CN102076774A

CN102076774A - Radiation-sensitive resin composition, laminate and method for producing the same, and semiconductor device

Info

Publication number: CN102076774A
Application number: CN2009801248251A
Authority: CN
Inventors: 矶贝幸枝
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2008-04-28
Filing date: 2009-04-27
Publication date: 2011-05-25
Anticipated expiration: 2029-04-27
Also published as: CN102076774B; KR20110008286A; WO2009133843A1; KR101586871B1; TW201005019A; JPWO2009133843A1; JP5488460B2; TWI488905B

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 the resin molding by this resin combination acquisition that is positioned on the substrate, more specifically, the present invention relates to be applicable to multilayer body and manufacture method and the semiconducter device that has the resin molding that obtains by this resin combination on the resin combination of making electronic units such as display element, integrated circuit component, solid-state imager, the substrate.

Background technology

In display element, integrated circuit component, solid-state imager, colour filter, thin film transistor and black matrix electronic units such as (black matrix), be provided with various resin moldings; as described resin molding, comprise the electrical insulating film etc. that is used to prevent these electronic unit generation deteriorations or damaged protective membrane, is used to make element surface or wiring realize the planarization film of planarization and is used to keep electrical insulating property.In addition, in elements such as film transistor type liquid crystal display device, integrated circuit component, be provided with to be used to make and be configured between lamellated a plurality of wiring insulating as the resin molding of interlayer dielectric.

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

In order to satisfy above-mentioned requirements, for example, disclose the radiation-sensitive composition that contains following compositions in the patent documentation 1: adhesive resin is the cyclic olefin base polymer; Radiosensitive compound; Organic solvent; Compound with acidic-group is the trimethoxysilyl phenylformic acid; And the compound with the-oxyl (ヒ De ロカ Le PVC Le オキシ yl) that is bonded on the Siliciumatom is γ-glycidoxypropyltrime,hoxysilane.

Disclose following radiation-sensitive composition in the patent documentation 2: it contains adhesive resin is that the organic insulation polymer shown in the formula (1), radiosensitive compound are light acid producing agent, organic solvent, compound with 2 acidic-groups is a 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]

The 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 record will cooperate bonding auxiliary agent in actual applications in the patent documentation 1, the adaptation between itself and the substrate is still not enough; The radiation-sensitive composition and the adaptation between the substrate of record are also insufficient in the patent documentation 2, 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 obtains improvement.

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 when 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 the zirconium atom, and have-oxyl or a hydroxyl that is bonded on this atom, above-mentioned have the compound (B) of acidic-group for being selected from fatty compounds, in aromatics and the 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 the specified quantitative scope.The inventor etc. have finished the present invention based on this discovery.

Thus, the invention provides a kind of resin combination, it contains adhesive resin (A), compound (B) with 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 the zirconium atom, and have-oxyl or a hydroxyl that is bonded on this atom, wherein, compound (C) with acidic-group is for being selected from fatty compounds, in aromatics and the 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, above-mentioned acidic-group with compound (B) of acidic-group is preferably carboxyl, sulfydryl or carboxyl methylene radical sulfenyl.

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

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

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), the polymkeric substance more than a kind in polysiloxane and the polyimide.

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

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 the resin molding that resin combination by the invention described above forms is arranged at the 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 to form above-mentioned resin molding on substrate.

In the manufacture method of the multilayer body of the invention described above, preferably has following step: on substrate, form after the above-mentioned resin molding, 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 the 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 to form above-mentioned resin molding on substrate, above-mentioned resin molding is shone active radioactive rays, thereby in above-mentioned resin molding, form the sub-image pattern, then, by developing solution is contacted with above-mentioned resin molding,, thereby above-mentioned resin molding is carried out patterning so that as seen the sub-image pattern change.

In the manufacture method of the multilayer body with patterned resin film of the invention described above, preferably has following step: on substrate, form after the above-mentioned patterned resin film, make the resin that forms above-mentioned patterned resin film carry out the step of crosslinking reaction.

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

The effect of invention

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

In addition; multilayer body of the present invention is because of having excellent electrical characteristic; shape-holding property; therefore the transparency and resistance to chemical reagents suit at for example display element; integrated circuit component; solid-state imager; colour filter; use as following electronic component-use material in the electronic units such as black matrix: be used to prevent these electronic unit generation deteriorations or damaged protective membrane; be used to make element surface or wiring to realize the planarization film of planarization; be used to keep the electrical insulating film of electrical insulating property (to comprise as thin type transistor type liquid crystal display device; the interlayer dielectric of the electrical insulating film of integrated circuit component; soldering-resistance layer etc.); micro lens; dividing plate electronic component-use materials such as (spacer).

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

Embodiment

Resin combination of the present invention contains adhesive resin (A), compound (B) with 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 the zirconium atom, and have-oxyl or a hydroxyl that is bonded on this atom, wherein, compound (B) with acidic-group is for being selected from fatty compounds, in aromatics and the 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, (A) there is no particular restriction for adhesive resin, be preferably cyclic olefin polymer, acrylic resin, cardo resin, polysiloxane or polyimide, wherein, especially preferably have the cyclic olefin polymer of protic polar group with protic polar group.

These adhesive resins (A) can be distinguished use separately, also can will be used in combination more than 2 kinds.

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

As the concrete example of protic polar group, can enumerate: hydroxyl, carboxyl (hydroxycarbonyl group), sulfonic group, phosphate etc. contain the polar group of Sauerstoffatom; Primary amino, secondary amino group, primary amide base, secondary amide base (imide) etc. contain the polar group of nitrogen-atoms; Sulfydryls etc. contain the polar group of sulphur atom; Or the like.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 among the present invention is meant the homopolymer or the multipolymer of the cyclic olefin monomers of have ring texture (alicyclic ring or aromatic nucleus) and carbon-to-carbon double bond.Can also have the unit that imports by other monomer beyond the cyclic olefin monomers in the cyclic olefin polymer.

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

In the cyclic olefin polymer with protic polar group, the protic polar group can be bonded on the cyclic olefin monomers unit, also can be bonded on cyclic olefin monomers other monomeric unit in addition, but preferably be bonded on the cyclic olefin monomers unit.

As the monomer that is used to constitute cyclic olefin polymer with protic polar group, can enumerate: have the protic polar group cyclic olefin monomers (a), have monomer (d) beyond cyclic olefin monomers (b), the cyclic olefin monomers (c) that does not have polar group and the cyclic olefin of other polar group beyond the protic polar group (below, abbreviate these monomers as monomer (a)～(d)).Wherein, monomer (d) can not have other polar group beyond protic polar group or the protic polar group, also can not have polar group fully.

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

Concrete example as 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] 12 carbon-4-alkene etc. contains the cyclic olefin of carboxyl; 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] 12 carbon-4-alkene etc. contains the cyclic olefin of hydroxyl; Or the like.Wherein, the cyclic olefin that preferably contains carboxyl.These cyclic olefin monomers (a) with protic polar group can be distinguished use separately, also can will be used in combination more than 2 kinds.

The concrete example of other polar group beyond the protic polar group that is had as the cyclic olefin monomers (b) with other polar group beyond the protic polar group can be enumerated: 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, uncle's amino, sulfonic group, acryl etc.Wherein, preferred 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 cyclic olefin, 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 with ester group ^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 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-sec.-propyl-4-methyl bicycle [2.2.2] suffering-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 cyclic olefin, for example can enumerate: 9-cyano group Fourth Ring [6.2.1.1 with cyano group ^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 cyclic olefin, for example can enumerate: 9-chlorotetracyclin [6.2.1.1 with halogen atom ^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.

Above-mentioned cyclic olefin monomers (b) with protic polar group other polar group in addition can be distinguished use separately, also can will be used in combination more than 2 kinds.

As the concrete example of the cyclic olefin monomers (c) that does not have polar group fully, can enumerate: dicyclo [2.2.1] hept-2-ene" (being 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, Dicyclopentadiene (DCPD)), Fourth Ring [10.2.1.0 8-diene (trivial name: ^2,11.0 ^4,9] 15 carbon-4,6,8,13-tetraene, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene (being 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) that do not have polar group fully can be distinguished use separately, also can will be used in combination more than 2 kinds.

As the concrete example of the monomer (d) beyond the 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 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; 1,4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, non-conjugated dienes such as 7-octadiene; Or the like.

Monomer (d) beyond these cyclic olefins can be distinguished use separately, also can will be used in combination more than 2 kinds.

Being used for the cyclic olefin polymer with protic polar group of the present invention can obtain by monomer (a) and the needed monomer that is selected from monomer (b)～(d) are carried out polymerization jointly.Polymerization and polymkeric substance can also further carry out hydrogenation.Be also included within the cyclic olefin polymer that uses among the present invention through the polymkeric substance behind the hydrogenation with protic polar group.

In addition, the cyclic olefin polymer with protic polar group that uses among the present invention can also obtain by following method: utilize known properties-correcting agent that the protic polar group is imported in the cyclic olefin polymer with protic polar group, and carry out hydrogenation as required.Hydrogenation also can carry out at importing protic polar group polymkeric substance before.In addition, can also utilize properties-correcting agent that the cyclic olefin polymer with protic polar group is carried out modification, and then import protic polar group based on properties-correcting agent.

The polymkeric substance that does not have the protic polar group can be by obtaining carrying out polymerization after above-mentioned monomer (b)～(d) arbitrary combination.

As the properties-correcting agent that is used to import the protic polar group, can use the compound that in a part, has protic polar group and reactive carbon-to-carbon unsaturated bond usually.

As the concrete example of this compounds, can enumerate: 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; 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-alcohol, 3-butene-2-alcohol, 3-methyl-3-butene-1-alcohol, 3-methyl-2-butene-1-alcohol, 2-methyl-3-butene-2-alcohol, 2-methyl-3-butene-1-alcohol, 4-amylene-1-ol, 4-methyl-4-amylene-1-ol, 2-hexen-1-ol; Or the like.

Modified-reaction as the cyclic olefin polymer that uses this properties-correcting agent carries out modification according to ordinary method and gets final product, and can carry out in the presence of radical initiator usually.

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

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

Polymkeric substance for being obtained by each monomer polymerization makes spent hydroprocessing catalyst carry out hydrogenation usually.

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

In above-mentioned hydrogenation catalyst, from can be under the situation that side reaction such as functional group modification does not take place to polymkeric substance the carbon-to-carbon unsaturated bond of the main chain viewpoint of carrying out selective hydrogenation consider, noble metal complexes catalyzer such as preferred rhodium, ruthenium, especially preferred coordination has and has highly to the nitrogen heterocyclic ring formula carbene compound of electronics or the ruthenium catalyst of phosphine class.

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

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

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

[Chemical formula 2]

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

[chemical formula 3]

[in the 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 is chosen wantonly and is had substituting group.K is an integer 0～2.]

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

R ' representative optional has the alkyl that substituent alkyl is generally the carbonatoms 1～7 of straight or branched, as the example, can enumerate alkyl such as methyl, ethyl, n-propyl, sec.-propyl.Optional have the aryl that substituent aryl is generally carbonatoms 6～10, as the example, can enumerate aryl such as phenyl, benzyl.Abovementioned alkyl or aryl have under the substituent situation, as the substituent example that imports on these alkyl or aryls, can enumerate: the alkyl of carbonatomss 1～4 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-; The aryl of carbonatomss 6～12 such as phenyl, xylyl, tolyl, naphthyl; Or the like.

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

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 ⁸With the example of the common 5 yuan of heterocycle structures that form of 2 carbon atoms of arbitrary combination and their institute's bondings, can enumerate the dicarboxylic anhydride structure [C (=O)-O-C (=O)-], the imide structure [C (=O)-N-C (=O)-] etc.This heterocycle has under the substituent situation, as the substituent example that imports on this heterocycle, can enumerate phenyl, naphthyl, anthryl etc.

The acrylic resin that uses among the present invention does not have particular restriction, but preferably to be selected from carboxylic acid with acryl, to have the carboxylic acid anhydride of acryl or to contain at least a homopolymer or multipolymer as neccessary composition in the acrylic compound of epoxy group(ing).

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

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

Concrete example as the acrylic compound that contains epoxy group(ing), can enumerate glycidyl acrylate, glycidyl methacrylate, α-Yi Jibingxisuan 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-Yi Jibingxisuan-6,7-epoxy heptyl ester etc.

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

Acrylic resin can be by be selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and contain in the unsaturated compound of epoxy group(ing) one of at least with acrylic ester monomer or acrylate beyond the formed multipolymer 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 phenoxy ethyl, (methyl) vinylformic acid 2-hydroxyl-(methyl) vinylformic acid phenoxyalkyl esters such as 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-butoxy ethyl ester, (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) vinylformic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-butyl cyclohexyl, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid three ring 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 the acrylate; so long as can be with above-mentioned carboxylic acid with acryl, have the carboxylic acid anhydride of acryl or contain the compound of the acrylic compound generation copolymerization of epoxy group(ing); then do not have particular restriction, for example can enumerate: vinyl benzyl methyl ether, vinyl glycidyl ether, vinylbenzene, alpha-methyl styrene, divinyl, isoprene etc. contain the free-radical polymerised compound of vinyl.

These compounds can be distinguished use separately, also can will be used in combination more than 2 kinds.

As above-mentioned monomeric polymerization process, carry out polymerization according to ordinary method and get final product, can adopt for example suspension polymerization, emulsion polymerization, solution polymerization process etc.

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

As the concrete example of the skeleton structure that forms can be enumerated constituting that bonding on the quaternary carbon atom of ring texture has two ring texturees: fluorene skeleton, bisphenol fluorene skeleton, two aminophenyl fluorene skeleton, have epoxy group(ing) fluorene skeleton, have the fluorene skeleton of acryl etc.

The cardo resin that uses among the present invention can have reaction between the functional group of this skeleton with cardo structure etc. and polymerization forms by bonding.The cardo resin has the structure (cardo structure) that main chain is connected with high spatial sterically hindered side chain by an element, and with the vertical substantially direction of main chain on have ring texture.

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

[chemical formula 4]

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

As monomer, for example can enumerate: two (glycidoxy phenyl) fluorenes type Resins, epoxy with cardo structure; Bisphenol fluorene type Resins, epoxy and acrylic acid condenses; 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes etc. of 9-contain the bisphenols of cardo structure; 9, two (cyano methyl) fluorenes of 9-etc. 9, two (cyano group alkyl) the fluorenes classes of 9-; 9, two (3-aminopropyl) fluorenes of 9-etc. 9, two (aminoalkyl group) fluorenes classes of 9-; Or the like.

The cardo resin is the polymkeric substance that is obtained by the monomer polymerization with cardo structure, but also can be the multipolymer that forms with the monomer of other copolymerization.

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

The structure of the polysiloxane that uses among the present invention there is no particular restriction, can preferably enumerate by the polysiloxane that mixes and its reaction is obtained more than a kind or 2 kinds with the organosilane shown in the formula (IV).

[chemical formula 5]

(in the 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 a plurality of 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, a plurality of 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 a plurality of R ₉Can be mutually the same, also can be different.And these alkyl, thiazolinyl, aryl are all optional to have substituting group, also can be not have substituent nothing to replace body, can select according to the characteristic of composition.Concrete example as 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, the 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 a plurality of R ₁₀Can be mutually the same, also can be different.And these alkyl, acyl group are all optional to have substituting group, also can be not have 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.During n=0, be four functional silanes; During n=1, be trifunctional silane; During n=2, be two functional silanes; During n=3, be simple function silane.

As the concrete example of the organosilane shown in the 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, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the n-hexyl triethoxyl silane, the decyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, phenyltrimethoxysila,e, phenyl triethoxysilane, the p-hydroxybenzene Trimethoxy silane, 1-(p-hydroxybenzene) ethyl trimethoxy silane, 2-(p-hydroxybenzene) ethyl trimethoxy silane, 4-hydroxyl-5-(p-hydroxybenzene carbonyl oxygen base) amyltrimethoxysilane, the trifluoromethyl Trimethoxy silane, the trifluoromethyl triethoxyl silane, 3,3,3-trifluoro propyl Trimethoxy silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 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; Simple function silane such as trimethylammonium methoxy silane, three normal-butyl Ethoxysilanes.

In above-mentioned organosilane,, preferably use trifunctional silane from considering by the anti-fragility and the hardness aspect of the resulting resin molding of resin combination of the present invention.In addition, these organosilanes may be used alone, or two or more kinds may be used in combination.

Polysiloxane among the present invention can obtain by making above-mentioned organosilane generation hydrolysis and part condensation.As hydrolysis and part condensation, can adopt ordinary method.For example, can in mixture, add solvent, water, as required and the catalyzer that uses, and carry out heated and stirred.Also can in whipping process, separate by product (alcohol such as methyl alcohol) and condensation by-product (water) by dephlegmate as required.

The polyimide that uses among the present invention can obtain by the polyimide precursor that is obtained by tetracarboxylic anhydride and diamine reactant is heat-treated.As the precursor that is used to obtain polyimide resin, comprise polyamic acid, poly amic acid ester, poly-different imide, polyamic acid sulphonamide (Port リアミ De acid ス Le ホ Application アミ De) etc.

As the acid dianhydride of the 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, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, 2, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2-, 1,1-two (3,4-dicarboxyl phenyl) ethane dianhydride, 1, two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 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, 2, aromatic series tetracarboxylic acid dianhydrides such as two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-; Or ethylene-dimalonic acid dianhydride, 1,2,3, aliphatics tetracarboxylic acid dianhydrides such as 4-cyclopentane tetracarboxylic acid dianhydride etc.These acid dianhydrides can use separately, also can will be used in combination more than 2 kinds.

Concrete example as the diamines of the 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, 1, two (4-amino-benzene oxygen) benzene of 4-, benzyne, mphenylenediamine, Ursol D, 1, the 5-naphthylene diamine, 2, the 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, 1, two (4-amino-benzene oxygen) benzene of 4-, 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 '-two (trifluoromethyl)-4,4 '-benzidine; Or the above-claimed cpd aromatic ring is replaced by alkyl or halogen atom and the compound that obtains; Or aliphatic cyclohexyl diamines, methylene-bis hexahydroaniline; Or the like.These diamines can use a kind separately, also can will be used in combination more than 2 kinds.

The polyimide that uses among the present invention can be synthetic by known method.Promptly, can be by optionally making up tetracarboxylic dianhydride and diamines, and make them at N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N known method such as react and synthesize in dinethylformamide, methyl-sulphoxide, HMPA, gamma-butyrolactone, the cyclopentanone isopolarity solvent.

The weight-average molecular weight (Mw) of the adhesive resin that uses among the present invention (A) is generally 1,000～1,000,000, preferred 1,500～100,000, 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), usually below 4, preferred below 3, more preferably below 2.5.

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

Compound (B) with acidic-group

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

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

These compounds (B) can be distinguished use separately, also can will be used in combination more than 2 kinds.

Number for acidic-group does not have particular restriction, but preferably has 2 above acidic-groups, especially preferably has 2 acidic-groups.Acidic-group can be mutually the same, also can be different.

Acidic-group as its concrete example, can be enumerated strong acid groups such as sulfonic group, phosphate so long as tart functional group gets final product; Slightly acidic groups such as carboxyl, sulfydryl and carboxyl methylene radical sulfenyl.Wherein, consider preferred carboxyl, sulfydryl or carboxyl methylene radical sulfenyl, especially preferred 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.Need to prove, for situation with 2 above acidic-groups, with 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 the organic acid conjugate base.PKa is pKa=-logKa.

In addition,, for example can measure hydrogen ion concentration, calculate by the concentration and the hydrogen ion concentration of respective substance again by using pH meter as the measuring method of pKa.

In the present invention, by using these acidic-groups, can make the resin molding that forms by resin combination of the present invention have excellent adaptation.

In the present invention, also optional other substituting group that has except that acid group of above-claimed cpd (B).

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

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

Formic acid, acetate, 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 (being also referred to as " oxalic acid "), propanedioic acid (being also referred to as " maleic acid "), Succinic Acid (being also referred to as " succsinic acid "), pentanedioic acid, hexanodioic acid (being also referred to as " adipic acid "), 1, the 2-cyclohexane dicarboxylic acid, 2-oxo propionic acid, the 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-1-butanols, 2,4-dimercapto-1, the 3-butyleneglycol, 1,3,4-tri-thiol-2-butanols, 3,4-dimercapto-1, the 2-butyleneglycol, 1,5-dimercapto-fatty compoundss such as 3-thia pentane;

Phenylformic acid, P-hydroxybenzoic acid, salicylic acid, the 2-naphthoic acid, tolyl acid, mesitylenic acid, trimethylbenzoic acid, the 3-phenylpropionic acid, 2 hydroxybenzoic acid, resorcylic acid, dimethoxybenzoic acid, benzene-1,2-dioctyl phthalate (being also referred to as " phthalic acid "), benzene-1,3-dioctyl phthalate (being also referred to as " m-phthalic acid "), benzene-1,4-dioctyl phthalate (being also referred to as " terephthalic acid "), benzene-1,2, the 3-tricarboxylic acid, benzene-1,2, the 4-tricarboxylic acid, benzene-1,3, the 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, the 2-Thiosalicylic acid, the 4-Thiosalicylic acid, 2-sulfydryl-6-naphthoic acid, 2-sulfydryl-7-naphthoic acid, 1, the 2-thioresorcin, 1, the 3-thioresorcin, 1, the 4-thioresorcin, 1,4-naphthyl disulfide phenol, 1,5-naphthyl disulfide phenol, 2,6-naphthyl disulfide phenol, 2,7-naphthyl disulfide phenol, 1,2,3-tri-thiol benzene, 1,2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1,2,3-three (mercapto methyl) benzene, 1,2,4-three (mercapto methyl) benzene, 1,3,5-three (mercapto methyl) benzene, 1,2,3-three (mercaptoethyl) benzene, 1,2,4-three (mercaptoethyl) benzene, 1,3, aromatics such as 5-three (mercaptoethyl) benzene;

Nicotinic acid, Yi Yansuan, 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-3,5-dioctyl phthalate etc. contains the five member ring heterocyclic compound of nitrogen-atoms; Thiophene-2, the 3-dioctyl phthalate, thiophene-2, the 4-dioctyl phthalate, thiophene-2, the 5-dioctyl phthalate, thiophene-3, the 4-dioctyl phthalate, thiazole-2, the 4-dioctyl phthalate, thiazole-2, the 5-dioctyl phthalate, thiazole-4, the 5-dioctyl phthalate, isothiazole-3, the 4-dioctyl phthalate, isothiazole-3, the 5-dioctyl phthalate, 1,2,4-thiadiazoles-2, the 5-dioctyl phthalate, 1,3,4-thiadiazoles-2, the 5-dioctyl phthalate, 3-amino-5-sulfydryl-1,2, the 4-thiadiazoles, 2-amino-5-sulfydryl-1,3, the 4-thiadiazoles, 3,5-dimercapto-1,2, the 4-thiadiazoles, 2,5-dimercapto-1,3, the 4-thiadiazoles, 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-) acetate, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) acetate, 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, 4-(2-sulfydryl-1,3,4-thiadiazoles-5-yl) sulfo-fourth sulfonic acid etc. contains the five member ring heterocyclic compound of nitrogen-atoms and sulphur atom;

Pyridine-2, the 3-dioctyl phthalate, pyridine-2, the 4-dioctyl phthalate, pyridine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, pyridine-3, the 4-dioctyl phthalate, pyridine-3, the 5-dioctyl phthalate, pyridazine-3, the 4-dioctyl phthalate, pyridazine-3, the 5-dioctyl phthalate, pyridazine-3, the 6-dioctyl phthalate, pyridazine-4, the 5-dioctyl phthalate, pyrimidine-2, the 4-dioctyl phthalate, pyrimidine-2, the 5-dioctyl phthalate, pyrimidine-4, the 5-dioctyl phthalate, pyrimidine-4, the 6-dioctyl phthalate, pyrazine-2, the 3-dioctyl phthalate, pyrazine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, triazine-2, the 4-dioctyl phthalate, 2-diethylamino-4,6-dimercapto s-triazine, 2-dipropyl amino-4,6-dimercapto s-triazine, 2-dibutylamino-4,6-dimercapto s-triazine, 2-anilino-4,6-dimercapto s-triazine, 2,4,6-tri-thiol s-triazine etc. contains the 6-membered heterocyclic compound of nitrogen-atoms.

Wherein, become the viewpoint that has the material of good adaptation with substrate from making the resin molding that is formed by resin combination, the number of its acidic-group is preferably more than 2, especially is preferably 2.

As compound with 2 acidic-groups, preferred oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, 1, the 2-cyclohexane cyclohexanedimethanodibasic, benzene-1,2-dioctyl phthalate (being also referred to as " phthalic acid "), benzene-1,3-dioctyl phthalate (being also referred to as " m-phthalic acid "), benzene-1,4-dioctyl phthalate (being 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, the 2-Thiosalicylic acid, the 4-Thiosalicylic acid, 2-sulfydryl-6-naphthoic acid, 2-sulfydryl-7-naphthoic acid, 1, the 2-thioresorcin, 1, the 3-thioresorcin, 1, the 4-thioresorcin, 1,4-naphthyl disulfide phenol, 1,5-naphthyl disulfide phenol, 2,6-naphthyl disulfide phenol, 2,7-naphthyl disulfide phenol etc. has the aromatics of 2 acidic-groups; Pyrroles-2, the 3-dioctyl phthalate, pyrroles-2, the 4-dioctyl phthalate, pyrroles-2, the 5-dioctyl phthalate, pyrroles-3, the 4-dioctyl phthalate, imidazoles-2, the 4-dioctyl phthalate, imidazoles-2, the 5-dioctyl phthalate, imidazoles-4, the 5-dioctyl phthalate, pyrazoles-3, the 4-dioctyl phthalate, pyrazoles-3, the 5-dioctyl phthalate, thiophene-2, the 3-dioctyl phthalate, thiophene-2, the 4-dioctyl phthalate, thiophene-2, the 5-dioctyl phthalate, thiophene-3, the 4-dioctyl phthalate, thiazole-2, the 4-dioctyl phthalate, thiazole-2, the 5-dioctyl phthalate, thiazole-4, the 5-dioctyl phthalate, isothiazole-3, the 4-dioctyl phthalate, isothiazole-3, the 5-dioctyl phthalate, 1,2,4-thiadiazoles-2, the 5-dioctyl phthalate, 1,3,4-thiadiazoles-2,5-dioctyl phthalate, (5-sulfydryl-1,2,4-thiadiazoles-3-base sulfo-) acetate, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfo-) acetate, pyridine-2, the 3-dioctyl phthalate, pyridine-2, the 4-dioctyl phthalate, pyridine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, pyridine-3, the 4-dioctyl phthalate, pyridine-3, the 5-dioctyl phthalate, pyridazine-3, the 4-dioctyl phthalate, pyridazine-3, the 5-dioctyl phthalate, pyridazine-3, the 6-dioctyl phthalate, pyridazine-4, the 5-dioctyl phthalate, pyrimidine-2, the 4-dioctyl phthalate, pyrimidine-2, the 5-dioctyl phthalate, pyrimidine-4, the 5-dioctyl phthalate, pyrimidine-4, the 6-dioctyl phthalate, pyrazine-2, the 3-dioctyl phthalate, pyrazine-2, the 5-dioctyl phthalate, pyridine-2, the 6-dioctyl phthalate, triazine-2,4-dioctyl phthalate etc. has the heterogeneous ring compound of 2 acidic-groups.

By using above-claimed cpd, can obtain following effect: have high adaptation between resin molding that forms by resin combination and the substrate.

With respect to adhesive resin (A) 100 weight parts, the content of the compound with acidic-group (B) in the resin combination of the present invention is generally 5～45 weight parts, preferred 7～40 weight parts, more preferably 10～30 weight part scopes.The consumption of compound (B) with acidic-group is in this scope the time, the resin combination that can obtain to have 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 that is selected from Siliciumatom, titanium atom, aluminium atom, the zirconium atom, and has the-oxyl that is bonded on this atom or the compound of hydroxyl.

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

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

When adhesive resin (A) is when having the resin of protic polar group, compound (D) be preferably especially have can with the compound of the functional group of protic polar group reaction.

Describedly can be preferably isocyanate group, sulfydryl, epoxy group(ing) or amino, more preferably epoxy group(ing) with the functional group of protic polar group reaction.

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

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, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-pentyl Trimethoxy silane, the n-hexyl Trimethoxy silane, the n-heptyl Trimethoxy silane, the n-octyl Trimethoxy silane, positive decyl Trimethoxy silane, to the styryl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-chloropropyl triethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl triethoxyl silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 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, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 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, trialkoxysilanes such as two (triethoxysilylpropyltetrasulfide) four thioethers;

Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, di dimethoxy silane, the di diethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, di-n-butyl dimethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, the di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, the di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, the 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, N-2-(amino-ethyl)-dialkoxy silicane classes such as 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 one 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, the stearic acid titanium, the diisopropoxy titanium diisostearate, (2-n-butoxy carbonyl benzoyl oxygen base) three titanium butoxide, two n-butoxies two (trolamines) close titanium, and PlainAct series (aginomoto Jinggong Co., Ltd system) etc. contains the compound of titanium atom;

Acetyl alkoxyl group diisopropyl acid aluminium etc. contains the compound of 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, the tetrem ethyl sodio acetoacetic ester closes the compound that zirconium, three butoxy zirconium stearates etc. contain zirconium atom.

This wherein, preferably contain Siliciumatom compound, contain the compound of titanium atom, more preferably contain the compound of Siliciumatom, especially preferably have and can and contain the compound of Siliciumatom with the functional group of protic polar group reaction.By having above-mentioned functional group, the adaptation in the time of can making resin combination of the present invention on being stacked to substrate is further enhanced.

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

As above-mentioned have can with the concrete example of the compound of the functional group of protic polar group reaction, especially preferred: the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 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, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 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 can will be used in combination more than 2 kinds.

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

In the present invention, with respect to adhesive resin (A) 100 weight parts, above-claimed cpd (B) is 10～50 weight parts, preferred 13～40 weight parts, especially preferred 15～35 weight parts with the total content of compound (D).If above-mentioned total amount less than 10 weight parts then can't obtain the effect that adaptation improves; On the contrary, if surpass 50 weight parts, then, can increase the decrement (subtracting the film amount) of filming when developing adding radiosensitive compound (E) when giving photosensitivity for resin combination.

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

Organic solvent (C)

There is no particular restriction for the organic solvent (C) that uses in the present invention.As its concrete example, can enumerate: aklylene glycol classes such as ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG; Alkylene glycol mono ethers such as ethylene glycol monomethyl ether, glycol monomethyl propyl ether, glycol monomethyl 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; 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; 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; Ketones such as methyl ethyl ketone, pimelinketone, 2-heptanone, 4-hydroxy-4-methyl-2 pentanone, pimelinketone, cyclopentanone; Methyl alcohol, ethanol, propyl alcohol, butanols, 3-methoxyl group-alcohols such as 3-methyl butanol; Tetrahydrofuran (THF), two

Ring-type ethers such as alkane; Cellosolve such as methylcellosolve acetate, ethyl cellosolve acetate ester class; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; 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-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, gamma-butyrolactone; N-methylformamide, N, amidess such as dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, N-methylacetamide, N,N-dimethylacetamide; Sulfoxide classes such as methyl-sulphoxide; Or the like.

Wherein, preferred Diethylene Glycol ethyl-methyl ether, propylene glycol monomethyl ether, cyclopentanone, N-N-methyl-2-2-pyrrolidone N-.

These organic solvents can be distinguished use separately, also can will be used in combination more than 2 kinds.With respect to adhesive resin (A) 100 weight parts, the consumption of organic solvent (C) is generally 20～10,000 weight part, preferred 50～5,000 weight part, more preferably 100～1,000 weight part scope.

Radiosensitive compound (E)

The radiosensitive compound (E) that uses among the present invention be can be under the situation of irradiation ultraviolet radiation or electron beam isoradial the compound of initiating chamical reaction.In the present invention, the compound that preferably can control the alkali dissolution of the resin molding that forms by resin combination of radiosensitive compound (E).

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

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

As quinone di-azido compound, can use for example by quinone diazido sulfonic acid halide and ester cpds with 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, can enumerate 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-methylethyl with phenol hydroxyl] phenyl] ethylidene] bis-phenol etc.Has the compound of phenol hydroxyl as except that above-mentioned other, can enumerate 2,3,4-trihydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, two (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) methane, 1,1 of 2-, 1-three (4-hydroxy-3-methyl phenyl) ethane, 1,1,2, the oligopolymer of 2-four (4-hydroxy phenyl) ethane, novolac resin, oligopolymer of obtaining through copolymerization by compound with 1 phenol hydroxyl and Dicyclopentadiene (DCPD) etc.

Wherein, preferred 1,2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE and condenses with compound of phenol hydroxyl, more preferably 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-and 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 the quinone diazide; can also use salt, halogenated organic compounds, α, known light acid producing agents such as α '-two (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 can will be used in combination more than 2 kinds.

With respect to adhesive resin (A) 100 weight parts, the content of radiosensitive compound (E) is 1～100 weight part, preferred 5～50 weight parts, more preferably 10～40 weight part scopes in the resin combination of the present invention.When the consumption of radiosensitive compound (E) is in this scope, when on any substrate, forming the resin molding that comprises resin combination of the present invention and the resin molding that forms being carried out patterning, in resin molding, radiation exposure portion and the radioactive rays not difference of the solubleness of irradiation portion in developing solution become big, be easy to carry out patterning by developing, 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 intramolecularly have more than 2, preferred more than 3 can with the material of the functional group of adhesive resin (A) reaction.The functional group that linking agent (F) is had does not have particular restriction so long as can get final product with the group that functional group in the adhesive resin, unsaturated link(age) etc. react, preferably can with the group of protic polar group reaction.

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: aliphatic polyamine classes such as hexamethylene-diamine; 4, aromatic polyamine classes such as 4 '-diamino-diphenyl ether, diamino diphenyl sulfone; 2, two (the 4 '-azido-benzylidene) pimelinketone, 4 of 6-, nitrine classes such as 4 '-diazido sulfobenzide; Nylon, polyhexamethylene diamines terephthalamide, polyhexamethylene isophthaloyl amine etc. are polyamide-based; N, N, N ', N ', N ", N " melamine class such as (six alkoxy methyls) trimeric cyanamide; N, N ', N ", N " '-glycoluril classes such as (four alkoxy methyls) glycoluril; Acrylic compound such as ethylene glycol bisthioglycolate (methyl) acrylate; Isocyanate ester compounds such as hexamethylene diisocyanate class polyisocyanates, isophorone diisocyanate class polyisocyanates, tolylene diisocyanate class polyisocyanates, hydrogenation diphenylmethanediisocyanate; 1,4-two (hydroxymethyl) hexanaphthene, 1,4-two (hydroxymethyl) norbornane; 1,3,4-trihydroxy-hexanaphthene; 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, polyphenol type Resins, epoxy, cyclic aliphatic epoxy resin, aliphatic glycidyl base ether, epoxy acrylic ester polymer.

As the concrete example of isocyanate ester compound, can enumerate: the CORONATE series (CORONATE L) that the TAKENATE series (B-815N, B-882N, B-874N) that DESMODULE series (DESMODULE BL3370, DESMODULEVPLS2253) that Sumika Bayer Urethane company makes and CRELAN series (CRELAN V1, CRELAN VPLS2256), MitsuiTakeda Chemicals company make, Nippon Polyurethane company make 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 " (above) by the manufacturing of Cytec Industries company, " NIKALAC MW-30HM ", " NIKALAC MW390 ", " NIKALAC MX-750 ", " NIKALAC MX-706 " (above) etc. by the manufacturing of Sanwa Chemical company.

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

Concrete example as epoxy compounds, can enumerate: the trifunctional epoxy compounds (trade(brand)name " XD-1000 " that with the Dicyclopentadiene (DCPD) is skeleton, Japan's chemical drug corporate system is made), 2,1 of two (the hydroxymethyl)-1-butanols of 2-, 2-epoxy-4-(2-Oxyranyle) hexanaphthene affixture (15 functionality cycloaliphatic epoxy resins with hexanaphthene skeleton and terminal epoxy groups, trade(brand)name " EHPE3150 ", Daicel chemical industrial company makes), 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 makes), 6-caprolactone (aliphatics ring-type four functionality Resins, epoxy, trade(brand)name " EPOLEAD GT401 " that epoxidation ethylene-dimalonic acid four (3-cyclohexenyl methyl esters) is modified.Daicel chemical industrial company makes), 3,4-epoxycyclohexyl methacrylic ester (trade(brand)name " CYCLOMER A400 ", Daicel chemical industrial company makes), 1,2,8,9-diepoxy limonene (trade(brand)name " CELOXIDE 3000 ", Daicel chemical industrial company makes), (3 ', 4 '-epoxy cyclohexane) methyl 3,4-epoxy cyclohexane manthanoate (trade(brand)name " CELOXIDE 2021 ", Daicel chemical industrial company makes), 1,2-epoxy-4-vinyl cyclohexane (trade(brand)name " CELOXIDE 2000 ", Daicel chemical industrial company makes) etc. has the epoxy compounds of alicyclic structure;

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

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

Molecular weight for linking agent (F) does not have particular restriction, but is generally 100～100,000, preferred 500～50,000, more preferably 1,000～10,000.Linking agent can be distinguished use separately, also can will be used in combination more than 2 kinds.

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

Other additive

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

As the concrete example of sensitizing agent, can enumerate the 2H-pyrido-(3,2-b)-1,4-

Piperazine-3 (4H)-ketone, 10H-pyrido-(3,2-b)-1,4-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 purpose of tensio-active agent to be: to prevent striped (striation, coating streak), improve development etc.As its concrete example, can enumerate: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether; Nonionic surface active agent such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene SUNSOFT Q-182S; Fluorine class tensio-active agent; Silicone based tensio-active agent; Sipacril 2739OF class tensio-active agent; Acrylic copolymer class tensio-active agent; Or the like.

Use the purpose 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 the phenolic antioxidant that is normally used for polymkeric substance, Phosphorus oxidation inhibitor, sulfur type antioxidant, lactone oxidation inhibitor etc.For example, as phenolic antioxidant, can enumerate 2, the 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 butyl phenol), 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, the 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 in the following substances any: material of the free radical that UV light absorber such as benzophenone, salicylate class, benzotriazole category, cyanoacrylate, metal complex salt class, hindered amines (HALS) etc. can be captured under the light action to be produced 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/three decyls 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 does not have particular restriction, 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); Compound (B) with acidic-group; Have the a kind of atom that is selected from Siliciumatom, titanium atom, aluminium atom, the zirconium atom and have the-oxyl that is bonded on this atom or the compound (D) of hydroxyl; Organic solvent (C); And other composition that uses as required.

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

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

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

Multilayer body

But the resin combination of multilayer body the application of the invention of the present invention forms resin molding and obtains on substrate.

In the present invention, substrate can use for example printed circuit substrate, silicon chip substrate, glass substrate, plastic base etc.In addition, the also preferred material that in field of display, uses, on glass substrate or plastic base etc., formed thin type transistor type liquid crystal display device, colour filter, black matrix etc. that adopts.

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

Above-mentioned film lay-up method is: resin combination is coated on B rank such as resin molding or metallic membrane film form with body material on after, remove by heat drying and to desolvate to obtain B rank film, then, this B rank film is stacked in method on the above-mentioned body material.The 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.The film lamination can adopt 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 resin film that forms on substrate is generally 0.1～100 μ m, preferred 0.5～50 μ m, more preferably 0.5～30 μ m.

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

The resin molding that forms on substrate is carried out when crosslinked, can select the method that is fit to according to the kind of linking agent, but be undertaken by heating usually.As heating means, for example can adopting, hot plate, baking oven etc. carry out.Heating temperature is generally 180～250 ℃, and can suitably select heat-up time according to size, thickness and the use equipment etc. of resin molding, for example, when using hot plate, is generally 5～60 minutes heat-up time; When using baking oven, be generally 30～90 minutes scopes heat-up time.As required, heating also can be carried out in the inactive gas atmosphere.As inactive gas, use oxygen-free and the gas of resin molding generation oxidation is got final product, for example can enumerate: nitrogen, argon gas, helium, neon, xenon, krypton gas etc.Wherein, preferred nitrogen and argon gas, special preferred nitrogen.The suitable especially oxygen content that adopts is that 0.1 volume % is following, the inactive gas below the preferred 0.01 volume %, especially preferably uses nitrogen.These inactive gass can be distinguished use separately, also can will be used in combination more than 2 kinds.

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

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

When forming the patterned resin film, at first, the resin molding that forms is shone active radioactive rays on substrate, form the sub-image pattern.As active radioactive rays, so long as the active radioactive rays that can make light acid producing agent activation and the alkali-soluble of the crosslinkable composite that comprises light acid producing agent is changed then do not have particular restriction.Specifically can use: light beams such as the ultraviolet ray of single wavelengths such as ultraviolet ray, g ray or i ray, KrF excimer laser, ArF excimer laser; Particle beam such as electron beam etc.Shine and form the sub-image method of patterning as utilizing these active radioactive rays to carry out optionally pattern-like, 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 particle beam such as electron beam draw etc.For the situation of using light beam as active radioactive rays, can be single wavelength light, also can mixed wavelengths light.Illuminate condition can suitably be selected according to employed active radioactive rays, and for example, under the situation of the light beam of use wavelength 200～450nm, irradiation dose is generally 10～1,000mJ/cm ², preferred 50～500mJ/cm ²Scope is determined according to irradiation time and illumination.After shining active radioactive rays as described above, as required, under the temperature about 60～130 ℃ resin molding is being carried out heat treated about 1～2 minute.

Then, the sub-image pattern that forms on resin molding is developed, so that its visibleization.In the present invention, above-mentioned steps is called " patterning ", will be called " patterned resin film " through the resin molding of patterning.As developing solution, use the aqueous solution of basic cpd usually.As basic cpd, can use for example an alkali metal salt, amine, ammonium salt.Basic cpd can be a mineral compound, also can be organic compound.As the concrete example of these compounds, can enumerate: sodium hydroxide, potassium hydroxide, yellow soda ash, water glass (sodium silicate), Starso an alkali metal salts such as (sodium metasilicate); Ammoniacal liquor; Primary amine such as ethamine, Tri N-Propyl Amine; Secondary amine such as diethylamine, di-n-propylamine; Tertiary amines such as triethylamine, methyl diethylamide; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline; Hydramine such as dimethylethanolamine, trolamine; Pyrroles, piperidines, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, cyclic amine such as 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N-Methyl pyrrolidone; Or the like.These basic cpds can be distinguished use separately, also can will be used in combination more than 2 kinds.

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

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 ℃, preferred 5～55 ℃, more preferably 10～30 ℃ of scopes, development time be generally 30～180 second scope.

Thus, on substrate, form after the patterned resin film of target, can utilize washing fluid that substrate is washed as required, with remove on the substrate, the development residue of substrate back and substrate end.After handling, utilize pressurized air or compressed nitrogen to remove residual washing fluid through flushing.

In addition, in order to make the light acid producing agent inactivation, can also shine active radioactive rays to whole base plate as required with patterned resin film.When shining active radioactive rays, can adopt illustrative method in the formation method of above-mentioned sub-image pattern.Can in the active radioactive rays of irradiation or after the irradiation, 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, can be to form after the patterned resin on the 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 the substrate.

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

Embodiment

Below, enumerate embodiment the present invention is more specifically illustrated, but the present invention is not subject to these embodiment fully.

Need to prove that in the present embodiment, " part " reaches " % " and represents that respectively " weight part " reaches " weight % " in the absence of particular determination.

Utilize following method that each characteristic is estimated.

(1) polymerisation conversion

Utilize the 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)

Utilization with the tetrahydrofuran (THF) be elutriant gel permeation chromatography the polystyrene conversion value.

(3) hydrogenation ratio

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

(4) adaptation

[measuring making] with sample

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

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

Subsequently, utilize baking oven 230 ℃ of heating bakings after 60 minutes down, thereby obtained adaptation mensuration multilayer body.

[mensuration of adaptation]

At the gained multilayer body, the sticking power tester (adhesion tester) that uses COTEC company to make is measured by check (proof) method.Based on measurement result, the adaptation of gained multilayer body is judged according to following standard.

◎: more than the 8MPa

Zero: more than the 5MPa and less than 8MPa

More than △: the 3MPa and less than 5MPa

*: less than 3MPa

[Production Example 1]

(manufacturing 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, 2,0.5 part of 2-Diisopropyl azodicarboxylate and propylene glycol monomethyl ether stir for 300 parts, in 80 ℃ carried out 5 hour heating on one side.Utilize the rotatory evaporator gained resin solution is concentrated, obtained solid component concentration and be 35% acrylic resin soln.

[Production Example 2]

(manufacturing) with cyclic olefin polymer of protic polar group

Will be as the 9-hydroxycarbonyl group Fourth Ring [6.2.1.1 of cyclic olefin monomers with protic polar group ^3,6.0 ^2,7] 12 carbon-60 parts in 4-alkene, as the Fourth Ring [6.2.1.1 that do not have the cyclic olefin monomers of protic polar group ^3,6.0 ^2,7] 40 parts in 12 carbon-4-alkene (being also referred to as " tetracyclododecane "), 1, (1,3-two for 2.8 parts of 5-hexadienes, dichloro benzal

Base imidazolidine-2-subunit) (tricyclohexyl phosphine) closes 0.05 part of ruthenium and Diethylene Glycol ethyl-methyl ether adds to for 400 parts in the withstand voltage glass reactor that has passed through nitrogen replacement, under agitation, carry out 2 hours polyreactions in 80 ℃, obtained containing the polymeric reaction solution of 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, the two chloroethoxy methylene-biss (tricyclohexyl phosphine) that add in the above-mentioned polymeric reaction solution that obtains as hydrogenation catalyst close 0.1 part of ruthenium, and under the pressure of 4MPa dissolving hydrogen 5 hours to carry out hydrogenation reaction.Then, in this solution, add 1 part of active carbon powder, again this solution was joined in the autoclave while stirring under 150 ℃, 4MPa pressure dissolving hydrogen 3 hours.Then, take out gained solution, solution is filtered, isolate gac, thereby obtained containing 476 parts of the hydrogenation reaction solution of the hydride 1B of Romp polymer 1A with the fluoro-resin filter made device of aperture 0.2 μ m.Filtration can be carried out under no 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 that the hydrogenation reaction solution of gained hydride 1B is concentrated, solid component concentration is adjusted to 35%, thereby has obtained the solution of hydride 1C (containing the cyclic olefin polymer of carboxyl) as the protic polar group.Output before and after concentrating, weight-average molecular weight, number-average molecular weight and the molecular weight distribution of hydride do not change.

[Production Example 3]

(manufacturing of cardo resin)

In the four neck flasks that have reflux exchanger, add bisphenol fluorene type Resins, epoxy 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 makes, 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 120～125 ℃ heating condition, carry out stirring in 1 hour, under 75～80 ℃, carry out 6 hours heated and stirred again, then, drop into 8.6 parts of glycidyl methacrylate, and under 80 ℃, carried out stirring in 8 hours.Utilize rotatory evaporator that the gained resin solution is concentrated, obtained the cardo resin solution of solid component concentration 35%.

[Production Example 4]

(manufacturing 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 (is 0.2 weight % with respect to the monomer that adds) in 55.8 parts of water.Then, flask is dipped in 70 ℃ the oil bath and carries out stirring in 1 hour, then, oil bath is warming up to 115 ℃ through 30 minutes.Heat up beginning after 1 hour, and the interior temperature of solution reaches 100 ℃, begins to have carried out 2 hours heated and stirred (interior temperature is 100～110 ℃) from this moment.Distill out 115 parts first alcohol and water altogether as by product.In the DAA of gained polysiloxane solution, add DAA and make its solid component concentration reach 35 weight %, thereby obtained polysiloxane solution.

[Production Example 5]

(manufacturing of polyimide)

In the dry air air-flow, in four neck flasks, add 4,102.5 parts of 9.61 parts in 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 make it in 40 ℃ of dissolvings down.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 under 50 ℃, carried out reaction in 3 hours.Utilize the rotatory evaporator this solution is concentrated, obtained solid component concentration and be 35% polyimide solution.

[Production Example 6]

(manufacturing that does not have the cyclic olefin polymer of protic polar group)

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

[embodiment 1]

Mixing as 100 parts of the acrylic resin solns that obtains in Production Example 1 of adhesive resin (A) (wherein, with solid component meter), as 1 of radiosensitive compound (E), 1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1, (Japan Synesis Company makes the condenses of 2-naphthoquinones two nitrine-5-SULPHURYL CHLORIDE (2.5 moles), " TS200 (goods name) ") 25 parts, as 20 parts in 2-(carboxyl methyl) phenylformic acid of the compound with acidic-group (B), as 8 parts of 92 parts in the Diethylene Glycol ethyl-methyl ether of organic solvent (C) and N-N-methyl-2-2-pyrrolidone N-s, as 10 parts of the 3-sulfydryl propyl trimethoxy silicanes of compound (D), 6-caprolactone (the Resins, epoxy of modifying as the epoxidation BTCA four (3-cyclohexenyl methyl esters) of linking agent (F) of aliphatics ring-type four functionalities, trade(brand)name " EPOLEAD GT401 ", the manufacturing of Daicel chemical industrial company) 20 part, 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 silicone based tensio-active agent (ProductName " KP341 ", the manufacturing of chemical industrial company of SHIN-ETSU HANTOTAI) 0.05 part, and carried out mixing and stirred.

After carrying out stirring in 30 minutes, mixture becomes homogeneous solution.With the aperture is that the tetrafluoroethylene filter made device of 0.45 μ m filters this solution, thereby has prepared resin combination 1D.

Then, use this resin combination 1D, obtain multilayer body according to the method described above, and its adaptation is estimated.The 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) all is illustrated in when being scaled solids component.

[embodiment 2～7]

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

The result is as shown in table 1.

[embodiment 8～14]

In embodiment 1, use the cyclic olefin polymer that obtains in the Production Example 2 as adhesive resin (A), the compound (B), compound (D) and the linking agent (F) that use kind shown in table 1～2 respectively are 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, prepared resin combination according to the method identical, obtained multilayer body then, and carried out the evaluation of adaptation at the gained multilayer body with embodiment 1.

The result is shown in table 1～2.

[embodiment 15～21]

In embodiment 1, use the cardo resin that obtains in the Production Example 3 as adhesive resin (A), the compound (B), compound (D) and the linking agent (F) that use kind shown in table 2～3 respectively are 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, prepared resin combination according to the method identical, obtained multilayer body then, and carried out the evaluation of adaptation at the gained multilayer body with embodiment 1.

The result is shown in table 2～3.

[embodiment 22～28]

In embodiment 1, use the polysiloxane that obtains in the Production Example 4 as adhesive resin (A), the compound (B), compound (D) and the linking agent (F) that use kind shown in table 3～4 respectively are 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, prepared resin combination according to the method identical, obtained multilayer body then, and carried out the evaluation of adaptation at the gained multilayer body with embodiment 1.

The result is shown in table 3～4.

[embodiment 29～35]

In embodiment 1, use the polyimide that obtains in the Production Example 5 as adhesive resin (A), the compound (B), compound (D) and the linking agent (F) that use kind shown in table 4～5 respectively are 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, prepared resin combination according to the method identical, obtained multilayer body then, and carried out the evaluation of adaptation at the gained multilayer body with embodiment 1.

The result is shown in table 4～5.

[embodiment 36～46]

In embodiment 1, the adhesive resin (A), compound (B), compound (D) and the linking agent (F) that use kind shown in table 5～6 respectively are 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, prepared resin combination according to the method identical with embodiment 1, obtain multilayer body then, and carried out the evaluation of adaptation at the gained multilayer body.Need to prove, in embodiment 46, as adhesive resin (A), use be the cyclic olefin polymer that does not have the protic polar group that in Production Example 6, obtains.

The result is shown in table 5～6.

[comparative example 1,2]

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

The result is as shown in table 7.

[comparative example 3,4]

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

The result is as shown in table 7.

[comparative example 5]

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

The 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 that uses in embodiment and the comparative example (B), acid ionization constant.

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

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

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

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

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

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

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

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

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

SR-4GL: poly-glycerine polyglycidyl ether compound (trade(brand)name " SR-4GL ", this pharmaceutical industries of slope Co., Ltd. makes)

GT401: the 6-caprolactone (Resins, epoxy 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 makes)

From the result of table 1～7 as can be known, when using the resin combination of embodiment 1～46 to form resin molding on substrate, the gained resin molding has high adaptation to substrate.Wherein, the resin combination of embodiment 1～46 contains adhesive resin (A), compound (B) with acidic-group, organic solvent (C), and has a Siliciumatom of being selected from, titanium atom, the aluminium atom, 1 kind of atom in the zirconium atom, and have the-oxyl that is bonded on this atom or a compound (D) of hydroxyl, and the compound (B) with acidic-group is selected from fatty compounds, in aromatics and the 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).

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

Claims

1. 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 that is selected from Siliciumatom, titanium atom, aluminium atom and the zirconium atom, and has-oxyl or the hydroxyl that is bonded on this atom, wherein,

Above-mentioned compound (B) with acidic-group is at least a kind that is selected from fatty compounds, aromatics and the heterogeneous ring compound,

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 acidic-group with compound (B) of acidic-group is carboxyl, sulfydryl or carboxyl methylene radical sulfenyl.

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

When having 2 above acidic-groups in the described compound (B) with acidic-group, its first acid ionization constant pKa1 is in 3.5～5.0 scopes.

5. according to each described resin combination in the claim 1～4, wherein, described compound (B) with acidic-group contains 2 above acidic-groups.

6. according to each described radiation-sensitive resin composition in the claim 1～5, it also contains linking agent (F).

7. radiation-sensitive resin composition according to claim 6, wherein, described linking agent (F) is an epoxy compounds.

8. resin combination according to claim 7, wherein, described epoxy compounds is the epoxy compounds with alicyclic structure.

9. according to each described resin combination in the claim 1～8, wherein, described adhesive resin (A) is for being selected from the polymkeric substance more than a kind in cyclic olefin polymer, acrylic resin, cardo resin, polysiloxane and the polyimide with protic polar group.

10. according to each described resin combination in the claim 1～9, wherein, described compound (D) still have can with the compound of the functional group of protic polar group reaction.

11. resin combination according to claim 10 wherein, can be isocyanate group, sulfydryl, epoxy group(ing) or amino with the functional group of protic polar group reaction in the described compound (D).

12. according to each described resin combination in the claim 1～11, wherein, the content of described compound (B) is more than or equal to the content of described compound (D).

13. the manufacture method of a multilayer body, it has following step: each described resin combination forms the step of resin molding in the use claim 1～12 on substrate.

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

The resin molding that is formed on the described substrate is shone 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,, thereby above-mentioned resin molding is carried out the step of patterning so that as seen the sub-image pattern change.

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

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

16. according to the manufacture method of each described multilayer body in the claim 13～15, it also has following step:

Make the crosslinked step of resin molding that is formed on the described substrate.

17. a multilayer body, it comprises substrate and is stacked on the resin molding that is formed by each described resin combination in the claim 1～12 on this substrate.

18. multilayer body according to claim 17, wherein, described resin molding is the patterned resin film.

19. a semiconducter device, it comprises claim 17 or 18 described multilayer body.