried out to the method for patterning, for example can enumerate, make in resin combination to contain radiation-sensitive compound (D), the resin combination that use contains radiation-sensitive compound (D), form the front resin molding of patterning, resin molding before patterning is irradiated to active radioactive ray and form the sub-image pattern, then the method for apparentization of pattern etc. by the resin molding contact developer solution that makes to have the sub-image pattern.
As active radioactive ray, as long as the alkali-soluble of the resin combination that can make the contained radiation-sensitive compound (D) of resin combination activate, make to contain radiation-sensitive compound (D) changes, be not particularly limited.Particularly, can use the light such as ultraviolet ray, KrF excimer laser, ArF excimer laser of the single wavelengths such as ultraviolet ray, g line or i line; The particle beams of electron beam and so on etc.As optionally being irradiated with pattern-like, these active radioactive ray form the method for sub-image pattern, get final product according to conventional method, can use such as utilizing reduced projection exposure device etc. to see through the method for the light such as desirable mask pattern irradiation ultraviolet radiation, g line, i line, KrF excimer laser, ArF excimer laser or utilizing method that the particle beams such as electron beam described etc.Using in the situation of light as active radioactive ray, can be single wavelength light, can be also mixed wavelengths light.Illuminate condition can suitably be selected according to the active radioactive ray that use, and for example, uses in the situation of the light that wavelength is 200～450nm, and exposure is generally 10～1,000mJ/cm 2, preferred 50～500mJ/cm 2scope, according to irradiation time and illumination, determine.After so active radioactive ray are irradiated in operation, as required, by resin molding heat treated about 1～2 minute at the temperature of 60～130 ℃ of left and right.
Then, the sub-image pattern that is formed at the resin molding before patterning is developed and made its apparentization.As developer solution, usually use the aqueous solution of alkali compounds.As alkali compounds, can use for example alkali metal salt, amine, ammonium salt.Alkali compounds can be both mineral compound, can be also organic compound.As the concrete example of these compounds, can enumerate: the alkali metal salts such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate; Ammoniacal liquor; The primary amine such as ethylamine, n-pro-pyl amine; The secondary amine such as diethylamide, di-n-propyl amine; The tertiary amines such as triethylamine, methyl diethylamide; The quaternary ammonium salts such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH, choline; The hydramine such as dimethylethanolamine, triethanolamine; Pyrroles, piperidines, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, cyclic amine such as 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, 1-METHYLPYRROLIDONE etc.These alkali compounds can be used separately respectively or combine two or more and use.
As the aqueous medium of buck solution, can use: water; The water-miscible organic solvent such as methyl alcohol, ethanol etc.Buck solution can be added with the surfactant of appropriate amount etc.
As the method for the resin molding contact developer solution that makes to have the sub-image pattern, can use methods such as puddling, spray-on process, infusion process.As development conditions, suitably to select get final product, development temperature is generally 0～100 ℃, preferably 5～55 ℃, the more preferably scope of 10～30 ℃, development time suitably selection in the scope of 30～180 seconds usually.
After so the operation purpose forms the target pattern resin molding, as required, in order to remove the development residue, can use washing fluid to rinse.After rinsing processing, utilize pressurized air or compressed nitrogen to remove remaining washing fluid.
And then, as required, in order to make contained radiation-sensitive compound (D) inactivation of resin combination, also can irradiate active radioactive ray to whole of semiconductor element substrate.The irradiation of active radioactive ray can utilize illustrative method in the formation of above-mentioned sub-image pattern.Can or after irradiation, resin molding be heated with the irradiation while.As heating means, can enumerate the method for example the semiconductor element substrate heated in electric hot plate or baking oven.Heating-up temperature is generally 100～300 ℃, the preferred scope of 120～200 ℃.
In the present invention, after resin molding carries out patterning, can carry out cross-linking reaction.Crosslinkedly get final product according to the method described above.
Resin combination of the present invention is to be combined with silane-modified resin (B) with specific ratio and to have acidic-group or the compound of hot latency acidic-group (C) and the composition that obtains in adhesive resin (A), therefore the pattern formative that the excellent storage stability of resin combination of the present invention, and the utilization of the resin molding that uses resin combination of the present invention to obtain develops and the transparency are excellent.And, according to the present invention, by the resin molding by such, being applied to the semiconductor element substrate, resin molding that can the semiconductor element substrate is contained carries out patterning accurately, and the semiconductor element substrate that can realize high performance can be provided thus.In addition, the transparency excellence of the resin molding that uses resin combination of the present invention to obtain therefore can be used suitably in requiring transparent purposes.
Embodiment
Below, enumerate embodiment and comparative example the present invention is described in further detail." part " in each example is just weight basis unless otherwise specified.
In addition, the definition of each characteristic and evaluation method are as follows.
<polymerisation conversion>
After polyreaction finishes, use the remaining quantity of the monomer in the gas chromatography determination reactant liquor, by this value, calculate polymerisation conversion.
<hydrogenation ratio>
Utilize 1the H-NMR spectrogram, obtain hydrogenation ratio with the form of the ratio of the carbon-to-carbon double bond molal quantity before the relative hydrogenation of carbon-to-carbon double bond molal quantity be hydrogenated.Take before hydrogenation is benchmark, with % by mole form obtain the ratio of the carbon-to-carbon double bond be hydrogenated.
<weight-average molecular weight, number-average molecular weight>
Use gel permeation chromatography (be called for short GPC, eastern Cao company system, will model " HLC-8020 ", use after 3 kinds of chromatographic columns combinations of TSKgel SuperH2000, TSKgel SuperH4000, TSKgel SuperH5000), calculate weight-average molecular weight and number-average molecular weight with the form of the molecular weight of polystyrene conversion.It should be noted that, as developing solvent, use tetrahydrofuran.
<development adaptation>
After resin combination is carried out to spin coating on silicon wafer, use electric hot plate 100 ℃ of prebake 2 minutes, form the thick resin molding of 2.5 μ m.Then, in order to make resin mold, forming pattern, via following mask, is 5mW/cm to 365nm and the light intensity of irradiating the desired time 2ultraviolet ray, described mask has 10 rectangle slits (being equivalent to spacing) that can see through light abreast, and the width that (is equivalent to line) between slit adjacent one another are identical with slit width (that is, can form the line of same widths and the mask of pitch pattern).It should be noted that, as mask, use width between slit width and adjacent slots to be respectively 8 kinds of the totals of 1 μ m, 2 μ m, 3 μ m, 4 μ m, 5 μ m, 10 μ m, 25 μ m and 50 μ m.
Then, use 0.4 % by weight tetramethylammonium hydroxide aqueous solution as developer solution, at 23 ℃, utilize puddling to carry out development treatment after 120 seconds, with ultrapure water, rinsed for 30 seconds.It should be noted that, puddling (パ De Le method) is to fill with developer solution standing method on resin molding.Utilize above method, on glass substrate, make and there is the resin molding (, thering are the line width of 1 μ m, 2 μ m, 3 μ m, 4 μ m, 5 μ m, 10 μ m, 25 μ m and 50 μ m and 8 kinds of resin moldings of spacing width) that transfer printing has the pattern (pattern of line and spacing) of mask.In the present embodiment, use has the resin combination of the radiation-sensitive energy of eurymeric and makes resin molding, therefore in this resin molding, the part that is positioned at the slit portion of mask is the part that has been removed resin molding, this part is called to spacing section, the part be positioned between the adjacent slots of mask is the remaining part that resin molding is arranged, and this part is called to line section.Then, by so operating the resulting glass substrate that has formed the figuratum resin molding of tool, be set as adaptation mensuration sample, utilize following methods to estimate adaptation.
That is, use observation by light microscope adaptation obtained above to measure and use sample, carry out thus the evaluation of adaptation.Particularly, at first, determine that there is the strippable substrate of having no way of in line section.If line section does not peel off, can say that adaptation is high.Online section has in situation about peeling off, and the maximum line section to how many μ m width of confirmation peels off, with following benchmark evaluation.The width of line section is less, more easily from substrate, peels off.Therefore, from the width of the line section of strippable substrate, maximum width is less can say that adaptation is higher.
Zero: do not exist line section to peel off.Even perhaps exist line section to peel off, the maximum line width that line section peels off is also below 3 μ m
△: the maximum line width that line section peels off is 4～5 μ m
*: the maximum line width that line section peels off is more than 10 μ m
<residue while developing>
Radiation sensitive resin composition is spin-coated on silicon wafer, then, uses electric hot plate 100 ℃ of prebake 2 minutes, form the thick resin molding of 2.5 μ m.Then, via the mask of the hole patterns of 8 μ m * 8 μ m, in air this resin molding irradiate 60 second 365nm and light intensity be 5mW/cm 2ultraviolet ray.Then, use 0.4 % by weight tetramethylammonium hydroxide aqueous solution 23 ℃ carry out 120 second development treatment after, rinse with ultrapure water the pattern that form contact hole 30 seconds.
Then, for the resin molding of the pattern with contact hole of acquisition like this, use scanning electron microscope (SEM), confirm to have or not dissolved residue in contact hole, use following benchmark evaluation.Do not observe the resin molding of dissolved residue, utilize the pattern formative excellence of developing, therefore preferably.
Zero: do not observe the development residue.
*: observe the development residue.
<hole state while firing>
During with above-mentioned development, the evaluation of residue is similarly irradiated 365nm for the resin molding of the pattern with contact hole obtained and light intensity is 5mW/cm in air 2100 seconds of ultraviolet ray.Then, the section of the pattern that utilizes electron microscope observation to obtain, the lower end width of mensuration pattern, using it as " the lower end width a of the pattern before baking and banking up with earth in advance ".Then, use baking oven at 230 ℃, the figuratum resin molding of resulting tool to be carried out baking and banking up with earth in advance in 1 hour, for resulting resin molding after baking and banking up with earth in advance, cross section with the electron microscope observation pattern, the shape of the upper end of evaluation pattern generating, and the lower end width of mensuration pattern, using it as " the lower end width b of the pattern after baking and banking up with earth in advance ".Then, obtain the ratio (b/a) of the lower end width b of the pattern after baking and banking up with earth in advance with respect to the lower end width a of the pattern before baking and banking up with earth in advance, estimated with following benchmark.
Zero: b/a is more than 0.8.
△: b/a is more than 0.5 and is less than 0.8.
*: b/a is less than 0.5 or the distortion of the shape of contact hole.
<the transparency>
Resin combination is spin-coated on to glass substrate (Corning company manufactures, " Corning1737 (trade name) ") upper, then, uses electric hot plate to bake and bank up with earth in advance 2 minutes at 100 ℃, the resin molding that the formation thickness is 2.5 μ m.Then, use 0.4 % by weight tetramethylammonium hydroxide aqueous solution carries out 120 second dip treating to this resin molding at 23 ℃ after, with ultrapure water, carry out cleaning in 30 seconds, then in air, irradiate 365nm and light intensity is 5mW/cm 2100 seconds of ultraviolet ray.Then, for the resin molding of irradiation ultraviolet radiation, use baking oven, at 230 ℃, heated 60 minutes bake and bank up with earth in advance, obtain thus the test sample formed by the glass substrate that is formed with resin molding.Then, for the test sample obtained, (Japan Spectroscopy Corporation's system, " ultraviolet-visible pectrophotometer V-560 (trade name) ", the mensuration of the transmissivity while carrying out wavelength 400nm, by the transparency of following benchmark evaluation resin molding to use spectrophotometer.It should be noted that, the transmissivity of resin molding is by will be without the glass substrate of resin molding as blank, and the scaled value of calculating when establishing the resin thickness and being 2 μ m is tried to achieve.
Zero: light transmittance is more than 90%
△: light transmittance is more than 80% and lower than 90%
*: light transmittance is lower than 80%
<storage stability>
After preparing resin combination, in 23 ℃, the environment of humidity 50%, place 7 days, then, during with above-mentioned development, the evaluation of residue, similarly to the resulting resin molding with contact hole pattern, is irradiated 365nm and light intensity is 5mW/cm in air 2100 seconds of ultraviolet ray.Then, the cross section of the pattern obtained with electron microscope observation post, measure the lower end width of pattern, using it as " placing the lower end width a ' of the pattern before the baking and banking up with earth in advance of resin combination after 7 days ".And, obtain resulting pattern lower end width a before baking and banking up with earth in advance in the evaluation of pattern lower end width a ' before the resin combination of placing after 7 days is baked and banked up with earth in advance and hole state when above-mentioned firing ratio (a '/a), with following benchmark, estimated.
Zero: a '/a is more than 0.95 and is below 1.05.
*: a '/a is lower than 0.95 or surpass 1.05.
" synthesis example 1 "
The preparation of<cyclic olefin polymer (A-1)>
In the glass voltage-resistant reactor processed through nitrogen displacement, pack into by N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,40 % by mole of 3-dicarboxyl acid imides and 4-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 100 parts of the monomer mixtures, 1 of 12 carbon-60 % by mole of formations of 9-alkene, (1,3-bis-for 2 parts of 5-hexadienes, dichloro
Figure BDA0000386244120000451
base imidazoline-2-subunit) (tricyclohexyl phosphine) benzal ruthenium (according to Org.Lett., the 1st volume, 953 pages, in 1999, the method for record is synthetic) 200 parts, 0.02 part and diglycol ethyl-methyl ether, stir on one side, at 80 ℃ make its reaction 4 hour on one side, polymerization liquid obtained.
Then, resulting polymerization liquid is packed in autoclave, with 150 ℃, hydrogen pressure 4MPa, stir and carry out hydrogenation in 5 hours, obtain polymkeric substance (A-1) solution that contains cyclic olefin polymer.The polymerisation conversion of resulting polymkeric substance is 99.7 % by weight, and the polystyrene conversion weight-average molecular weight is 7,150, and number-average molecular weight is 4,690, and molecular weight distribution is 1.52, and hydrogenation ratio is 99.7%.In addition, the solid component concentration of resulting cyclic olefin polymer solution is 34.4 % by weight.
" synthesis example 2 "
The preparation of<acrylate copolymer (A-2)>
Pack 2 in the flask that possesses cooling tube and stirring machine, 2 '-azo is two-200 parts, (2,4-methyl pentane nitrile) 7 parts and diglycol ethyl-methyl ether.Then, 16 parts of methacrylic acids, the methacrylic acid three ring [5.2.1.0 that pack into 2,6] 3 parts of decane-16 parts of 8-base esters, 20 parts of acrylic acid 2-methyl cyclohexyls, 40 parts of glycidyl methacrylate, 10 parts of styrene and α-methyl styrene dimers, and, after carrying out the nitrogen displacement, start slowly to stir.Then, make the temperature of solution increase 70 ℃, by keeping this temperature 4 hours, obtain the polymer solution that contains acrylate copolymer (A-2).The polystyrene conversion weight-average molecular weight (Mw) of acrylate copolymer (A-2) is 8,000, and molecular weight distribution (Mw/Mn) is 2.3.In addition, the solid component concentration of resulting acrylate copolymer (A-2) solution is 34.4 % by weight.
" synthesis example 3 "
The preparation of<poly-(methyltrimethoxy silane)>
32 parts of 136 parts of the methyltrimethoxy silane of packing in the flask that stirring apparatus, backflow cooling tube and thermometer are installed and methyl alcohol.Then, limit is by them in stirring at normal temperature, and limit dripped following aqueous solution with 5 minutes, and described aqueous solution is to dissolve 0.1 part of concentrated hydrochloric acid at 13.5 parts of ion exchange waters (for methyltrimethoxy silane, 0.75 molar equivalent) to obtain, successive reaction 4 hours.Then, after reaction in 4 hours, the backflow cooling tube is replaced with to fractionating column, the distillation of then carrying out 30 minutes low boiling point components under 80 ℃ of temperature, normal pressure is removed, afterwards, by distilling, remove until 100 ℃ of temperature, pressure 0.3KPa are gathered (methyltrimethoxy silane).While utilizing gel permeation chromatography (GPC) to analyze resulting poly-(methyltrimethoxy silane), the weight-average molecular weight of resulting poly-(methyltrimethoxy silane) is 490 (polystyrene conversion).
" synthesis example 4 "
The preparation of<silane-modified epoxy resin (B-1) solution>
Add 960.0 parts of 800.0 parts of bisphenol A type epoxy resins (epoxide equivalent 480g/eq) and diethylene glycol dimethyl ether in the reaction unit that possesses stirring machine, cooling tube and thermometer, 80 ℃ of dissolvings.Then, add wherein poly-(methyltrimethoxy silane) 605.0 parts that obtain in synthesis example 3 and as 2.3 parts of the dibutyl tin laurates of catalyzer, 80 ℃ of separating methanol reactions of carrying out 5 hours, obtain silane-modified epoxy resin (B-1) solution.In addition, the weight (weight ratio) of weight/bisphenol-type epoxy resin that the effective constituent of resulting silane-modified epoxy resin (after solidifying) is 50 % by weight, silicon dioxide conversion is 0.51, and epoxide equivalent is 1400g/eq.In addition, poly-(methyltrimethoxy silane) maintains 87 % by mole of utilizations of the methoxyl of partial condensate composition 1h-NMR determines.
" synthesis example 5 "
The preparation of<silane-modified phenolics (B-2)>
Possessing during stirring machine, water trap, temperature take into account the reaction unit of nitrogen ingress pipe, add phenolic varnish type phenolics (waste river chemical industry (strain) system, trade name TAMANOL759) poly-(methyltrimethoxy silane) 590.3 parts obtained in 800 parts, synthesis example 3,100 ℃ of melting mixing.Add wherein as 3 parts of the dibutyl tin laurates of catalyzer, at 110 ℃, carry out separating methanol reaction in 7 hours, in addition, by 80 parts of distillation for removing methanol thus, obtain silane-modified phenolics (B-2).
" synthesis example 6 "
<contain epoxy radicals the methoxy silane partial condensate manufacture>
Possessing during stirring machine, water trap, temperature take into account the reaction unit of nitrogen ingress pipe, poly-(methyltrimethoxy silane) 9140 parts obtained in 1400 parts of epoxy prapanols and the synthesis example 3 of packing into, after nitrogen flows down warming while stirring to 90 ℃, add 2.2 parts of dibutyl tin laurates to make its reaction.In reaction, use the water trap distillation to remove generated methyl alcohol, reach the approximately moment of 630 parts in its amount and carry out cooling.From heating up to the needed time till cooling be 6 hours.Then, 13kPa with about 10 minutes methyl alcohol remaining in by system approximately 30 parts of decompressions remove, obtain the alkoxy silane partial condensate that contains epoxy radicals.
" synthesis example 7 "
The preparation of<silane-modified polyamic acid (B-3)>
In possessing stirring machine, cooling tube, temperature and taking into account 3 mouthfuls of flasks of 2L of nitrogen ingress pipe, add 4,1170 parts of 112 parts, 4 '-diamino-diphenyl ether and 1-METHYLPYRROLIDONEs, after room temperature is fully mixed, limit is cooled to below 60 ℃, limit adds 118 parts of pyromellitic dianhydride, stirs synthesizing polyamides acid 30 minutes.The polyimide conversion solid remainder of resulting polyamic acid is 15 % by weight.Then, add 500 parts of 1-METHYLPYRROLIDONEs, be warming up to 80 ℃, add 40.2 parts of alkoxy silane partial condensates that contains epoxy radicals obtaining in synthesis example 6 and as 0.24 part of the glyoxal ethyline of catalyzer, 80 ℃ of reactions 4 hours.Then, after reaction in 4 hours, be cooled to room temperature, obtain solidifying the silane-modified polyamic acid (B-3) of remainder 12 % by weight.
" synthesis example 8 "
<contain glycidyl ether the tetramethoxy-silicane partial condensate manufacture>
Possessing during stirring machine, water trap, temperature take into account the reaction unit of nitrogen ingress pipe, the diglycidyl 1 of packing into, 400 parts and the tetramethoxy-silicane partial condensate (chemistry that rubs (strain) system more, the mean number of Si in trade name " methyl silicate 51 ", 1 molecule is 4, number-average molecular weight 480) 8,957.9 part, after nitrogen flows down warming while stirring to 90 ℃, add as 2.0 parts of the dibutyl tin laurates of catalyzer, make its reaction.In reaction, use water trap that the distillation of the methyl alcohol of generation is removed, reach the approximately moment of 550 parts in its amount and carry out cooling.From heating up to the needed time till cooling be 5 hours.Then, 13kPa with about 10 minutes methyl alcohol remaining in by system approximately 68 parts of decompressions remove, obtain the tetramethoxy-silicane partial condensate that contains glycidyl ether.
" synthesis example 9 "
The manufacture of<silane-modified acrylic resin (B-4)>
Possessing stirring machine, cooling tube, temperature is taken into account in the reaction unit of gas introduction tube, 1461 parts of the diethylene glycol dimethyl ether of packing into, after nitrogen flows down and is warmed up to 100 ℃, respectively with within 1 hour, dripping by 25 parts of 417 parts of butyl methacrylates and 83.3 parts of mix monomers that form of Hydroxyethyl Acrylate and di-tert-butyl peroxides, again respectively with within 1 hour, dripping by 10 parts of 250 parts of methyl methacrylates and 83.3 parts of mix monomers that form of methacrylic acid and di-tert-butyl peroxides, and then make its reaction 3 hours at 120 ℃, obtaining solid constituent is the acrylic polymers solution that contains carboxyl of 37 % by weight.The number-average molecular weight of the resulting acrylic acid series polymeric compounds that contains carboxyl is 50,000, acid value (take solid component meter) is 65mgKOH/g.
Then, 30 parts of same reaction units of packing into of 152 parts of the tetramethoxy-silicane partial condensates that contains glycidyl ether that obtain in 700 parts of the acrylic polymers solution that contains carboxyl that will be prepared by said method, synthesis example 8 and methyl alcohol, at nitrogen, flow down, 80 ℃ make its reaction 6 hours, obtain thus solidifying the silane-modified acrylic resin (B-4) that remainder is 38.3 % by weight.
" embodiment 1 "
The preparation of<resin combination>
291 parts of cyclic olefin polymer (A-1) solution obtained in the synthesis example 1 of mixing as adhesive resin (A) (with cyclic olefin polymer (A-1), counting 100 parts), as 359 parts, the diglycol ethyl-methyl ether of solvent, 20 parts of silane-modified epoxy resin (B-1) solution obtained in synthesis example 4 as silane-modified resin (B) (with silane-modified epoxy resin (B-1), counting 10 parts), as 1 of the compound (C) with acidic-group or hot latency acidic-group, 2, 3 parts of 4-benzene tricarbonic acids, as radiation-sensitive compound (D) by 1, 1, 3-tri-(2, 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, 30 parts of the condensation products that 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2 moles) forms, and as 3 of crosslinking chemical (E), 4-epoxy radicals cyclohexenyl group methyl-3 ', 30 parts of 4 '-epoxy radicals cyclohexene carboxylate esters, after it is dissolved, utilize the teflon filter made device that aperture is 0.45 μ m to filter, prepare resin combination.
Then, use resin combination obtained above, the adaptation of being developed, residue while developing, every evaluation of hole state, the transparency and storage stability while firing.Result is illustrated in table 1.
" embodiment 2 "
Except will be as 1,2 of the compound (C) with acidic-group or hot latency acidic-group, 4-benzene tricarbonic acid's use level changes to beyond 10 parts from 3 parts, and operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" embodiment 3 "
To change to 60 parts (with silane-modified epoxy resin (B-1), counting 30 parts) from 20 parts as the use level of silane-modified epoxy resin (B-1) solution of silane-modified resin (B), and will be as 1 of the compound (C) with acidic-group or hot latency acidic-group, 2,4-benzene tricarbonic acid's use level changes to 2 parts from 3 parts, in addition, operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" embodiment 4 "
Except as crosslinking chemical (E), use N, N, N ', N ', N ' ', N ' '-10 parts of (hexamethoxy methyl) melamine class crosslinking chemicals replace 3,4-epoxy radicals cyclohexenyl group methyl-3 ', beyond 4 '-epoxy radicals cyclohexene carboxylate ester, operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" embodiment 5 "
Except use 5 parts of isocyanuric acid three (2,3-epoxypropyl) esters to replace 3,4-epoxy radicals cyclohexenyl group methyl-3 ' as crosslinking chemical (E), beyond 4 '-epoxy radicals cyclohexene carboxylate ester, operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" embodiment 6 "
Except use the 10 parts of replacement silane-modified epoxy resins of silane-modified phenolics (B-2) (B-1) that obtain in synthesis example 5 as silane-modified resin (B), operation similarly to Example 5, obtain resin combination, similarly estimated.Result is illustrated in table 1.
" embodiment 7 "
Except as crosslinking chemical (E), using 2-(3,4-epoxy radicals cyclohexyl) beyond 20 parts of replacement isocyanuric acid three (2,3-epoxypropyl) esters of ethyl trimethoxy silane, operation similarly to Example 6, obtain resin combination, similarly estimated.Result is illustrated in table 1.
" embodiment 8 "
As the compound (C) with acidic-group or hot latency acidic-group, use 5 parts of the propylene glycol monomethyl ether solution of 1,2,4-benzene tricarbonic acid three (1-propoxyl group ethyl) ester (with 1,2,4-benzene tricarbonic acid three (1-propoxyl group ethyl) ester is counted 3 parts) replace 1,2,4-benzene tricarbonic acid, in addition, operation, obtain resin combination similarly to Example 7, similarly estimated.Result is illustrated in table 1.
" embodiment 9 "
Use 83 parts of silane-modified polyamic acid (B-3) solution (in 10 parts of silane-modified polyamic acids (B-3)) that obtain in synthesis example 7 as silane-modified resin (B), replace silane-modified epoxy resin (B-1) solution, in addition, operation similarly to Example 1, obtain resin combination, similarly estimated.Result is illustrated in table 1.
" embodiment 10 "
As silane-modified resin (B), use 26 parts of silane-modified acrylic resin (B-4) solution (with silane-modified acrylic resin (B-4), counting 10 parts) that obtain in synthesis example 9, replace silane-modified epoxy resin (B-1) solution, in addition, operation similarly to Example 1, obtain resin combination, similarly estimated.Result is illustrated in table 1.
" embodiment 11 "
291 parts of acrylate copolymer (A-2) solution obtained in the synthesis example 2 of mixing as adhesive resin (A) (with acrylate copolymer (A-2), counting 100 parts), as 359 parts, the diglycol ethyl-methyl ether of solvent, 20 parts of silane-modified epoxy resin (B-1) solution obtained in synthesis example 4 as silane-modified resin (B) (with silane-modified epoxy resin (B-1), counting 10 parts), as 1 of the compound (C) with acidic-group or hot latency acidic-group, 2, 5 parts of the propylene glycol monomethyl ether solution of 4-benzene tricarbonic acid three (1-propoxyl group ethyl) ester are (with 1, 2, 4-benzene tricarbonic acid three (1-propoxyl group ethyl) ester is counted 3 parts), as radiation-sensitive compound (D) by 1, 1, 3-tri-(2, 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, 30 parts of the condensation products of 2-naphthoquinones two nitrine-5-sulphonic acid chloride compound (2 moles), and as the 2-(3 of crosslinking chemical (E), 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane is 10 parts, after it is dissolved, prepare resin combination with the teflon filter made device filtration of aperture 0.45 μ m.Then, for resulting resin combination, estimated similarly to Example 1.Result is illustrated in table 1.
" embodiment 12 "
Except use the 10 parts of replacement silane-modified epoxy resins of silane-modified phenolics (B-2) (B-1) that obtain in synthesis example 5 as silane-modified resin (B), operation obtains resin combination similarly to Example 11, is similarly estimated.Result is illustrated in table 1.
" comparative example 1 "
Except mismatching as 1,2 of the compound (C) with acidic-group or hot latency acidic-group, beyond the 4-benzene tricarbonic acid, operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" comparative example 2 "
Except will be as 1,2 of the compound (C) with acidic-group or hot latency acidic-group, 4-benzene tricarbonic acid's use level changes to beyond 0.3 part from 3 parts, and operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" comparative example 3 "
Except will be as 1,2 of the compound (C) with acidic-group or hot latency acidic-group, 4-benzene tricarbonic acid's use level changes to beyond 30 parts from 3 parts, and operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" comparative example 4 "
Except mismatching silane-modified epoxy resin (B-1) solution as silane-modified resin (B), operation, obtain resin combination similarly to Example 1, similarly estimated.Result is illustrated in table 1.
" comparative example 5 "
Except mismatching the acrylate copolymer (A-2) as adhesive resin (A), and will be made as beyond 100 parts as the use level of the silane-modified phenolics (B-2) of silane-modified resin (B), operation obtains resin combination similarly to Example 12, is similarly estimated.Result is illustrated in table 1.
As shown in table 1, be combined with silane-modified resin (B) and there is acidic-group or the excellent storage stability of the resin combination of the compound of hot latency acidic-group (C) with specific ratio in adhesive resin (A), and, the pattern formative excellence that the utilization of the resin molding that uses this resin combination to obtain is developed, and there is the high transparency (embodiment 1～12).
On the other hand, the weight ratio of mismatching the situation of the compound (C) with acidic-group or hot latency acidic-group and " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group " is too high, reach in 33.3 situation the development adaptation of resulting resin molding and hole state difference (comparative example 1,2) while firing.
The weight ratio of " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group " is too low, be only in 0.3 situation, the storage stability of resulting resin combination is poor, when making resin molding, result can produce development residue (comparative example 3) in addition.
In addition, in the situation that do not coordinate silane-modified resin (B), the development adaptation is poor, the adaptation of the developing pattern when the developing pattern width is attenuated insufficient (comparative example 4).
In addition, in the situation that do not coordinate adhesive resin (A), the storage stability of resulting resin combination is poor, in addition, when making resin molding, as a result the development residue, while firing the hole state and the transparency poor (comparative example 5).

Claims (8)

1. a resin combination, it contains adhesive resin (A), silane-modified resin (B) and has acidic-group or the compound of hot latency acidic-group (C), wherein,
The ratio of described silane-modified resin (B) and the described compound (C) with acidic-group or hot latency acidic-group is counted " silane-modified resin (B)/have the compound (C) of acidic-group or hot latency acidic-group "=0.5～20 with weight ratio.
2. resin combination as claimed in claim 1, wherein,
Described silane-modified resin (B) is to be selected from that at least one macromolecular material in polyester, polyamide, polyimide, polyamic acid, epoxy resin, acryl resin, urethane resin and phenolics and silicon compound carry out chemical bonding and the compound that obtains.
3. resin combination as claimed in claim 2, wherein,
Described silicon compound is the partial hydrolysis condensation product of the silicon compound shown in the silicon compound shown in following formula and/or following formula,
(R 8) r-Si-(OR 9) 4-r
In above-mentioned formula, the integer that r is 0～3, R 8for thering is alkyl, the aryl of carbon number 6～20 or the unsaturated aliphatic base of carbon number 2～10 with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 8when a plurality of, a plurality of R 8identical or different separately, R 9for hydrogen atom maybe can have the alkyl with the carbon number 1～10 of the functional group of carbon atom Direct Bonding, R 9when a plurality of, a plurality of R 9identical or different separately.
4. resin combination as described as any one in claim 1～3, wherein,
Described silane-modified resin (B) containing proportional with respect to described adhesive resin (A) 100 weight portions, be 1～100 weight portion.
5. resin combination as described as any one in claim 1～4, wherein,
Described adhesive resin (A) is for having cyclic olefin polymer or the acryl resin of protic polar group.
6. resin combination as described as any one in claim 1～5, it also contains radiation-sensitive compound (D).
7. resin combination as described as any one in claim 1～6, it also contains crosslinking chemical (E).
8. a semiconductor element substrate, it possesses the resin molding formed by the described resin combination of any one in claim 1～7.
CN2012800148101A 2011-03-30 2012-03-29 Resin composition and semiconductor element substrate Pending CN103443707A (en)

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