CN102076774B - Radiation-sensitive resin composition, laminate and method for producing the same, and semiconductor device - Google Patents

Abstract

Disclosed is a resin composition containing a binder resin (A), a compound (B) having an acidic group, an organic solvent (C) and a compound (D) having one atom selected from a silicon atom, a titanium atom, an aluminum atom and a zirconium atom, and a hydrocarbyloxy group or a hydroxy group bonded to the atom. The resin composition is characterized in that the compound (B) having an acidic group is composed of at least one compound selected from the group consisting of aliphatic compounds, aromatic compounds and heterocyclic compounds, and the total amount of the compound (B) and the compound (D) is 10-50 parts by weight relative to 100 parts by weight of the binder resin (A). Also disclosed are a laminate which is obtained by arranging a resin film composed of the resin composition on a substrate and a semiconductor device composed of the laminate.

Description

Radiation-sensitive resin composition, multilayer body and manufacture method thereof and semiconducter device

Technical field

The present invention relates to resin combination and multilayer body, described multilayer body comprises substrate and is positioned at the resin molding being obtained by this resin combination on substrate, more specifically, the present invention relates to be applicable to manufacture multilayer body and manufacture method and the semiconducter device on the resin combination, substrate of the electronic units such as display element, integrated circuit component, solid-state imager with the resin molding being obtained by this resin combination.

Background technology

In the electronic units such as display element, integrated circuit component, solid-state imager, colour filter, thin film transistor and black matrix (black matrix), be provided with various resin moldings; as described resin molding, comprise for prevent these electronic units there is deteriorated or damaged protective membrane, for making element surface or wiring realize the planarization film of planarization and for keeping the electrical insulating film etc. of electrical insulating property.In addition, in the elements such as film transistor type liquid crystal display device, integrated circuit component, be provided with the resin molding as interlayer dielectric for making to be configured to insulate between multiple wirings of stratiform.

In the past, as the resin material that is used to form these resin moldings, conventional was the heat-curing resin materials such as epoxy resin.But along with the densification of wiring and device in recent years, as these resin materials, require to use the new type resin material that there is good adaptation with substrate and there is the excellent electric characteristics such as low-dielectric.

In order to meet above-mentioned requirements, for example, the radiation-sensitive composition that contains following compositions is disclosed in patent documentation 1: adhesive resin is cyclic olefin base polymer; Radiosensitive compound; Organic solvent; The compound with acidic-group is trimethoxysilyl phenylformic acid; And the compound with the-oxyl (ヒ De ロ カ Le PVC Le オ キ シ yl) being bonded on Siliciumatom is γ-glycidoxypropyltrime,hoxysilane.

Following radiation-sensitive composition is disclosed in patent documentation 2: it contains adhesive resin is that the organic insulation polymer shown in formula (1), radiosensitive compound are light acid producing agent, organic solvent, the compound with 2 acidic-groups is phthalic acid.According to the record of patent documentation 2, above-mentioned radiation-sensitive composition not only can form fine pattern, can also seek the raising of electrical specification.

[Chemical formula 1]

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2005-292277 communique

Patent documentation 2: TOHKEMY 2005-171259 communique (No. 2005/127355 specification sheets of U.S. Patent Application Publication)

Summary of the invention

The problem that invention will solve

The inventor etc. find after deliberation: although the radiation-sensitive composition of recording in patent documentation 1 will coordinate bonding auxiliary agent in actual applications, the adaptation between itself and substrate is still not enough; Adaptation between radiation-sensitive composition and the substrate of recording in patent documentation 2 is also insufficient, must further improve.

Thus, the object of the present invention is to provide a kind of resin combination, it has excellent thermotolerance, solvent resistance, surface hardness, insulativity, flatness, the transparency, resistance to chemical reagents and low-dielectric etc., and its adaptation is improved.

In addition, another object of the present invention is to provide the manufacture method of a kind of multilayer body and this multilayer body, wherein, described multilayer body has the resin molding that substrate obtains with being formed on this resin combination of use on this substrate.

The method of dealing with problems

In order to reach above-mentioned purpose, the inventor etc. have passed through deep research, found that: the effect that can obtain while using following resin combination, described resin combination has the compound (B) of acidic-group by combination in adhesive resin (A), organic solvent (C) and compound (D) and obtain, described compound (D) has the Siliciumatom of being selected from, titanium atom, 1 kind of atom in aluminium atom and zirconium atom, and there is the-oxyl or the hydroxyl that are bonded on this atom, the above-mentioned compound (B) with acidic-group is for being selected from fatty compounds, in aromatics and heterogeneous ring compound at least a kind, and with respect to above-mentioned adhesive resin (A) 100 weight parts, the total content of above-claimed cpd (B) and above-claimed cpd (D) is in specified quantitative scope.The inventor etc. have completed the present invention based on this discovery.

Thus, the invention provides a kind of resin combination, it contains adhesive resin (A), there is the compound (B) of acidic-group, organic solvent (C) and compound (D), described compound (D) has the Siliciumatom of being selected from, titanium atom, 1 kind of atom in aluminium atom and zirconium atom, and there is the-oxyl or the hydroxyl that are bonded on this atom, wherein, there is the compound (B) of acidic-group for being selected from fatty compounds, in aromatics and heterogeneous ring compound at least a kind, and with respect to 100 parts by weight resin, the total content of compound (B) and compound (D) is 10～50 weight parts.

In resin combination of the present invention, preferably further contain radiosensitive compound (E).

In resin combination of the present invention, the acidic-group of the above-mentioned compound (B) with acidic-group is preferably carboxyl, sulfydryl or carboxyl methylene radical sulfenyl.

In resin combination of the present invention, the preferably scope more than 3.5 and below 5.0 of acid ionization constant pKa (for the situation with more than 2 acidic-group, being the first acid ionization constant pKa1) of the acidic-group of the above-mentioned compound (B) with acidic-group.

In resin combination of the present invention, the above-mentioned compound (B) with acidic-group preferably contains more than 2 acidic-group.

In resin combination of the present invention, preferably further contain linking agent (F).

In resin combination of the present invention, above-mentioned linking agent (F) is preferably epoxy compounds.

In resin combination of the present invention, above-mentioned epoxy compounds is preferably the epoxy compounds with alicyclic structure.

In resin combination of the present invention, above-mentioned adhesive resin (A) is preferably and is selected from cyclic olefin polymer, acrylic resin, cardo resin (the cardo resin with protic polar group, axle shape resin, カ Le De Trees fat), more than a kind polymkeric substance in polysiloxane and polyimide.

In resin combination of the present invention, above-claimed cpd (D) is preferably the compound further with the functional group that can react with protic polar group.And the functional group that can react with protic polar group in above-claimed cpd (D) is preferably isocyanate group, sulfydryl, epoxy group(ing) or amino.

In addition,, in resin combination of the present invention, the content of above-claimed cpd (B) is preferably more than the content of above-claimed cpd (D).

According to the present invention, provide a kind of multilayer body that has the resin molding being formed by the resin combination of the invention described above at substrate superimposed layer.

The multilayer body of the invention described above can obtain by the manufacture method of multilayer body, and the manufacture method of described multilayer body comprises, uses resin combination on substrate, to form above-mentioned resin molding.

In the manufacture method of the multilayer body of the invention described above, preferably there is following step: form above-mentioned resin molding on substrate after, make the step of the resin crosslinks that forms above-mentioned resin molding.

In the multilayer body of the invention described above, above-mentioned resin molding can be patterned resin film.

Above-mentioned resin molding is that the multilayer body of patterned resin film can obtain by the manufacture method of following multilayer body, the manufacture method of described multilayer body comprises: use resin combination of the present invention on substrate, to form above-mentioned resin molding, above-mentioned resin molding is irradiated to active radioactive rays, thereby in above-mentioned resin molding, form sub-image pattern, then, by developing solution is contacted with above-mentioned resin molding, so that sub-image pattern changes as seen, thereby above-mentioned resin molding is carried out to patterning.

In the manufacture method of the multilayer body with patterned resin film of the invention described above, preferably there is following step: form above-mentioned patterned resin film on substrate after, the resin that makes to form above-mentioned patterned resin film carries out the step of crosslinking reaction.

In addition, according to the present invention, provide a kind of semiconducter device of the multilayer body that comprises the invention described above.

The effect of invention

Resin combination of the present invention, because having excellent electrical characteristic, is easy to pattern form to design, and in the transparency and the resistance to chemical reagents still after heat with height shape-holding property, excellence, therefore applicable to various uses.

In addition, multilayer body of the present invention is because having excellent electrical characteristic, shape-holding property, the transparency and resistance to chemical reagents, therefore suitable to for example display element, integrated circuit component, solid-state imager, colour filter, in the electronic units such as black matrix as following electronic component-use materials'use: for preventing that these electronic units from deteriorated or damaged protective membrane occurring, for making element surface or wiring realize the planarization film of planarization, for keeping the electrical insulating film of electrical insulating property (to comprise as thin crystal cast liquid crystal display device, the interlayer dielectric of the electrical insulating film of integrated circuit component, soldering-resistance layer etc.), micro lens, the electronic component-use materials such as dividing plate (spacer).

Multilayer body of the present invention is because having excellent adaptation, therefore can be by splitting being suppressed in electronic unit manufacturing step, improve yield rate, in addition, can eliminate the fault that cannot normally work that the goods that comprise electronic unit cause because environment for use changes.Thus, can realize at an easy rate the making of the goods that are built-in with well behaved electronic unit.

Embodiment

Resin combination of the present invention contains adhesive resin (A), there is the compound (B) of acidic-group, organic solvent (C) and compound (D), described compound (D) has the Siliciumatom of being selected from, titanium atom, 1 kind of atom in aluminium atom and zirconium atom, and there is the-oxyl or the hydroxyl that are bonded on this atom, wherein, there is the compound (B) of acidic-group for being selected from fatty compounds, in aromatics and heterogeneous ring compound at least a kind, and with respect to adhesive resin (A) 100 weight parts, compound (B) is 10～50 weight parts with the total content of compound (D).

adhesive resin (A)

In the present invention, there is no particular restriction for adhesive resin (A), be preferably cyclic olefin polymer, acrylic resin, cardo resin, polysiloxane or the polyimide with protic polar group, wherein, especially preferably there is the cyclic olefin polymer of protic polar group.

These adhesive resins (A) can be distinguished use separately, also two or more can be used in combination.

Described protic polar group, refers to comprise to be positioned at atom and the hydrogen atom of periodictable the 15th family or the 16th family and to be positioned at periodictable the 15th family or the atom of the 16th family and the group of hydrogen atom Direct Bonding.As the atom that is positioned at periodictable the 15th family or the 16th family, be preferably and be positioned at the 1st cycle of periodictable the 15th family or the 16th family or the atom in the 2nd cycle, more preferably Sauerstoffatom, nitrogen-atoms or sulphur atom, is especially preferably Sauerstoffatom.

As the concrete example of protic polar group, can enumerate: the polar group that hydroxyl, carboxyl (hydroxycarbonyl group), sulfonic group, phosphate etc. contain Sauerstoffatom; The polar group that primary amino, secondary amino group, primary amide base, secondary amide base (imide) etc. contain nitrogen-atoms; The polar group that sulfydryl etc. contain sulphur atom; Etc..Wherein, preferably contain the polar group of Sauerstoffatom, more preferably carboxyl.

In the present invention, there is no particular restriction for the number that is bonded in the protic polar group on the cyclic olefin polymer with protic polar group, and, diverse protic polar group can be comprised.

Described cyclic olefin polymer in the present invention, refers to homopolymer or the multipolymer of the cyclic olefin monomers of have ring texture (alicyclic ring or aromatic nucleus) and carbon-to-carbon double bond.In cyclic olefin polymer, can also there is the unit being imported by other monomer beyond cyclic olefin monomers.

In the entire infrastructure unit of cyclic olefin polymer, the ratio of cyclic olefin monomers unit is generally 30～100 % by weight, preferably 50～100 % by weight, more preferably 70～100 % by weight.

Having in the cyclic olefin polymer of protic polar group, protic polar group can be bonded on cyclic olefin monomers unit, also can be bonded on other monomeric unit beyond cyclic olefin monomers, but preferably be bonded on cyclic olefin monomers unit.

As the monomer for forming the cyclic olefin polymer with protic polar group, can enumerate: have protic polar group cyclic olefin monomers (a), there is monomer (d) beyond cyclic olefin monomers (b), the cyclic olefin monomers (c) without polar group and the cyclic olefin of other polar group beyond protic polar group (following, by these monomers referred to as monomer (a)～(d)).Wherein, monomer (d) can not have other polar group beyond protic polar group or protic polar group, also can not have polar group completely.

In the present invention, there is the cyclic olefin polymer of protic polar group preferably by monomer (a) and monomer (b) and/or monomer (c) formation, more preferably formed by monomer (a) and monomer (b).

As the concrete example of monomer (a), can enumerate: 5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5-methyl-5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5-carboxyl methyl-5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxyl carbonyl dicyclo [2.2.1] hept-2-ene", 9-hydroxycarbonyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-hydroxycarbonyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9,10-dihydroxyl carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] cyclic olefin that contains carboxyl such as 12 carbon-4-alkene; 5-(4-hydroxy phenyl) dicyclo [2.2.1] hept-2-ene", 5-methyl-5-(4-hydroxy phenyl) dicyclo [2.2.1] hept-2-ene", 9-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] cyclic olefin that contains hydroxyl such as 12 carbon-4-alkene; Etc..Wherein, preferably contain the cyclic olefin of carboxyl.These cyclic olefin monomers (a) with protic polar group can be distinguished use separately, also two or more can be used in combination.

The concrete example of other polar group beyond the protic polar group having as the cyclic olefin monomers (b) with other polar group beyond protic polar group, can enumerate: ester group (general name of alkoxy carbonyl and aryloxycarbonyl), N-substituted imides base, epoxy group(ing), halogen atom, cyano group, carbonyl oxygen base carbonyl (the acid anhydrides residue of dicarboxylic acid), alkoxyl group, carbonyl, tertiary amino, sulfonic group, acryl etc.Wherein, preferably ester group, N-substituted imides base and cyano group, more preferably ester group and N-substituted imides base, especially preferably N-substituted imides base.

As the concrete example of monomer (b), can enumerate following cyclic olefin.

As the cyclic olefin with ester group, for example can enumerate: 5-acetoxyl group dicyclo [2.2.1] hept-2-ene", 5-methoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-methyl-5-methoxycarbonyl dicyclo [2.2.1] hept-2-ene", 9-acetoxyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methoxycarbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-ethoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-positive propoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-isopropoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-n-butoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-methoxycarbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-ethoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-positive propoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-isopropoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-n-butoxy carbonyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene etc.

As the cyclic olefin with N-substituted imides base, for example can enumerate: N-phenyl dicyclo [2.2.1] heptan-5-alkene-2,3-imide, N-(2-ethylhexyl)-1-isopropyl-4-methyl dicyclo [2.2.2] be pungent-5-alkene-2,3-imide, N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-imide, N-[(2-ethyl butoxy) ethoxycarbonyl propyl]-dicyclo [2.2.1] heptan-5-alkene-2,3-imide etc.

As the cyclic olefin with cyano group, for example can enumerate: 9-cyano group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-cyano group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 5-cyano-bicyclo [2.2.1] hept-2-ene" etc.

As the cyclic olefin with halogen atom, for example can enumerate: 9-chlorotetracyclin [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl-9-chlorotetracyclin [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene etc.

The above-mentioned cyclic olefin monomers (b) with protic polar group other polar group in addition can be distinguished use separately, also two or more can be used in combination.

As the concrete example of cyclic olefin monomers (c) completely without polar group, can enumerate: dicyclo [2.2.1] hept-2-ene" (also referred to as " norbornylene "), 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] ten carbon-3,8-diene (trivial name: Dicyclopentadiene (DCPD)), Fourth Ring [10.2.1.0 ^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] 15 carbon-5,12-diene, cyclopentenes, cyclopentadiene, 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] 15 carbon-12-alkene etc.

These cyclic olefin monomers (c) completely without polar group can be distinguished use separately, also two or more can be used in combination.

As the concrete example of the monomer (d) beyond cyclic olefin, can enumerate chain alkene.As chain alkene, for example 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 carbonatomss 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 dienes such as 7-octadiene; Etc..

Monomer (d) beyond these cyclic olefins can be distinguished use separately, also two or more can be used in combination.

Can obtain by monomer (a) and the needed monomer that is selected from monomer (b)～(d) are carried out to polymerization jointly for the cyclic olefin polymer with protic polar group of the present invention.Polymerization and polymkeric substance can also further carry out hydrogenation.Polymkeric substance after hydrogenation is also included within the cyclic olefin polymer with protic polar group using in the present invention.

In addition, the cyclic olefin polymer with protic polar group using in the present invention can also obtain by following method: utilize known properties-correcting agent that protic polar group is imported in the cyclic olefin polymer without protic polar group, and carry out hydrogenation as required.Hydrogenation also can carry out for importing protic polar group polymkeric substance before.In addition, can also utilize properties-correcting agent to carry out modification to the cyclic olefin polymer with protic polar group, and then import the protic polar group based on properties-correcting agent.

The polymkeric substance without protic polar group can be by obtaining carrying out polymerization after the arbitrary combination of above-mentioned monomer (b)～(d).

As the properties-correcting agent for importing protic polar group, conventionally can use the compound in a part with protic polar group and reactive carbon-to-carbon unsaturated bond.

As the concrete example of this compounds, can enumerate: the unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, angelicic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, atropic acid, styracin; The unsaturated alcohols such as vinyl carbinol, methyl ethylene methyl alcohol, crotyl alcohol, methylallyl 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..

As the modified-reaction of cyclic olefin polymer that uses this properties-correcting agent, carry out modification according to ordinary method, conventionally can under the existence of radical initiator, carry out.

As for monomer (a) and monomer (the b)～monomer (d) that is selected from are optionally carried out to the polymerization process of polymerization jointly, carry out polymerization according to ordinary method, for example, can adopt ring-opening polymerization method or addition polymerization method.

As polymerizing catalyst, preferably use the such as metal complex of molybdenum, ruthenium, osmium etc.These polymerizing catalysts can be distinguished use separately, also two or more can be used in combination.With regard to the amount of polymerizing catalyst, the metallic compound with in polymerizing catalyst: the molar ratio computing of cyclic olefin, be generally 1: 100～1: 2,000,000, preferably 1: 500～1: 1,000,000, more preferably 1: 1,000～1: 500,000 scopes.

For the polymkeric substance being obtained by each monomer polymerization, conventionally make spent hydroprocessing catalyst carry out hydrogenation.

As hydrogenation catalyst, can use for example normally used hydrogenation catalyst in the time carrying out the hydrogenation of olefin(e) compound.Specifically can use Ziegler-type homogeneous catalyst, noble metal complexes catalyzer and carried noble metal class catalyzer etc.

In above-mentioned hydrogenation catalyst, from can be not there is not the side reactions such as functional group modification to polymkeric substance in the carbon-to-carbon unsaturated bond of the main chain viewpoint of carrying out selective hydrogenation consider, the noble metal complexes catalyzer such as preferred rhodium, ruthenium, especially preferred coordination has and has highly to the nitrogenous heterocyclic carbene compound of electronics or the ruthenium catalyst of phosphine class.

Through the hydrogenation ratio of hydrogenation post polymerization owner chain conventionally more than 90%, preferably more than 95%, more preferably more than 98%.Hydrogenation ratio is within the scope of this time, and the thermotolerance of adhesive resin (A) is excellent, therefore preferred especially.

The hydrogenation ratio of adhesive resin (A) can pass through ¹h-NMR spectrum is measured.For example, can obtain by the ratio of the mole number of carbon-to-carbon double bond before the carbon-to-carbon double bond mole number of over hydrogenation and hydrogenation.

In the present invention, as the cyclic olefin polymer with protic polar group, the particularly preferably polymkeric substance with structural unit shown in formula (I) as follows, more preferably has the polymkeric substance of structural unit shown in structural unit shown in formula (I) and formula (II).

[Chemical formula 2]

[in formula (I), R ¹～R ⁴represent independently of one another hydrogen atom or-X _n(X is divalent organic group to-R ' base; N is 0 or 1; R ' is for optionally having substituent alkyl, optionally having substituent aryl or a protic polar group.)。R ¹～R ⁴in be one of at least that R ' is protic polar group-X _n-R ' base.M is integer 0～2.]

[chemical formula 3]

[in formula (II), R ⁵～R ⁸2 carbon atoms with arbitrary combination and their institute's bondings form ring structure jointly, and this ring structure is to contain Sauerstoffatom or nitrogen-atoms as 3～5 yuan of heterocycle structures that become annular atoms.In addition, this heterocycle optionally has substituting group.K is integer 0～2.]

In general formula (I), as the example of the divalent organic group of X representative, can enumerate methylene radical, ethylidene and carbonyl etc.

The alkyl that optionally has substituent alkyl and be generally the carbonatoms 1～7 of straight or branched of R ' representative, as the example, can enumerate the alkyl such as methyl, ethyl, n-propyl, sec.-propyl.Optionally there is the aryl that substituent aryl is generally carbonatoms 6～10, as the example, can enumerate the aryl such as phenyl, benzyl.Abovementioned alkyl or aryl have in substituent situation, as the substituent example importing on these alkyl or aryls, can enumerate: the alkyl of the carbonatomss 1～4 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-; The aryl of the carbonatomss 6～12 such as phenyl, xylyl, tolyl, naphthyl; Etc..

As the protic polar group of R ' representative, can enumerate group as above.

In general formula (II), as R ⁵～R ⁸with the common 3 yuan of heterocycle structures that form of 2 carbon atoms of arbitrary combination and their institute's bondings, can enumerate epoxy construction etc.In addition, as R ⁵～R ⁸the example of 5 yuan of heterocycle structures that jointly form with 2 carbon atoms of arbitrary combination and their institute's bondings, can enumerate dicarboxylic anhydride structure [C (=O)-O-C (=O)-], imide structure [C (=O)-N-C (=O)-] etc.This heterocycle has in substituent situation, as the substituent example importing on this heterocycle, can enumerate phenyl, naphthyl, anthryl etc.

The acrylic resin using in the present invention is not particularly limited, but preferably has at least one homopolymer as neccessary composition or multipolymer in carboxylic acid, the acrylic compound that has the carboxylic acid anhydride of acryl or contain epoxy group(ing) of acryl to be selected from.

As the concrete example of carboxylic acid with acryl, can enumerate (methyl) vinylformic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid etc.;

As the concrete example of carboxylic acid anhydride with acryl, can enumerate maleic anhydride, citraconic anhydride etc.;

As the concrete example of the acrylic compound that contains epoxy group(ing), can enumerate glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, vinylformic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-ethylacrylate-6,7-epoxy heptyl ester etc.

Wherein, preferably (methyl) vinylformic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxy heptyl ester etc.In the present invention, described " (methyl) vinylformic acid " refers to any in methacrylic acid and vinylformic acid.

Acrylic resin can be by the unsaturated compound that is selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and contain epoxy group(ing) one of at least with acrylic ester monomer or acrylate beyond the multipolymer that forms of other copolymerisable monomer.As other acrylic ester monomer, can be listed below: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid amyl group (ペ Application チ Le) ester, (methyl) vinylformic acid amyl group (ア ミ Le) ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl, (methyl) alkyl acrylates such as (methyl) vinylformic acid isooctadecane base ester,

(methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid phenoxyalkyl esters such as (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy-ethyl ester, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-methoxyl group butyl ester, polyethyleneglycol (methyl) acrylate, oxyethyl group Diethylene Glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, oxyethyl group polypropylene glycol (methyl) acrylate, polyalkylene glycol (methyl) acrylate such as Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-butyl cyclohexyl, (methyl) vinylformic acid two encircle pentyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid three and encircle (methyl) vinylformic acid cycloalkyl esters such as decyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester etc.Wherein, preferred (methyl) butyl acrylate, (methyl) EHA, (methyl) lauryl acrylate, (methyl) isodecyl acrylate and (methyl) vinylformic acid 2-ethoxy ethyl ester etc.

As the copolymerisable monomer beyond acrylate; as long as can with the compound of the above-mentioned carboxylic acid with acryl, the acrylic compound generation copolymerization that there is the carboxylic acid anhydride of acryl or contain epoxy group(ing); be not particularly limited, for example can enumerate: the free-radical polymerised compound that vinyl benzyl methyl ether, vinyl glycidyl ether, vinylbenzene, alpha-methyl styrene, divinyl, isoprene etc. contain vinyl.

These compounds can be distinguished use separately, also two or more can be used in combination.

As the polymerization process of above-mentioned monomer, carry out polymerization according to ordinary method, can adopt for example suspension polymerization, emulsion polymerization, solution polymerization process etc.

Described cardo resin is to have cardo structure (cardo structure), have and have the resin of the skeleton structure of two ring texturees forming bonding on the quaternary carbon atom of ring texture.Generally speaking, cardo structure is the structure that bonding has phenyl ring on fluorenes ring.

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 group(ing) fluorene skeleton, there is the fluorene skeleton of acryl etc.

The cardo resin using in the present invention can have reaction between the functional group of this skeleton with cardo structure etc. and polymerization forms by bonding.Cardo resin has the structure (cardo structure) main chain being connected with the side chain of high spatial steric hindrance by an element, and has ring texture in the direction substantially vertical with main chain.

There is the example of cardo structure of epoxy group(ing) glycidyl ether structure suc as formula shown in (III).

[chemical formula 4]

(in formula (III), n represents integer 0～10.)

As the monomer with cardo structure, for example can enumerate: two (glycidoxy phenyl) fluorenes type epoxy resin; Bisphenol fluorene type epoxy resin and acrylic acid condenses; Two (4-hydroxy phenyl) fluorenes, 9 of 9,9-, the bisphenols that two (the 4-hydroxy-3-methyl phenyl) fluorenes etc. of 9-contain 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 group) fluorenes classes of 9-; Etc..

Cardo resin is the polymkeric substance obtaining by having the monomer polymerization of cardo structure, can be also with other can copolymerization the multipolymer that forms of monomer.

As the polymerization process of above-mentioned monomer, as long as carry out polymerization according to ordinary method, for example, can adopt ring-opening polymerization method, addition polymerization method etc.

The structure of the polysiloxane using in the present invention there is no particular restriction, can preferably enumerate by by the one kind or two or more mixing of the organosilane shown in formula (IV) the polysiloxane that its reaction is obtained.

[chemical formula 5]

(in formula (IV), R ₉any group in the aryl of the alkyl of expression hydrogen, carbonatoms 1～10, the thiazolinyl of carbonatoms 2～10, carbonatoms 6～15, and multiple R ₉can be mutually the same, also can be different.R ₁₀any group in the aryl of the alkyl of expression hydrogen, carbonatoms 1～6, the acyl group of carbonatoms 1～6, carbonatoms 6～15, multiple R ₁₀can be mutually the same, also can be different.N represents integer 0～3.)

The R of formula (IV) ₉any group in the aryl of the alkyl of expression hydrogen, carbonatoms 1～10, the thiazolinyl of carbonatoms 2～10, carbonatoms 6～15, and multiple R ₉can be mutually the same, also can be different.And these alkyl, thiazolinyl, aryl all optionally have substituting group, can be also not there is substituent nothing to replace body, can select according to the characteristic of composition.As the concrete example of alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, positive decyl, trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro propyl, 3-glycidoxy propyl group, 2-(3,4-epoxycyclohexyl) ethyl, 3-aminopropyl, 3-sulfydryl propyl group, 3-isocyanic ester 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.

The R of formula (IV) ₁₀any group in the aryl of the alkyl of expression hydrogen, carbonatoms 1～6, the acyl group of carbonatoms 1～6, carbonatoms 6～15, and multiple R ₁₀can be mutually the same, also can be different.And these alkyl, acyl group all optionally have substituting group, can be also not there is substituent nothing to replace body, can select according to the characteristic of composition.As the concrete example of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl.As the concrete example of acyl group, can enumerate ethanoyl.As the concrete example of aryl, can enumerate phenyl.

The n of formula (IV) represents integer 0～3.When n=0, be four functional silanes; When n=1, be trifunctional silane; When n=2, be two functional silanes; When n=3, be simple function silane.

As the concrete example of the organosilane shown in formula (IV), can enumerate: four functional silanes such as tetramethoxy-silicane, tetraethoxysilane, tetrem acyloxy silane, tetraphenoxy-silicane alkane, methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, methyl three n-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, n-hexyl Trimethoxy silane, n-hexyl triethoxyl silane, decyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, 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, trifluoromethyl Trimethoxy silane, trifluoromethyl triethoxyl silane, 3,3,3-trifluoro propyl Trimethoxy silane, 3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, the trifunctional silane such as 3-sulfydryl propyl trimethoxy silicane, two functional silanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diacetoxy silane, di-n-butyl dimethoxy silane, dimethoxydiphenylsilane, the simple function silane such as trimethylammonium methoxy silane, three normal-butyl Ethoxysilanes.

In above-mentioned organosilane, from the viewpoint of resistance to cracking and the hardness of the resin molding that obtained by resin combination of the present invention, preferably use trifunctional silane.In addition, these organosilanes may be used alone, or two or more kinds may be used in combination.

Polysiloxane in the present invention can be by obtaining above-mentioned organosilane generation hydrolysis and part condensation.As hydrolysis and part condensation, can adopt ordinary method.For example, can be to adding solvent, water, as required and the catalyzer using in mixture, and carry out heated and stirred.Also can be as required by dephlegmate solution by product (alcohol such as methyl alcohol) and condensation by-product (water) in whipping process.

The polyimide using in the present invention can be by heat-treating and obtain the polyimide precursor being obtained by tetracarboxylic anhydride and diamine reactant.As the precursor for obtaining polyimide resin, comprise polyamic acid, poly amic acid ester, polyisoimide, polyamic acid sulphonamide (Port リ ア ミ De acid ス Le ホ Application ア ミ De) etc.

As the acid dianhydride of raw material that can be used as polyimide, specifically can enumerate: pyromellitic acid dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-xenyl tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-xenyl tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic acid dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2,2-, 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-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, the aromatic series tetracarboxylic acid dianhydrides such as two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, or ethylene-dimalonic acid dianhydride, 1,2,3, the aliphatics tetracarboxylic acid dianhydrides such as 4-cyclopentane tetracarboxylic acid dianhydride etc.These acid dianhydrides can be used alone, and also two or more can be used in combination.

As the concrete example of diamines of raw material that can be used as polyimide, 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, benzyne, mphenylenediamine, Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine, 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, or above-claimed cpd aromatic ring is replaced by alkyl or halogen atom and the compound that obtains, or aliphatic cyclohexyl diamines, methylene-bis hexahydroaniline, etc..These diamines can be used alone a kind, also two or more can be used in combination.

The polyimide using in the present invention can be synthetic by known method.; can be by optionally combining tetracarboxylic dianhydride and diamines; and make them at METHYLPYRROLIDONE, N; the known method such as in N-N,N-DIMETHYLACETAMIDE, DMF, methyl-sulphoxide, HMPA, gamma-butyrolactone, cyclopentanone isopolarity solvent, reacting synthesizes.

The weight-average molecular weight (Mw) of the adhesive resin (A) using in the present invention is generally 1,000～1,000,000, preferably 1,500～100, and 000, more preferably 2,000～10,000 scope.

As the molecular weight distribution of adhesive resin (A), in the ratio of weight-average molecular weight/number-average molecular weight (Mw/Mn), conventionally below 4, preferably below 3, more preferably below 2.5.

Weight-average molecular weight (Mw) and the molecular weight distribution of adhesive resin (A) can adopt gel permeation chromatography.For example, can, take tetrahydrofuran (THF) equal solvent as elutriant, obtain with the form of polystyrene conversion molecular weight.

there is the compound (B) of acidic-group

In the present invention, use and there is the compound (B) of acidic-group as the neccessary composition of resin combination.

There is the compound (B) of acidic-group as long as there is acidic-group, there is no particular restriction, but preferred fat compounds of group, aromatics, heterogeneous ring compound, more preferably aromatics, heterogeneous ring compound.By using above-claimed cpd as the compound (B) with acidic-group, can make adaptation be further enhanced.

These compounds (B) can be distinguished use separately, also two or more can be used in combination.

Number for acidic-group is not particularly limited, but preferably has more than 2 acidic-group, especially preferably has 2 acidic-groups.Acidic-group can be mutually the same, also can be different.

Acidic-group, as long as acid functional group, as its concrete example, can be enumerated the strong acid group such as sulfonic group, phosphate; The slightly acidic groups such as carboxyl, sulfydryl and carboxyl methylene radical sulfenyl.Wherein, consider preferably carboxyl, sulfydryl or carboxyl methylene radical sulfenyl, especially preferably carboxyl from the viewpoint that can further improve adaptation.In addition, from the viewpoint of development sensitivity and storage stability, in above-mentioned acidic-group, preferred acid dissociation constant pKa is more than 3.5 and the group of 5.0 following scopes.It should be noted that, for the situation with more than 2 acidic-group, using the first dissociation constant pKa1 as acid ionization constant.In addition,, under thin aqueous conditions, pKa is acid ionization constant Ka=[H ₃o ⁺] [B ^-]/[BH].Wherein, BH represents organic acid, B ^-represent organic acid conjugate base.PKa is pKa=-logKa.

In addition, as the measuring method of pKa, for example, can measure hydrogen ion concentration by use pH meter, then be calculated by concentration and the hydrogen ion concentration of respective substance.

In the present invention, by using these acidic-groups, can make the resin molding being formed by resin combination of the present invention there is excellent adaptation.

In the present invention, above-claimed cpd (B) also optionally has other substituting group except acidic-group.

As this class substituting group, can enumerate the alkyl such as alkyl, aryl; In addition, can also enumerate the alkyl etc. that the following polar group that does not contain the polar group of proton, do not contained proton by these replaces: halogen atom; Alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group; The amino, acyl amino, urea groups, sulfamyl amino, alkoxycarbonyl amino, the aryloxycarbonyl amino that are replaced by alkyl, aryl or heterocyclic radical; Alkylthio, arylthio, heterocycle sulfenyl; Etc..

As the concrete example of compound (B), can be listed below:

Formic acid, acetic acid, propionic acid, butyric acid, pentane acid, butyric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxyacetic acid, R-Glyceric acid, oxalic acid (also referred to as " oxalic acid "), propanedioic acid (also referred to as " maleic acid "), succinic acid (also referred to as " succsinic acid "), pentanedioic acid, hexanodioic acid (also referred to as " adipic acid "), 1, 2-cyclohexane dicarboxylic acid, Acetylformic acid, 2-hydroxy-butanedioic acid, 2-hydroxy propane tricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid(DMSA), 2, 3-dimercapto-1-propyl alcohol, 1, 2, 3-tri-thiol propane, 2, 3, 4-tri-thiol-n-butyl alcohol, 2, 4-dimercapto-1, 3-butyleneglycol, 1, 3, 4-tri-thiol-2-butanols, 3, 4-dimercapto-1, 2-butyleneglycol, 1, the fatty compoundss such as 5-dimercapto-3-thia pentane,

Phenylformic acid, P-hydroxybenzoic acid, salicylic acid, 2-naphthoic acid, tolyl acid, mesitylenic acid, trimethylbenzoic acid, 3-phenylpropionic acid, 2 hydroxybenzoic acid, resorcylic 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 "), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, mellitic acid, biphenyl-2,2 '-dioctyl phthalate, 2-(carboxyl methyl) phenylformic acid, 3-(carboxyl methyl) phenylformic acid, 4-(carboxyl methyl) phenylformic acid, 2-(carboxyl carbonyl) phenylformic acid, 3-(carboxyl carbonyl) phenylformic acid, 4-(carboxyl carbonyl) phenylformic acid, 2-Thiosalicylic acid, 4-Thiosalicylic acid, 2-sulfydryl-6-naphthoic acid, 2-sulfydryl-7-naphthoic acid, 1,2-thioresorcin, 1,3-thioresorcin, Isosorbide-5-Nitrae-thioresorcin, Isosorbide-5-Nitrae-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 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, γ-picolinic 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-2,3-dioctyl phthalate, thiophene-2,4-dioctyl phthalate, thiophene-2,5-dioctyl phthalate, thiophene-3,4-dioctyl phthalate, thiazole-2,4-dioctyl phthalate, thiazole-2,5-dioctyl phthalate, thiazole-4,5-dioctyl phthalate, isothiazole-3,4-dioctyl phthalate, isothiazole-3,5-dioctyl phthalate, 1,2,4-thiadiazoles-2,5-dioctyl phthalate, 1,3,4-thiadiazoles-2,5-dioctyl phthalate, 3-amino-5-sulfydryl-1,2,4-thiadiazoles, 2-amino-5-sulfydryl-1,3,4-thiadiazoles, 3,5-dimercapto-1,2,4-thiadiazoles, 2,5-dimercapto-1,3,4-thiadiazole, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfanilyl radical) succsinic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfanilyl radical) succsinic acid, (5-sulfydryl-1,2,4-thiadiazoles-3-base sulfo-) acetic acid, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) acetic acid, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfo-) propionic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) propionic acid, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfo-) succsinic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) succsinic acid, 4-(3-sulfydryl-1,2,4-thiadiazoles-5-yl) sulfo-fourth sulfonic acid, the five member ring heterocyclic compound that 4-(2-sulfydryl-1,3,4-thiadiazoles-5-yl) sulfo-fourth sulfonic acid etc. contains nitrogen-atoms and sulphur atom,

Pyridine-2, 3-dioctyl phthalate, pyridine-2, 4-dioctyl phthalate, pyridine-2, 5-dioctyl phthalate, pyridine-2, 6-dioctyl phthalate, pyridine-3, 4-dioctyl phthalate, pyridine-3, 5-dioctyl phthalate, pyridazine-3, 4-dioctyl phthalate, pyridazine-3, 5-dioctyl phthalate, pyridazine-3, 6-dioctyl phthalate, pyridazine-4, 5-dioctyl phthalate, pyrimidine-2, 4-dioctyl phthalate, pyrimidine-2, 5-dioctyl phthalate, pyrimidine-4, 5-dioctyl phthalate, pyrimidine-4, 6-dioctyl phthalate, pyrazine-2, 3-dioctyl phthalate, pyrazine-2, 5-dioctyl phthalate, pyridine-2, 6-dioctyl phthalate, triazine-2, 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, become the viewpoint with substrate with the material of good adaptation from the resin molding that can make to be formed by resin combination, the number of its acidic-group is preferably more than 2, is especially preferably 2.

As the compound with 2 acidic-groups, preferably oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, 1, 2-cyclohexane cyclohexanedimethanodibasic, benzene-1, 2-dioctyl phthalate (also referred to as " phthalic acid "), benzene-1, 3-dioctyl phthalate (also referred to as " m-phthalic acid "), benzene-1, 4-dioctyl phthalate (also referred to as " terephthalic acid ") biphenyl-2, 2 '-dioctyl phthalate, 2-(carboxyl methyl) phenylformic acid, 3-(carboxyl methyl) phenylformic acid, 4-(carboxyl methyl) phenylformic acid, 2-Thiosalicylic acid, 4-Thiosalicylic acid, 2-sulfydryl-6-naphthoic acid, 2-sulfydryl-7-naphthoic acid, 1, 2-thioresorcin, 1, 3-thioresorcin, 1, 4-thioresorcin, 1, 4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2, 6-naphthalenedithiol, 2, 7-naphthalenedithiol etc. has the aromatics of 2 acidic-groups, 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-3,5-dioctyl phthalate, thiophene-2,3-dioctyl phthalate, thiophene-2,4-dioctyl phthalate, thiophene-2,5-dioctyl phthalate, thiophene-3,4-dioctyl phthalate, thiazole-2,4-dioctyl phthalate, thiazole-2,5-dioctyl phthalate, thiazole-4,5-dioctyl phthalate, isothiazole-3,4-dioctyl phthalate, isothiazole-3,5-dioctyl phthalate, 1,2,4-thiadiazoles-2,5-dioctyl phthalate, 1,3,4-thiadiazoles-2,5-dioctyl phthalate, (5-sulfydryl-1,2,4-thiadiazoles-3-base sulfo-) acetic acid, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) acetic acid, pyridine-2,3-dioctyl phthalate, pyridine-2,4-dioctyl phthalate, 2,5-Pyridinedicarboxylic acid, pyridine-2,6-dioctyl phthalate, pyridine-3,4-dioctyl phthalate, pyridine-3,5-dioctyl phthalate, pyridazine-3,4-dioctyl phthalate, pyridazine-3,5-dioctyl phthalate, pyridazine-3,6-dioctyl phthalate, pyridazine-4,5-dioctyl phthalate, pyrimidine-2,4-dioctyl phthalate, pyrimidine-2,5-dioctyl phthalate, pyrimidine-4,5-dioctyl phthalate, pyrimidine-4,6-dioctyl phthalate, pyrazine-2,3-dioctyl phthalate, pyrazine-2,5-dioctyl phthalate, pyridine-2,6-dioctyl phthalate, triazine-2,4-dioctyl phthalate etc. has the heterogeneous ring compound of 2 acidic-groups.

By using above-claimed cpd, can obtain following effect: between the resin molding being formed by resin combination and substrate, there is high adhesion.

With respect to adhesive resin (A) 100 weight parts, the content of the compound with acidic-group (B) in resin combination of the present invention is generally 5～45 weight parts, preferably 7～40 weight parts, more preferably 10～30 weight part scopes.The consumption of compound (B) with acidic-group within the scope of this time, can obtain the resin combination with excellent liquid stability.

compound (D)

In the present invention, use the neccessary composition of following compound (D) as resin combination: compound (D) has the a kind of atom being selected from Siliciumatom, titanium atom, aluminium atom, zirconium atom, and there is the-oxyl that is bonded on this atom or the compound of hydroxyl.

Wherein, preferably there is the compound that is bonded in the-oxyl on Siliciumatom or titanium atom.

In addition, above-mentioned-oxyl is preferably the-oxyl of carbonatoms 1～18.

When adhesive resin (A) is while having the resin of protic polar group, compound (D) is particularly preferably the compound with the functional group that can react with protic polar group.

The described functional group that can react with protic polar group is preferably isocyanate group, sulfydryl, epoxy group(ing) or amino, more preferably epoxy group(ing).

As the concrete example of compound (D), can be listed below:

The tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane;

Methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, n-pentyl Trimethoxy silane, n-hexyl Trimethoxy silane, n-heptyl Trimethoxy silane, n-octyl Trimethoxy silane, positive decyl Trimethoxy silane, to styryl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl triethoxyl silane, 3-TSL 8330, APTES, N-2-(amino-ethyl)-3-TSL 8330, N-phenyl-3-TSL 8330, 2-hydroxyethyl Trimethoxy silane, 2-hydroxyethyl triethoxyl silane, 2-hydroxypropyl Trimethoxy silane, 2-hydroxypropyl triethoxyl silane, 3-hydroxypropyl Trimethoxy silane, 3-hydroxypropyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) 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 (trimethoxysilyl propoxy-methyl) trimethylene oxide, 3-ethyl (triethoxysilyl propoxy-methyl) trimethylene oxide, 3-triethoxysilyl-N-(1,3-dimethyl butyrate fork) propylamine, the trialkoxysilanes such as two (triethoxysilylpropyltetrasulfide) four thioethers,

Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, diη-propyl dimethoxy silane, diη-propyl diethoxy silane, diisopropyl dimethoxy silane, di-isopropyl diethoxy silane, di-n-butyl dimethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, 3-glycidoxy propyl group methyldiethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, the dialkoxy silicane classes such as N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane,

In addition, also can enumerate the compound that methyl triacetoxysilane, dimethyl diacetoxy silane, trade(brand)name X-12-414, KBP-44 (Shin-Etsu Chemial Co., Ltd's system), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (Toray Dow Corning Co., Ltd. system) etc. contain Siliciumatom;

Tetraisopropoxy titanium, four titanium n-butoxide, four (2-ethyl hexyl oxy) titanium, isopropoxy ethohexadiol titanium (チ タ ニ ウ system-i-プ ロ Port キ シ オ Network チ レ Application グ リ コ レ mono-ト), diisopropoxy two (methyl ethyl diketone) closes titanium, the third dioxy base two (methyl aceto acetate) closes titanium, three n-butoxy Stearinsaeure titaniums, diisopropoxy distearyl acid titanium, stearic acid titanium, diisopropoxy titanium diisostearate, (2-n-butoxy carbonyl benzoyl oxygen base) three titanium butoxide, two n-butoxies two (trolamine) close titanium, and the compound that contains titanium atom such as PlainAct series (aginomoto Jinggong Co., Ltd system),

The compound that acetyl alkoxyl group diisopropyl acid aluminium etc. contains aluminium atom;

Four n-propoxyzirconium, four n-butoxy zirconiums, tetrem ethyl sodio acetoacetic ester close zirconium, three butoxy acetylacetic esters and close zirconium, single butoxy acetylacetic ester two (methyl aceto acetate) and close that zirconium, dibutoxy two (methyl aceto acetate) close zirconium, tetrem ethyl sodio acetoacetic ester closes the compound that zirconium, three butoxy zirconium stearates etc. contain zirconium atom.

This wherein preferably contains the compound of Siliciumatom, the compound that contains titanium atom, more preferably contains the compound of Siliciumatom, especially preferably has the functional group that can react with protic polar group and the compound that contains Siliciumatom.By thering is above-mentioned functional group, can make the adaptation of resin combination of the present invention in the time being stacked on substrate be further enhanced.

As the above-mentioned functional group that can react with protic polar group, can enumerate amino, sulfydryl, isocyanate group, glycidoxy, epoxy group(ing), urea groups, preferably glycidoxy, epoxy group(ing).

As the concrete example of the above-mentioned compound with the functional group that can react with protic polar group, especially preferred: 3-TSL 8330, APTES, N-2-(amino-ethyl)-3-TSL 8330, N-phenyl-3-TSL 8330, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl triethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 3-triethoxysilyl-N-(1, 3-dimethyl butyrate fork) propylamine, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane.

These compounds (D) can be distinguished use separately, also two or more can be used in combination.

With respect to adhesive resin (A) 100 weight parts, the content of compound in resin combination of the present invention (D) is 1～40 weight part, preferably 3～30 weight parts, more preferably 5～25 weight part scopes.The consumption of compound (D) within the scope of this time, can fully improve the adaptation between resin molding and the substrate being formed by resin combination, therefore preferred.

In the present invention, with respect to adhesive resin (A) 100 weight parts, the total content of above-claimed cpd (B) and compound (D) is 10～50 weight parts, preferably 13～40 weight parts, especially preferred 15～35 weight parts.If above-mentioned total amount less than 10 weight parts, cannot obtain the effect that adaptation improves; On the contrary, if exceed 50 weight parts,, in the time that the radiosensitive compound of interpolation (E) is given photosensitivity for resin combination, can increase the decrement (subtract film amount) of film in the time developing.

In addition, in the present invention, the content of above-claimed cpd (B) is preferably more than the content of compound (D), and more preferably the content of above-claimed cpd (B) is higher than the content of compound (D).By making the content of compound (B) more than the content of compound (D), can give play to good result to the raising of adaptation.

organic solvent (C)

There is no particular restriction for the organic solvent (C) using in the present invention.As its concrete example, can enumerate: the aklylene glycol classes such as ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG; The alkylene glycol mono ethers such as ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol list tertbutyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol single-butyl ether, diethylene glycol monomethyl ether, TC, DPGME, DPGME, dihydroxypropane single-ethyl ether, triethylene glycol monomethyl ether, triethylene glycol list ethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethyl ether; The aklylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol ethyl-methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether, dipropylene glycol ethyl-methyl ether, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether, triethylene glycol ethyl-methyl ether, tripropylene glycol ethyl-methyl ether; The alkylene glycol monoalkyl ethers ester classes such as propylene glycol monomethyl ether, DPGME acetic ester, propylene glycol list ethyl ether acetic ester, propylene glycol list n-propyl ether acetic ester, propylene glycol monoisopropyl ether acetic ester, propylene glycol list n-butyl ether acetic ester, propylene glycol list isobutyl ether acetic ester, propylene glycol list sec-butyl ether acetic acid ester, propylene glycol list tertbutyl ether acetic ester; The ketones such as methyl ethyl ketone, pimelinketone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, pimelinketone, cyclopentanone; The alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, 3-methoxyl group-3-methyl butanol; Tetrahydrofuran (THF), two the ring-type ethers such as alkane; The cellosolve such as methylcellosolve acetate, ethyl cellosolve acetate ester class; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; The ester classes such as ethyl acetate, butylacetate, ethyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl-butyrate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, gamma-butyrolactone; The amidess such as N-METHYLFORMAMIDE, DMF, METHYLPYRROLIDONE, N-methylacetamide, N,N-dimethylacetamide; The sulfoxide types such as methyl-sulphoxide; Etc..

Wherein, preferred Diethylene Glycol ethyl-methyl ether, propylene glycol monomethyl ether, cyclopentanone, METHYLPYRROLIDONE.

These organic solvents can be distinguished use separately, also two or more can be used in combination.With respect to adhesive resin (A) 100 weight parts, the consumption of organic solvent (C) is generally 20～10,000 weight part, preferably 50～5,000 weight part, more preferably 100～1,000 weight part scope.

radiosensitive compound (E)

In resin combination of the present invention, preferably further contain radiosensitive compound (E).

The radiosensitive compound (E) using in the present invention be can be the in the situation that of irradiation ultraviolet radiation or electron beam isoradial the compound of initiating chamical reaction.In the present invention, the compound that radiosensitive compound (E) preferably can be controlled the alkali dissolution of the resin molding being formed by resin combination.

In the present invention, preferably use light acid producing agent as radiosensitive compound (E).

As radiosensitive compound (E), can enumerate the triazo-compounds such as such as acetophenone compound, triarylsulfonium salt, quinone di-azido compound etc., preferably triazo-compound, especially preferably quinone di-azido compound.

As quinone di-azido compound, for example can use by quinone diazido sulfonic acid halide and there is the ester cpds of the compound formation of phenol hydroxyl.As the concrete example of quinone diazido sulfonic acid halide, can enumerate 1,2-naphthoquinones, two nitrine-5-SULPHURYL CHLORIDE, 1,2-naphthoquinones two nitrine-4-SULPHURYL CHLORIDE, 1,2-benzoquinones two nitrine-5-SULPHURYL CHLORIDE etc.As the typical example of 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.There is the compound of phenol hydroxyl as other except above-mentioned, 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, the oligopolymer of 1,2,2-tetra-(4-hydroxy phenyl) ethane, novolac resin, by thering is the compound of 1 phenol hydroxyl and oligopolymer that Dicyclopentadiene (DCPD) obtains through copolymerization etc.

Wherein, preferably 1,2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE and the condenses of compound with phenol hydroxyl, more preferably 1,1,3-tri-(2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, the condenses of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.5 moles).

As light acid producing agent; except quinone diazide; can also use salt, halogenated organic compounds, α, the known light acid producing agents such as α '-bis-(alkylsulfonyl) diazo methane compound, alpha-carbonyl-α '-alkylsulfonyl diazo methane compound, sulphones, organic acid acetic compound, organic amide compound, organic imide compound.

These radiosensitive compounds can be distinguished use separately, also two or more can be used in combination.

With respect to adhesive resin (A) 100 weight parts, in resin combination of the present invention, the content of radiosensitive compound (E) is 1～100 weight part, preferably 5～50 weight parts, more preferably 10～40 weight part scopes.In the time that the consumption of radiosensitive compound (E) is within the scope of this, when forming the resin molding that comprises resin combination of the present invention and the resin molding forming is carried out to patterning on any substrate, in resin molding, radiation exposure portion and the radioactive rays not difference of the solubleness of irradiation portion in developing solution become large, be easy to carry out patterning by development, and can obtain high radiosensitivity, therefore preferred.

linking agent (F)

In the present invention, preferably further contain the composition of linking agent (F) as resin combination.

As linking agent (F), use be in molecule, to there are 2 above, preferred materials of 3 the above functional groups that can react with adhesive resin (A).The functional group that linking agent (F) has as long as can with adhesive resin in the group that reacts such as functional group, unsaturated link(age), be not particularly limited the group that preferably can react with protic polar group.

As described functional group, can enumerate for example amino, hydroxyl, epoxy group(ing), isocyanate group etc., more preferably amino, epoxy group(ing) and isocyanate group, further preferred epoxy group(ing).

As the concrete example of linking agent (F), 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 '-azido-benzylidene) pimelinketone, 4 of 2,6-, the nitrine classes such as 4 '-diazido sulfobenzide; Nylon, polyhexamethylene diamines terephthalamide, polyhexamethylene isophthaloyl amine etc. are polyamide-based; N, N, N ', N ', N ", the N " melamine class such as (six alkoxy methyls) trimeric cyanamide; N, N ', N ", the N " '-glycoluril classes such as (four alkoxy methyls) glycoluril; The acrylic compound such as ethylene glycol bisthioglycolate (methyl) acrylate; The isocyanate ester compounds such as hexamethylene diisocyanate class polyisocyanates, isophorone diisocyanate class polyisocyanates, tolylene diisocyanate class polyisocyanates, hydrogenation diphenylmethanediisocyanate; Isosorbide-5-Nitrae-bis-(hydroxymethyl) hexanaphthene, Isosorbide-5-Nitrae-bis-(hydroxymethyl) norbornane; 1,3,4-trihydroxy-hexanaphthene; The epoxy compoundss such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, many phenol-type epoxy resins, cyclic aliphatic epoxy resin, aliphatic glycidyl base ether, epoxy acrylic ester polymer.

As the concrete example of isocyanate ester compound, can enumerate: the TAKENATE series (B-815N, B-882N, B-874N) that the DESMODULE series (DESMODULE BL3370, DESMODULEVPLS2253) that Sumika Bayer Urethane company manufactures and CRELAN series (CRELAN V1, CRELAN VPLS2256), MitsuiTakeda Chemicals company manufacture, the CORONATE series (CORONATE L) that Nippon Polyurethane company manufactures etc.

As the concrete example of melamine class, can enumerate: " CYMEL 300 ", " CYMEL 301 ", " CYMEL 303 ", " CYMEL 350 ", " CYMEL 1123 ", " CYMEL 370 ", " CYMEL771 ", " CYMEL 272 ", " MYKOTE 102 ", " CYMEL 325 ", " CYMEL 327 ", " CYMEL 703 ", " CYMEL 712 ", " MYKOTE 105 ", " MYKOTE 106 ", " CYMEL266 ", " CYMEL 267 ", " CYMEL 285 ", " CYMEL 232 ", " CYMEL 235 ", " CYMEL 236 ", " CYMEL 238 ", " MYKOTE 506 ", " CYMEL 701 ", " CYMEL272 ", " CYMEL 212 ", " CYMEL 253 ", " CYMEL 254 ", " MYKOTE 508 ", " CYMEL 1128 ", " MYKOTE 130 ", " CYMEL 202 ", " CYMEL 207 " (being manufactured by Cytec Industries company above), " NIKALAC MW-30HM ", " NIKALAC MW390 ", " NIKALAC MX-750 ", " NIKALAC MX-706 " (being manufactured by Sanwa Chemical company above) etc.

As the concrete example of glycoluril class, can enumerate: " CYMEL 1170 ", " CYMEL 1172 " (being manufactured by Cytec Industries company above), " NIKALAC MX-270 " (being manufactured by Sanwa Chemical company above) etc.

As the concrete example of epoxy compounds, can enumerate: the trifunctional epoxy compounds (trade(brand)name " XD-1000 " take Dicyclopentadiene (DCPD) as skeleton, chemical drug company of Japan manufactures), 2, 1 of two (the hydroxymethyl)-n-butyl alcohols of 2-, 2-epoxy-4-(2-Oxyranyle) hexanaphthene affixture (has 15 functionality cycloaliphatic epoxy resins of hexanaphthene skeleton and terminal epoxy groups, trade(brand)name " EHPE3150 ", Daicel chemical industrial company manufactures), epoxidation 3-tetrahydrobenzene-1, 6-caprolactone (the aliphatics ring-type trifunctional epoxy resin that 2-dicarboxylic acid two (3-cyclohexenyl methyl esters) is modified, trade(brand)name " EPOLEAD GT301 ", Daicel chemical industrial company manufactures), 6-caprolactone (the aliphatics ring-type four functionality epoxy resin that epoxidation ethylene-dimalonic acid four (3-cyclohexenyl methyl esters) is modified, trade(brand)name " EPOLEAD GT401 ".Daicel chemical industrial company manufactures), 3, 4-epoxycyclohexyl methacrylic ester (trade(brand)name " CYCLOMER A400 ", Daicel chemical industrial company manufactures), 1, 2, 8, 9-diepoxy limonene (trade(brand)name " CELOXIDE 3000 ", Daicel chemical industrial company manufactures), (3 ', 4 '-epoxy cyclohexane) methyl 3, 4-epoxy cyclohexane manthanoate (trade(brand)name " CELOXIDE 2021 ", Daicel chemical industrial company manufactures), 1, 2-epoxy-4-vinyl cyclohexane (trade(brand)name " CELOXIDE 2000 ", Daicel chemical industrial company manufactures) etc. there is the epoxy compounds of alicyclic structure,

Aromatic amine type multi-functional epoxy compound (trade(brand)name " H-434 ", Dongdu changes into industrial and manufactures), cresols phenolic varnish type multi-functional epoxy compound (trade(brand)name " EOCN-1020 ", chemical drug company of Japan manufactures), phenol phenolic varnish type multi-functional epoxy compound (EPIKOTE 152, 154, Japan EpoxyResins company manufactures), there is multi-functional epoxy compound (the trade(brand)name EXA-4700 of naphthalene skeleton, Dainippon Ink and Chemicals, Inc manufactures), chain-like alkyl multi-functional epoxy compound (trade(brand)name " SR-TMP ", Ban Ben pharmaceutical industries Co., Ltd. manufactures), multi-functional epoxy's polyhutadiene (trade(brand)name " EPOLEAD PB3600 ", Daicel chemical industrial company manufactures), polyglycidyl ether compound (the trade(brand)name " SR-GLG " of glycerine, Ban Ben pharmaceutical industries Co., Ltd. manufactures), two glycerine polyglycidyl ether compound (trade(brand)names " SR-DGE ", Ban Ben pharmaceutical industries Co., Ltd. manufactures), poly-glycerine polyglycidyl ether compound (trade(brand)name " SR-4GL ", Ban Ben pharmaceutical industries Co., Ltd. manufactures) etc. do not there is the epoxy compounds of alicyclic structure.

Wherein, preferably epoxy compounds, can improve the adaptation between resin molding and the substrate being obtained by resin combination of the present invention owing to having the epoxy compounds of alicyclic structure, therefore more preferred.

Molecular weight for linking agent (F) is not particularly limited, but is generally 100～100,000, preferably 500～50,000, more preferably 1,000～10,000.Linking agent can be distinguished use separately, also two or more can be used in combination.

With respect to adhesive resin (A) 100 weight parts, the content of linking agent in resin combination of the present invention (F) is generally 0.1～200 weight part, preferably 1～150 weight part, more preferably 5～100 weight part scopes.The consumption of linking agent within the scope of this time, can obtain sufficient thermotolerance, therefore preferred.

other additive

Not destroying in the scope of effect of the present invention, in resin combination of the present invention, can also optionally contain other additives such as sensitizing agent, tensio-active agent, the acidogenic agent of hiding (the raw drug of potential Suan development), oxidation inhibitor, photostabilizer, defoamer, pigment, dyestuff etc.

As the concrete example of sensitizing agent, can enumerate 2H-pyrido-(3,2-b)-Isosorbide-5-Nitrae- piperazine-3 (4H)-one class, 10H-pyrido-(3,2-b)-Isosorbide-5-Nitrae-benzo thiazides, urazole class, hydantoins, malonyl-ureas, glycine anhydride class, I-hydroxybenzotriazole class, tetraoxypyrimidine class, maleimide etc.

In the present invention, preferably contain the composition of tensio-active agent as resin combination.

Use the object of tensio-active agent to be: to prevent striped (striation, coating streak), improve developability etc.As its concrete example, can enumerate: the polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; The polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether; The nonionic surface active agent such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene SUNSOFT Q-182S; Fluorine class tensio-active agent; Organosilicone surfactants; Sipacril 2739OF class tensio-active agent; Acrylic copolymer class tensio-active agent; Etc..

Use the object of potential acidogenic agent to be: the thermotolerance and the resistance to chemical reagents that improve resin combination of the present invention.As its concrete example, can enumerate: can acidic cationic polymerisation catalyst, i.e. sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt etc. under heating condition.Wherein, preferred sulfonium salt and benzothiazolium salt.

As oxidation inhibitor, can use and be normally used for the phenolic antioxidant of polymkeric substance, Phosphorus oxidation inhibitor, sulfur type antioxidant, lactone oxidation inhibitor etc.For example, as phenolic antioxidant, can enumerate 2, 6-di-tert-butyl-4-methy phenol, p methoxy phenol, styrenated phenol, Octadecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 4, 4 '-Ding fork two (3 methy 6 tert butyl phenol), 4, 4 '-thiobis (3 methy 6 tert butyl phenol), tetramethylolmethane four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], alkylation bis-phenol etc.As Phosphorus oxidation inhibitor, can enumerate triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester etc.As sulfur type antioxidant, can enumerate Tyox B etc.

In the present invention, as the composition of resin combination, preferably contain photostabilizer.

Photostabilizer can be any in following substances: UV light absorber, the hindered aminess (HALS) etc. such as benzophenone, salicylate class, benzotriazole category, cyanoacrylate, metal complex salt class can be captured in the material of the free radical producing under light action etc.Wherein, HALS is the compound with piperidine structure, for composition of the present invention, and less painted and good stability, therefore preferred.As concrete compound, can enumerate: sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, 1,2,2,6,6-pentamethyl--4-piperidyl/tri-decyl 1,2,3,4-butane tetracarboxylic acid esters, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) ester etc.

the preparation method of resin combination

The preparation method of resin combination of the present invention is not particularly limited, as long as utilize known method that each moiety of resin combination of the present invention is mixed, described each moiety comprises: adhesive resin (A); There is the compound (B) of acidic-group; There is the a kind of atom being selected from Siliciumatom, titanium atom, aluminium atom, zirconium atom and there is the-oxyl that is bonded on this atom or the compound (D) of hydroxyl; Organic solvent (C); And as required and use other composition.

There is no particular restriction for blending means, preferably each moiety of resin combination is dissolved or dispersed in organic solvent (C) and obtains solution or dispersion liquid, and the method that this solution or dispersion liquid are mixed.Thus, resin combination of the present invention obtains with the form of solution or dispersion liquid.

As each moiety of resin combination of the present invention is dissolved or dispersed in to the method in organic solvent (C), as long as according to ordinary method.Specifically can enumerate: the method that uses agitating vane and magnetic stirring apparatus to stir, is used the method for high speed homogenizer, decollator, planetary mixer, biaxial rneader, ball mill, three-roller etc. etc.In addition, can also be in each composition be dissolved or dispersed in to organic solvent (C) after, utilizing such as aperture is that the strainer etc. of 0.5 μ m left and right filters.

Solid component concentration when each moiety of resin combination of the present invention is dissolved or dispersed in organic solvent (C) is generally 1～70 % by weight, preferably 5～60 % by weight, more preferably 10～50 % by weight.Solid component concentration is within the scope of this time, and film uniformity, the flatness etc. of the resin molding of steady dissolution, coating on substrate and formation can be obtained height balance.

multilayer body

Multilayer body of the present invention can the application of the invention resin combination on substrate, form resin molding and obtain.

In the present invention, substrate can use such as printed circuit substrate, silicon chip substrate, glass substrate, plastic base etc.In addition, also preferably adopt material that use, formed thin crystal cast liquid crystal display device, colour filter, black matrix etc. on glass substrate or plastic base etc. in field of display.

Be not particularly limited for the method that forms resin molding on substrate, can use the such as method such as coating method, film lay-up method.Coating method is for example: after resin combination is coated on substrate, carry out heat drying with the method except desolventizing.As resin combination being coated on to the method on substrate, for example can adopt: spray method, spin-coating method, rolling method, mould are coated with the whole bag of tricks such as method, spread coating, method of spin coating, excellent painting method, screen painting method.Heat drying condition because of kind and the ratio of mixture of each composition different, but Heating temperature is generally 30～150 ℃, preferably 60～120 ℃, is generally 0.5～90 minute heat-up time, preferably 1～60 minute, more preferably 1～30 minute.

Above-mentioned film lay-up method is: form with after on body material resin combination being coated on to the B such as resin molding or metallic membrane rank films, remove desolventizing with acquisition B rank film by heat drying, then, this B rank film is stacked in to the method on above-mentioned body material.Heat drying condition can suitably be selected according to the kind of each composition, ratio of mixture, but Heating temperature is generally 30～150 ℃, is generally 0.5～90 minute heat-up time.Film lamination can adopt the pressing machines such as pressure level press, pressing machine, vacuum laminator, vacuum pressing-combining machine, roll-type laminating machine to carry out.

The thickness of the resin molding forming on substrate is generally 0.1～100 μ m, preferably 0.5～50 μ m, more preferably 0.5～30 μ m.

In the present invention, after can forming resin molding on substrate, carry out the crosslinking reaction of resin.

When the resin molding that makes to form on substrate is cross-linked, can selects applicable method according to the kind of linking agent, but conventionally be undertaken by heating.As heating means, can adopt such as hot plate, baking oven etc. to carry out.Heating temperature is generally 180～250 ℃, and can suitably select heat-up time according to the size of resin molding, thickness and use equipment etc., for example, while using hot plate, is generally 5～60 minutes heat-up time; While using baking oven, be generally 30～90 minutes scopes heat-up time.As required, heating also can be carried out in inactive gas atmosphere.As inactive gas, use oxygen-free and can not make resin molding that the gas of oxidation occurs, for example can enumerate: nitrogen, argon gas, helium, neon, xenon, Krypton etc.Wherein, preferred nitrogen and argon gas, particularly preferably nitrogen.Suitable especially employing oxygen content is that 0.1 volume % is following, the preferred inactive gas below 0.01 volume %, especially preferably uses nitrogen.These inactive gass can be distinguished use separately, also two or more can be used in combination.

In the multilayer body forming at the resin molding being formed by substrate and use resin combination of the present invention, can make resin molding patterning on substrate, obtain patterned resin film.

The patterned resin film forming on substrate can obtain by following method: for example resin molding is irradiated to active radioactive rays and form sub-image pattern, then make developing solution contact with the resin molding with sub-image pattern, so that pattern is changed as seen.

In the time forming patterned resin film, first, the resin molding forming is irradiated to active radioactive rays on substrate, form sub-image pattern.As active radioactive rays, as long as making light acid producing agent activate and make the active radioactive rays that the alkali-soluble of the crosslinkable composite that comprises light acid producing agent changes to be not particularly limited.Specifically can use: the light beams such as the ultraviolet ray of the single wavelengths such as ultraviolet ray, g ray or i ray, KrF excimer laser, ArF excimer laser; The particle beam such as electron beam etc.As the method for utilizing these active radioactive rays to carry out pattern-like optionally to irradiate to form sub-image pattern, as long as according to ordinary method, for example can enumerate: utilize the method across light beams such as required mask pattern irradiation ultraviolet radiation, g ray, i ray, KrF excimer laser, ArF excimer laser such as reduced projection exposure apparatus, or utilize method that the particle beam such as electron beam draw etc.For the situation that uses light beam as active radioactive rays, can be single wavelength light, also can mixed wavelengths light.Illuminate condition can suitably be selected according to used active radioactive rays, for example, uses in the situation of light beam of wavelength 200～450nm, and irradiation dose is generally 10～1,000mJ/cm ², preferred 50～500mJ/cm ²scope, determines according to irradiation time and illumination.After irradiating as described above active radioactive rays, as required, at the temperature of 60～130 ℃ of left and right, resin molding is carried out to the heat treated about 1～2 minute.

Then, the sub-image pattern forming on resin molding is developed, so that it is changed as seen.In the present invention, above-mentioned steps is called to " patterning ", the resin molding through patterning is called to " patterned resin film ".As developing solution, conventionally use the aqueous solution of basic cpd.As basic cpd, can use for example an alkali metal salt, amine, ammonium salt.Basic cpd can be mineral compound, can be also organic compound.As the concrete example of these compounds, can enumerate: an alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, water glass (sodium silicate), Starso (sodium metasilicate); Ammoniacal liquor; The primary amine such as ethamine, Tri N-Propyl Amine; The secondary amine such as diethylamine, di-n-propylamine; The tertiary amines such as triethylamine, methyl diethylamide; The quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline; The hydramine such as dimethylethanolamine, trolamine; Pyrroles, piperidines, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, the cyclic amines such as 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N-Methyl pyrrolidone; Etc..These basic cpds can be distinguished use separately, also two or more can be used in combination.

As the aqueous medium of alkali aqueous solution, can use: water, the water-miscible organic solvents such as methyl alcohol, ethanol.Alkali aqueous solution can be the solution that has added tensio-active agent of appropriate amount etc.

As the method that developing solution is contacted with the resin molding with sub-image pattern, can adopt the methods such as (paddle) method, spray method, pickling process that for example stir.As development conditions, can suitably select, but development temperature is generally 0～100 ℃, preferably 5～55 ℃, more preferably 10～30 ℃ of scopes, development time be generally 30～180 second scope.

Thus, form the patterned resin film of target on substrate after, can utilize as required washing fluid to rinse substrate, removing on substrate, the development residue of substrate back and substrate end.Through after rinsing processing, utilize pressurized air or compressed nitrogen to remove residual washing fluid.

In addition,, in order to make light acid producing agent inactivation, can also irradiate active radioactive rays to the whole substrate with patterned resin film as required.While irradiating active radioactive rays, can adopt illustrative method in the formation method of above-mentioned sub-image pattern.Can in irradiating active radioactive rays or after irradiating, heat resin molding.As heating means, can enumerate the method for for example utilizing hot plate or in baking oven, substrate being heated.Temperature is generally 100～300 ℃, preferred 120～200 ℃ of scopes.

In the present invention, after can being to form patterned resin on substrate, carry out the crosslinking reaction of patterned resin.

Crosslinked if according to the above-mentioned crosslinked same method that is formed at the resin molding on substrate.

The multilayer body that is formed with patterned resin film on multilayer body of the present invention, particularly substrate can be used as various electronic units, particularly semiconducter device.

Embodiment

Below, enumerate embodiment the present invention is carried out to more specific detail, but the present invention is not limited to these embodiment completely.

It should be noted that, in the present embodiment, in situation about being not particularly limited, " part " and " % " represents respectively " weight part " and " % by weight ".

Utilize following method to evaluate each characteristic.

(1) polymerisation conversion

Utilize gas chromatography determination levels of residual monomers, and calculate polymerisation conversion by this measured value.

(2) weight-average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn)

The polystyrene conversion value of having utilized gel permeation chromatography take tetrahydrofuran (THF) as elutriant.

(3) hydrogenation ratio

Utilize ¹h-NMR measures, and is obtained the ratio of the carbon-to-carbon double bond mole number of the carbon-to-carbon double bond mole number being hydrogenated before with respect to hydrogenation, using this as hydrogenation ratio by this measured value.

(4) adaptation

[measuring the making with sample]

The resin combination obtaining in each embodiment, comparative example is spin-coated on to glass substrate [Corning company, Corning 1737 (goods name)] on, then, utilize hot plate at 90 ℃, to carry out 2 minutes prebake conditions, formed the resin molding of thickness 2.5 μ m.In air, this resin molding is carried out to the uviolizing in 40 seconds across the mask with given pattern, this ultraviolet ray is 5mW/cm in the light intensity at 365nm place ².

Then, use the tetramethylammonium hydroxide aqueous solution of 0.4 % by weight at 25 ℃, carried out 60 second development treatment, then, rinsed for 30 seconds with ultrapure water, formed pattern.

Subsequently, utilize baking oven at 230 ℃, to heat baking after 60 minutes, thereby obtained adaptation mensuration multilayer body.

[mensuration of adaptation]

For gained multilayer body, use the adhesion-force tester (adhesion tester) that COTEC company manufactures to measure by check (proof) method.Based on measurement result, according to following standard, the adaptation of gained multilayer body is judged.

◎: more than 8MPa

Zero: 5MPa is above and be less than 8MPa

△: 3MPa is above and be less than 5MPa

×: be less than 3MPa

[Production Example 1]

(manufacture of acrylic resin)

On one side in nitrogen gas stream to 30 parts of 20 parts of vinylbenzene, 25 parts of butyl methacrylate, 25 parts of 2-EHAs, methacrylic acid, 2,300 parts of 0.5 part of 2-Diisopropyl azodicarboxylate and propylene glycol monomethyl ether stir, and have carried out heating in 5 hours on one side in 80 ℃.Utilize the rotatory evaporator to concentrate gained resin solution, the acrylic resin soln that to have obtained solid component concentration be 35%.

[Production Example 2]

(thering is the manufacture of the cyclic olefin polymer of protic polar group)

Using as the 9-hydroxycarbonyl group Fourth Ring [6.2.1.1 of cyclic olefin monomers with protic polar group ^3,6.0 ^2,7] 60 parts, 12 carbon-4-alkene, as the Fourth Ring [6.2.1.1 of cyclic olefin monomers without protic polar group ^3,6.0 ^2,7] 40 parts, 12 carbon-4-alkene (also referred to as " tetracyclododecane "), 1,2.8 parts of 5-hexadienes, dichloro benzal (1,3-bis- base imidazolidine-2-subunit) (tricyclohexyl phosphine) close 400 parts, 0.05 part of ruthenium and Diethylene Glycol ethyl-methyl ether and add to through in the withstand voltage glass reactor of nitrogen replacement, under agitation, carry out 2 hours polyreactions in 80 ℃, obtained the polymeric reaction solution that contains Romp polymer 1A.Polymerisation conversion is more than 99.9%.The weight-average molecular weight of this polymkeric substance 1A is 3,200, number-average molecular weight is 1,900, molecular weight distribution is 1.68.

Then, to adding and close 0.1 part of ruthenium as two chloroethoxy methylene-biss (tricyclohexyl phosphine) of hydrogenation catalyst in polymeric reaction solution obtained above, and under the pressure of 4MPa, dissolve hydrogen 5 hours to carry out hydrogenation reaction.Then, in this solution, add 1 part of active carbon powder, then this solution is joined in autoclave while stirring under 150 ℃, 4MPa pressure and dissolves hydrogen 3 hours.Then, take out gained solution, solution is filtered with the fluoro-resin strainer processed of aperture 0.2 μ m, isolate gac, thereby obtained 476 parts of the hydrogenation reaction solution of the hydride 1B that contains Romp polymer 1A.Filtration can be without carrying out under blocked state.Wherein, the solid component concentration in the hydrogenation reaction solution that contains hydride 1B of gained is 20.6%, and the output of hydride 1B is 98.1 parts.The weight-average molecular weight of gained hydride 1B is 4,430, number-average molecular weight is 2,570, molecular weight distribution is 1.72.Hydrogenation ratio is 99.9%.

Use Rotary Evaporators to concentrate the hydrogenation reaction solution of gained hydride 1B, solid component concentration is adjusted to 35%, thereby has obtained the solution of hydride 1C (containing the cyclic olefin polymer of carboxyl as protic polar group).Output before and after concentrated, weight-average molecular weight, number-average molecular weight and the molecular weight distribution of hydride do not change.

[Production Example 3]

(manufacture of cardo resin)

In the four neck flasks with reflux exchanger, add bisphenol fluorene type epoxy resin and acrylic acid equivalent reactant (acid number 1.28mgKOH/g, epoxy equivalent (weight) 21,300 that solid component concentration 50%, solids component convert.Chemical company of Nippon Steel manufactures, ProductName " ASF-400 " solution) 198.53 parts of 50% propylene glycol monomethyl ether solution, and add 0.45 part of 39.54 parts of benzophenone tetracarboxylic dianhydride, 8.13 parts of succinyl oxides, 48.12 parts of propylene glycol monomethyl ether and triphenylphosphine, under the heating condition of 120～125 ℃, carry out stirring for 1 hour, at 75～80 ℃, carry out again 6 hours heated and stirred, then, drop into 8.6 parts of glycidyl methacrylate, and at 80 ℃, carried out stirring for 8 hours.Utilize rotatory evaporator to concentrate gained resin solution, obtained the cardo resin solution of solid component concentration 35%.

[Production Example 4]

(manufacture of polysiloxane)

In three-necked flask, add 74.91 parts of methyltrimethoxy silanes, 150.36 parts of 69.41 parts of phenyltrimethoxysila,e and Pyrantons (DAA), at room temperature stir on one side, added following phosphate aqueous solution through 10 minutes on one side, described phosphate aqueous solution is the aqueous solution that is dissolved with 0.338 part of phosphoric acid (being 0.2 % by weight with respect to the monomer adding) in 55.8 parts of water.Then, flask is dipped in the oil bath of 70 ℃ and carries out stirring for 1 hour, then, through 30 minutes, oil bath is warming up to 115 ℃.Heat up and start after 1 hour, the interior temperature of solution reaches 100 ℃, from now starting to have carried out 2 hours heated and stirred (interior temperature is 100～110 ℃).Distill out the first alcohol and water that amounts to 115 parts as by product.In the DAA solution of gained polysiloxane, add DAA and make its solid component concentration reach 35 % by weight, thereby obtained polysiloxane solution.

[Production Example 5]

(manufacture of polyimide)

In dry air air-flow, in four neck flasks, add 4,102.5 parts of 9.61 parts, 4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] 17.3 parts of sulfones, 1.24 parts of two (3-aminopropyl) tetramethyl disiloxanes and cyclopentanone dissolve it at 40 ℃.Then, add 6.54 parts of pyromellitic acid dianhydrides, 3,3 ', 4,9.67 parts of 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,30 parts of 12.41 parts of 4 '-diphenyl ether tetracarboxylic acid dianhydrides and cyclopentanone, and at 50 ℃, carried out reaction in 3 hours.Utilize the rotatory evaporator to concentrate this solution, the polyimide solution that to have obtained solid component concentration be 35%.

[Production Example 6]

(not thering is the manufacture of the cyclic olefin polymer of protic polar group)

In Production Example 2, as cyclic olefin monomers, use Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 100 parts, 12 carbon-4-alkene replaces 9-hydroxycarbonyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 60 parts, 12 carbon-4-alkene, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 40 parts, 12 carbon-4-alkene, in addition, carry out ring-opening polymerization and hydrogenation according to the method identical with Production Example 2, obtain Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] solution of ring-opening polymerization polymer hydride (not thering is the cyclic olefin polymer of protic polar group) of 12 carbon-4-alkene.

[embodiment 1]

Mix as 100 parts of the acrylic resin solns obtaining in Production Example 1 of adhesive resin (A) (wherein, with solid component meter), as 1 of radiosensitive compound (E), 1, 3-tri-(2, 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, (Synesis Company of Japan manufactures the condenses of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.5 moles), " TS200 (goods name) ") 25 parts, as 20 parts, 2-(carboxyl methyl) phenylformic acid of compound (B) with acidic-group, as 8 parts of 92 parts, the Diethylene Glycol ethyl-methyl ether of organic solvent (C) and METHYLPYRROLIDONEs, as 10 parts of the 3-sulfydryl propyl trimethoxy silicanes of compound (D), 6-caprolactone (the epoxy resin of aliphatics ring-type four functionalities of modifying as the epoxidation BTCA four (3-cyclohexenyl methyl esters) of linking agent (F), trade(brand)name " EPOLEAD GT401 ", Daicel chemical industrial company manufactures) 20 parts, as (1 of age resister, 2, 2, 6, 6-pentamethyl--4-piperidyl/tridecyl)-1, 2, 3, 5 parts of 4-ethylene-dimalonic acid esters, and organosilicone surfactants (ProductName " KP341 ", chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 0.05 part, and carry out mix and blend.

After carrying out stirring in 30 minutes, mixture becomes homogeneous solution.This solution is filtered with the tetrafluoroethylene strainer processed that aperture is 0.45 μ m, thereby prepared resin combination 1D.

Then, use this resin combination 1D, obtain according to the method described above multilayer body, and its adaptation is evaluated.Result is as shown in table 1.

It is pointed out that in table 1～7, it is 100 parts that the use level of adhesive resin (A) is all illustrated in while being scaled solids component.

[embodiment 2～7]

In embodiment 1, use respectively compound (B), compound (D) and the linking agent (F) of kind shown in table 1 as compound (B), compound (D) and linking agent (F), and the addition that makes them is the amount shown in table 1, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 1.

[embodiment 8～14]

In embodiment 1, use the cyclic olefin polymer obtaining in Production Example 2 as adhesive resin (A), use respectively compound (B), compound (D) and the linking agent (F) of kind shown in table 1～2 as compound (B), compound (D) and linking agent (F), and the addition that makes them is the amount shown in table 1～2, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 1～2.

[embodiment 15～21]

In embodiment 1, use the cardo resin obtaining in Production Example 3 as adhesive resin (A), use respectively compound (B), compound (D) and the linking agent (F) of kind shown in table 2～3 as compound (B), compound (D) and linking agent (F), and the addition that makes them is the amount shown in table 2～3, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 2～3.

[embodiment 22～28]

In embodiment 1, use the polysiloxane obtaining in Production Example 4 as adhesive resin (A), use respectively compound (B), compound (D) and the linking agent (F) of kind shown in table 3～4 as compound (B), compound (D) and linking agent (F), and the addition that makes them is the amount shown in table 3～4, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 3～4.

[embodiment 29～35]

In embodiment 1, use the polyimide obtaining in Production Example 5 as adhesive resin (A), use respectively compound (B), compound (D) and the linking agent (F) of kind shown in table 4～5 as compound (B), compound (D) and linking agent (F), and the use level that makes them is the amount shown in table 4～5, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 4～5.

[embodiment 36～46]

In embodiment 1, use respectively adhesive resin (A), compound (B), compound (D) and the linking agent (F) of kind shown in table 5～6 as adhesive resin (A), compound (B), compound (D) and linking agent (F), and the use level that makes them is the amount shown in table 5～6, in addition, prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.It should be noted that, in embodiment 46, as adhesive resin (A), use be the cyclic olefin polymer without protic polar group obtaining in Production Example 6.

Result is as shown in table 5～6.

[comparative example 1,2]

Except the addition of compound (B) and compound (D) is changed to the amount shown in table 7, prepare each resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 7.

[comparative example 3,4]

Except only using respectively the a kind of compound (B) shown in table 7 or only using independent a kind of compound (D) as compound (B), compound (D), prepare each resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 7.

[comparative example 5]

Except not only not using compound (B) but also not using compound (D), prepare resin combination according to the method identical with embodiment 1, then obtain multilayer body, and carried out the evaluation of adaptation for gained multilayer body.

Result is as shown in table 7.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

Wherein, in table 1～7, (pKa or pKa1) is as follows for the acidic-group number of the compound (B) using in embodiment and comparative example, acid ionization constant.

1,2-cyclohexane cyclohexanedimethanodibasic: acidic-group number is 2, pKa1 is about 4.87

Hexanodioic acid: acidic-group number is 2, pKa1 is 4.26

Phenylformic acid: acidic-group number is 1, pKa is 4～4.2

Phthalic acid: acidic-group number is 2, pKa1 is 2.95

2-(carboxyl methyl) phenylformic acid: acidic-group number is 2, pKa1 is 4～4.5

Pyrazine-2,3-dioctyl phthalate: acidic-group number is 2, pKa1 is below 2.95

2,4,6-tri-thiol s-triazine: acidic-group number is 3, pKa1 is 2.5

(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) acetic acid: acidic-group number is 2, pKa1 is 2.7

In addition,, in table 1～7, the linking agent (F) using in embodiment and comparative example is as follows.

SR-4GL: poly-glycerine polyglycidyl ether compound (trade(brand)name " SR-4GL ", Ban Ben pharmaceutical industries Co., Ltd. manufactures)

GT401: the 6-caprolactone (epoxy resin of aliphatics ring-type four functionalities that epoxidation ethylene-dimalonic acid four (3-cyclohexenyl methyl esters) is modified.Trade(brand)name " EPOLEAD GT401 ".Daicel chemical industrial company manufactures)

From the result of table 1～7, when the resin combination of use embodiment 1～46 forms resin molding on substrate, gained resin molding has high adhesion to substrate.Wherein, the resin combination of embodiment 1～46 contains adhesive resin (A), there is the compound (B) of acidic-group, organic solvent (C), and there is the Siliciumatom of being selected from, titanium atom, aluminium atom, 1 kind of atom in zirconium atom, and there is the-oxyl that is bonded on this atom or the compound (D) of hydroxyl, and the compound (B) with acidic-group is selected from fatty compounds, in aromatics and heterogeneous ring compound at least a kind, and, with respect to adhesive resin (A) 100 weight parts, compound (B) is 10～50 scopes with the total content of compound (D).

On the other hand, the total content of compound (B) and compound (D) not in the situation of the comparative example 1 and 2 in scope given to this invention, only use the situation of any comparative example of a kind 3 and 4 in compound given to this invention (B) and compound (D) and not only do not use compound (B) but also do not use the comparative example 5 of compound (D), resin molding is low with respect to the adaptation of substrate, insufficient.

Claims (18)

1. a resin combination, it contains adhesive resin (A), has the compound (B) of acidic-group, organic solvent (C) and compound (D),

Described compound (D) has the a kind of atom being selected from Siliciumatom, titanium atom, aluminium atom and zirconium atom, and has the-oxyl or the hydroxyl that are bonded on this atom, wherein,

The above-mentioned compound (B) with acidic-group is at least a kind that is selected from fatty compounds, aromatics and heterogeneous ring compound, and contains more than 2 acidic-group, and described acidic-group is carboxyl, sulfydryl or carboxyl methylene radical sulfenyl,

With respect to above-mentioned adhesive resin (A) 100 weight parts, the content of described compound (B) is 5～45 weight parts,

With respect to above-mentioned adhesive resin (A) 100 weight parts, the total content of above-claimed cpd (B) and above-claimed cpd (D) is 10～50 weight parts.

2. resin combination according to claim 1, it also contains radiosensitive compound (E).

3. resin combination according to claim 1 and 2, wherein, described in there is the compound (B) of acidic-group the acid ionization constant pKa of acidic-group in 3.5～5.0 scopes,

In the time having more than 2 acidic-group in the described compound (B) with acidic-group, its first acid ionization constant pKal is in 3.5～5.0 scopes.

4. resin combination according to claim 1 and 2, it also contains linking agent (F).

5. resin combination according to claim 4, wherein, described linking agent (F) is epoxy compounds.

6. resin combination according to claim 5, wherein, described epoxy compounds is the epoxy compounds with alicyclic structure.

7. resin combination according to claim 1 and 2, wherein, described adhesive resin (A) is for being selected from the more than a kind polymkeric substance in cyclic olefin polymer, acrylic resin, cardo resin, polysiloxane and the polyimide with protic polar group.

8. resin combination according to claim 1 and 2, wherein, described compound (D) still has the compound of the functional group that can react with protic polar group.

9. resin combination according to claim 8, wherein, the functional group that can react with protic polar group in described compound (D) is isocyanate group, sulfydryl, epoxy group(ing) or amino.

10. resin combination according to claim 1 and 2, wherein, the content of described compound (B) is more than or equal to the content of described compound (D).

The manufacture method of 11. 1 kinds of multilayer body, it has following step: the resin combination in right to use requirement 1～10 described in any one forms the step of resin molding on substrate.

The manufacture method of 12. multilayer body according to claim 11, it also has following step:

The resin molding being formed on described substrate is irradiated to active radioactive rays, on above-mentioned resin molding, form the step of sub-image pattern; And,

Developing solution is contacted with above-mentioned resin molding, so that sub-image pattern changes as seen, thereby above-mentioned resin molding is carried out to the step of patterning.

The manufacture method of 13. multilayer body according to claim 12, it also has following step:

The patterned resin film being formed on described substrate is heated, so that the step that pattern form changes.

The manufacture method of 14. multilayer body according to claim 11, it also has following step:

Make to be formed at the crosslinked step of resin molding on described substrate.

15. 1 kinds of multilayer body, it comprises substrate and is stacked on the resin molding that the resin combination by described in any one in claim 1～10 on this substrate forms.

16. multilayer body according to claim 15, wherein, described resin molding is patterned resin film.

17. 1 kinds of semiconducter device, it comprises the multilayer body described in claim 15.

18. 1 kinds of semiconducter device, it comprises the multilayer body described in claim 16.