CN107429069A

CN107429069A - Resin combination, laminate structure and its manufacture method

Info

Publication number: CN107429069A
Application number: CN201680014598.7A
Authority: CN
Inventors: 沟口晃
Original assignee: Sumitomo Electric Industries Ltd
Current assignee: Sumitomo Electric Industries Ltd
Priority date: 2015-03-09
Filing date: 2016-03-08
Publication date: 2017-12-01
Also published as: WO2016143802A1; JPWO2016143802A1

Abstract

It is an object of the invention to provide a kind of resin combination, its readily selected adaptation for meeting the additive of purposes, and being easy to improve formed resin bed and metal level.According to the resin combination of one embodiment of the invention, it is the resin combination comprising synthetic resin and additive, wherein, the energy level for the lowest unoccupied molecular orbital that the semiempirical molecular orbital by using AM1 methods of above-mentioned additive is calculated and calculated is below 0.2eV.Relative to the synthetic resin of 100 mass parts, the content of additive is preferably more than 0.1 mass parts below 10 mass parts.Additive is preferably substituted or non-substituted heterocyclic compound.Heterocyclic compound preferably has amino, mercapto or combinations thereof.Synthetic resin preferably comprises the resin with polar group.Resin with polar group is preferably polyimides, polyesterimide, polyester, polyamidoimide, phenoxy resin or combinations thereof.

Description

Resin combination, laminate structure and its manufacture method

Technical field

The present invention relates to resin combination, laminate structure and its manufacture method.

Background technology

Electric wire, printed circuit board (PCB) as the inscape of electrical equipment, automobile etc. etc. are to include metal level and stacking The laminate structure of resin bed at least a portion of the metal level.In these laminate structures, it is desirable to metal level with The excellent adhesion of resin bed, it is difficult to splitting occurs.

The method for meeting above-mentioned requirements have (such as) form the method for surface-treated layer on the metal layer, in metal level and tree Method of prime coat etc. is formed between lipid layer.In addition resin bed is formed also by the resin combination containing such additive Method, the additive is to have the function that to improve the additive (adaptation enhancer) with the adaptation of metal level.It is used as this Resin combination, it is proposed that (such as) contain the mercaptan compounds such as hexadecyl mercaptan or polysulfide polymer as additive Resin combination (with reference to Japanese Unexamined Patent Publication 08-218007 publications and Japanese Unexamined Patent Publication 2011-192514 publications).

In addition, as other resin combinations, it is proposed that contain pentaerythrite fourth class mercaptan compound as additive Resin combination (with reference to Japanese Unexamined Patent Application Publication No. 2014/024767 publication).For the resin combination, when forming resin bed, Above-mentioned additive promotes the dissolution for the metal ingredient for coming from metal level and the diffusion to resin bed, as a result, setting The metallic particles as caused by the precipitation of the metal ingredient of above-mentioned diffusion is formd in lipid layer, the metallic particles improve metal level with The adaptation of resin bed.

[prior art literature]

[patent document]

[patent document 1] Japanese Unexamined Patent Publication 08-218007 publications

[patent document 2] Japanese Unexamined Patent Publication 2011-192514 publications

No. 2014/024767 publication of [patent document 3] Japanese Unexamined Patent Application Publication

The content of the invention

[the problem to be solved in the present invention]

However, for above-mentioned conventional resin combination, even if for the similar additive of structure transitivity, its is closely sealed Property raising effect also have larger difference, unless be actually formed laminate structure, be otherwise difficult to predict formed resin bed with The adaptation of metal level.In addition, the additive types for confirming to have excellent adaptation raising effect are only limited to less species.Its As a result, above-mentioned conventional resin combination, which is difficult to selector, shares the additive on way, and it is difficult to improve formed resin The adaptation of layer and metal level.

The present invention is completed based on the above situation, and it is an object of the invention to provide a kind of resin combination, and its is easy The additive on way is shared in selector, and is easy to improve the adaptation of formed resin bed and metal level.

[means for solving problem]

It is comprising closing for the resin combination involved by the one embodiment of the invention completed of solving the above problems The resin combination of resin and additive, in the resin combination, above-mentioned additive by using AM1 The energy level for the lowest unoccupied molecular orbital that the semiempirical molecular orbital of (Austin Model 1) method is calculated and calculated is below -0.2eV.

In addition, it is for the resin combination involved by the another embodiment of the invention completed of solving the above problems Resin combination comprising synthetic resin and additive, in the resin combination, the reduction potential of above-mentioned additive for- Below more than 1.20V -0.30V.

It is bag for the laminate structure involved by the further embodiment of the invention completed of solving the above problems Include the laminate structure of metal level and the resin bed being layered at least a portion surface of the metal level, above-mentioned resin bed by Resin combination comprising synthetic resin and additive is formed, the semiempirical by using AM1 methods point of above-mentioned additive The energy level for the lowest unoccupied molecular orbital that sub-track is calculated and calculated is below -0.2eV.

It is bag for the laminate structure involved by the further embodiment of the invention completed of solving the above problems Include the laminate structure of metal level and the resin bed being layered at least a portion surface of the metal level, above-mentioned resin bed by Resin combination comprising synthetic resin and additive is formed, and the reduction potential of above-mentioned additive is more than -1.20V -0.30V Below.

For the system of the laminate structure involved by the further embodiment of the invention completed of solving the above problems The method of making is the laminate structure for including metal level and the resin bed being layered at least a portion surface of the metal level Manufacture method, the manufacture method include the step of being coated at least a portion surface of above-mentioned metal level using resin combination, on State resin combination and include synthetic resin and additive, the semiempirical molecular orbital by using AM1 methods of above-mentioned additive The energy level for the lowest unoccupied molecular orbital for calculating and calculating is below -0.2eV.

For the system of the laminate structure involved by the further embodiment of the invention completed of solving the above problems The method of making is the laminate structure for including metal level and the resin bed being layered at least a portion surface of the metal level Manufacture method, the manufacture method include the step of being coated at least a portion surface of above-mentioned metal level using resin combination, on State resin combination and include synthetic resin and additive, the reduction potential of above-mentioned additive is below more than -1.20V -0.30V.

Here, " lowest unoccupied molecular orbital " refers to the minimum track of energy level among the molecular orbit that is not occupied by electronics.

[The effect of invention]

Meet the additive of purposes according to the resin combination of one embodiment of the invention is readily selected, and be easy to Improve the adaptation of formed resin bed and metal level.According to the resin of the laminate structure of another embodiment of the present invention The excellent adhesion of layer and metal level.It can be held according to the manufacture method of the laminate structure of the further embodiment of the present invention The laminate structure of the excellent adhesion of resin bed and metal level is provided easily and reliably.

Brief description of the drawings

[Fig. 1] is the schematic cross sectional views for showing laminate structure according to the third embodiment of the invention.

The conductor and the schematic expanded view of the near interface of resin bed that [Fig. 2] is Fig. 1.

[Fig. 3] is the schematic cross sectional views for showing laminate structure according to the fourth embodiment of the invention.

Embodiment

[explanation of embodiment of the present invention]

Resin combination according to one embodiment of the invention is the resin combination comprising synthetic resin and additive Thing, the energy level of lowest unoccupied molecular orbital that the semiempirical molecular orbital by using AM1 methods of above-mentioned additive is calculated and calculated for- Below 0.2eV.

Synthetic resin and additive are included by the resin combination, and above-mentioned additive by using AM1 methods The semiempirical molecular orbital energy level of lowest unoccupied molecular orbital that calculates and calculate be below -0.2eV, the resin bed and metal formed The excellent adhesion of layer.In addition, for the resin combination, as long as the energy level that lowest unoccupied molecular orbital can be used is below -0.2eV Various additives, in addition the energy level of lowest unoccupied molecular orbital easily can be calculated from the structural formula of additive.Therefore, the resin combination It is readily selected to meet the additive of purposes, and it is easy to improve the adaptation of formed resin bed and metal level.Although pass through The resin combination and be still not clear the reason for the excellent adhesion of the resin bed that is formed and metal level, but can (such as) it is as follows Inferred on ground.That is, if the energy level of lowest unoccupied molecular orbital is negative value, given off energy by receiving electronics, if most The energy level of low-altitude track is on the occasion of then absorbing energy by receiving electronics, the value of the energy level of lowest unoccupied molecular orbital is smaller, it is meant that It is easy to receive electronics and be changed into anion.Therefore, by the energy of the lowest unoccupied molecular orbital of additive contained in the resin combination The value of level is below -0.2eV, golden as caused by the oxidation (cationization) of metal level so as to be promoted when forming resin bed Belong to the dissolution of composition and the diffusion to resin bed, as a result, forming metallic particles in above-mentioned resin bed.Here, the metal Particle has the combination for strengthening the resin bed as caused by the chemical crosslinking of resin and the interface of mitigation resin bed and metal level attached Discontinuities of physical characteristic such as the thermal coefficient of expansion of near resin bed, Young's modulus and other effects.In addition, the metallic particles also has Following effect：Improve the density of resin bed and make even density due to preferentially being separated out in relative low density region；Produce With the high-density aggregation as resin bed and the near interface of metal level caused by the bumps of layer on surface of metal increase same grappling Effect etc..It is understood that by the metallic particles, the resin combination can improve formed resin bed and metal level Adaptation.

Relative to the above-mentioned synthetic resin of 100 mass parts, the content of additive is preferably more than 0.1 mass parts 10 mass parts Below.By this way, by making additive relative to the content of 100 mass parts synthetic resin in above-mentioned particular range, so that The adaptation of formed resin bed and metal level can more be improved.

Above-mentioned additive can be substituted or non-substituted heterocyclic compound.The energy level of the lowest unoccupied molecular orbital of heterocyclic compound It is smaller.Therefore, by making additive be substituted or non-substituted heterocyclic compound, the energy level that can be easy to make lowest unoccupied molecular orbital is upper Scope is stated, as a result, it is possible to further improve the adaptation of formed resin bed and metal level.Here, " heterocyclic compound Thing " refers to the central compound containing the atom beyond carbon atom in the atom for forming ring of cyclic compound.

Above-mentioned heterocyclic compound can have amino, mercapto or combinations thereof.With amino, mercapto or they The energy level of the lowest unoccupied molecular orbital of the compound of combination is smaller.Therefore, by above-mentioned heterocyclic compound have amino, mercapto or it Combination, so as to be easy to further reduce lowest unoccupied molecular orbital energy level, as a result, can further improve formed resin The adaptation of layer and metal level.

Above-mentioned synthetic resin can include the resin with polar group.By this way, tool is included by synthetic resin The resin of polarized group, so as to can further improve the adaptation of formed resin bed and metal level.Here, " there is pole Property group resin " can be main chain on have polar group resin, or on side chain have polar group resin.

The above-mentioned resin with polar group can be polyimides, polyesterimide, polyester, polyamidoimide, benzene Epoxide resin or combinations thereof.By this way, it is polyimides by the resin for making to have polar group, polyester acyl Asia Amine, polyester, polyamidoimide, phenoxy resin or combinations thereof, so as to can further improve formed resin bed with The adaptation of metal level.Here, " polyimides " also polyimide precursor such as including polyamic acid.

Resin combination according to another embodiment of the invention is the resin group comprising synthetic resin and additive Compound, the reduction potential of above-mentioned additive is below more than -1.20V -0.30V.

Synthetic resin and additive are included by the resin combination, and the reduction potential of above-mentioned additive is above-mentioned model Enclose, the resin bed and the excellent adhesion of metal level formed.In addition, for the resin combination, as long as reduction electricity can be used Position is the various additives of above range, and reduction potential can easily be surveyed by using the solution of above-mentioned additive monomer in addition It is fixed.Therefore, the resin combination is readily selected meets the additive of purposes, and is easy to improve formed resin bed and metal The adaptation of layer.Although by make the reduction potential of above-mentioned additive by above range so as to improve the resin bed formed with The reason for adaptation of metal level, is still not clear, but can (such as) inferred as follows.That is, above-mentioned additive The higher situation of reduction potential, i.e. the less situation of absolute value of reduction potential mean to be easy to receive electronics and be changed into it is cloudy from Son.Therefore, by making the reduction potential of the above-mentioned additive in the resin combination for above range and relatively higher (absolute Value is smaller), the situation that the value of the energy level of the lowest unoccupied molecular orbital with making above-mentioned additive is below -0.2eV is identical, can promote by upper State electronic receipt caused by additive.As a result, oxidation (the cation by metal level is promoted when forming resin bed Change) caused by metal ingredient dissolution and diffusion to resin bed, so as to form metallic particles in above-mentioned resin bed.By This is believed that the effect that can play the adaptation that above-mentioned resin bed and metal level are improved as caused by above-mentioned metallic particles Fruit.Here, " reduction potential " is referred to using the solution of additive monomer as sample, working electrode and right is used as using platinum electrode Electrode, and use silver/silver chloride electrode, so as to determine cyclic voltammogram, to be calculated as reference electrode by the cyclic voltammogram The value gone out.

Laminate structure according to the further embodiment of the present invention is to include metal level and be layered in the metal The laminate structure of resin bed at least a portion surface of layer, above-mentioned resin bed is by including the tree of synthetic resin and additive Oil/fat composition and formed, the semiempirical molecular orbital by using AM1 methods of above-mentioned additive calculates and the lowest empty that calculates The energy level of track is below -0.2eV.

Because the resin bed of the laminate structure is formed by the resin combination, thus metal level and resin bed is closely sealed Property is excellent.

The main component of above-mentioned metal level can be copper.By this way, can by making the main component of metal level be copper Further improve the adaptation of metal level and resin bed.Further, since the cost of copper and the balance of electric conductivity are excellent, thus can It is adapted to use metal level as conductor.Here, " main component " refers to the most composition of content, such as content is 50 matter Measure more than % composition.

Laminate structure according to the further embodiment of the present invention is to include metal level and be layered in the metal The laminate structure of resin bed at least a portion surface of layer, above-mentioned resin bed is by including the tree of synthetic resin and additive Oil/fat composition and formed, the reduction potential of above-mentioned additive is below more than -1.20V -0.30V.

Because the resin bed of the laminate structure is formed by above-mentioned resin combination, thus metal level and resin bed is close Conjunction property is excellent.

Manufacture method according to the laminate structure of the further embodiment of the present invention is to include metal level and layer The manufacture method of the laminate structure for the resin bed being stacked at least a portion surface of the metal level, the manufacture method include adopting The step of at least a portion surface of above-mentioned metal level is coated to resin combination, above-mentioned resin combination include synthetic resin and Additive, the energy of the lowest unoccupied molecular orbital calculated by using the semiempirical molecular orbital calculating of AM1 methods of above-mentioned additive Level is below -0.2eV.

The manufacture method of the laminate structure can to easily and reliably provide the excellent adhesion of metal level and resin bed Laminate structure.

Manufacture method according to the laminate structure of the further embodiment of the present invention is to include metal level and layer The manufacture method of the laminate structure for the resin bed being stacked at least a portion surface of the metal level, the manufacture method include adopting The step of at least a portion surface of above-mentioned metal level is coated to resin combination, above-mentioned resin combination include synthetic resin and Additive, the reduction potential of above-mentioned additive is below more than -1.20V -0.30V.

[detailed description of embodiment of the present invention]

Hereinafter, the resin combination according to embodiment of the present invention, stacking will be tied while with reference to appropriate reference Structure body and its manufacture method are described in detail.

[resin combination]

The resin combination includes synthetic resin and additive.The resin combination can also not damage effect of the present invention In the range of include other any conditions.

(synthetic resin)

Synthetic resin is the matrix resin of the resin combination.Can be the tree with polar group as synthetic resin Fat, or the resin without polar group.As the polar group, can include (such as) described later include hetero atom Group etc..One kind can be used alone in synthetic resin, or can combine two or more and use.

As the resin with polar group, can include (such as) polyimides, polyamidoimide, polyester, polyester The epoxy resin such as acid imide, phenoxy resin, melmac, polyvinyl chloride, the copolymer etc. of alkene and polar monomer.

Polyimides is the resin for having imide bond (imide) in intramolecular.Polyimides can by (such as) In the following manner and obtain, i.e. using as the tetrabasic carboxylic acid of acid constituents or its acid anhydrides and as the diamine compound of amine component anti- Answer and polycondensation reaction is carried out in solvent, then the polyimide precursor of gained is carried out dehydration closed-loop by heating etc..

As above-mentioned tetrabasic carboxylic acid or its acid anhydrides, can include (such as) pyromellitic acid anhydride, 3,3 ', 4,4 '-hexichol first Ketone tetracarboxylic dianhydride, benzene -1,2,3,4- tetracarboxylic dianhydrides, naphthalene -2,3,6,7- tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl tetracarboxylic acid Acid dianhydride, 2,2 ", 3,3 "-p- terphenyl tetracarboxylic dianhydride, 2,2- double (carboxy phenyls of 2,3- bis-) propane dianhydride, double (2,3- dicarboxyls Phenyl) ether dianhydride, double (carboxy phenyls of 2,3- bis-)-methane dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, double (2,3- bis- Carboxy phenyl) sulfone dianhydride, 1,1- double (carboxy phenyls of 2,3- bis-) ethane dianhydride, the embedding benzene -3,4,9,10- tetracarboxylic dianhydrides of hexichol, phenanthrene -1, Aromatic tetracarboxylic acid's dianhydride such as 2,7,8- tetracarboxylic dianhydrides；The alicyclic acid anhydrides such as pentamethylene -1,2,3,4- tetracarboxylic dianhydrides；Pyrrole Hete rocyclic derivatives such as piperazine -2,3,5,6- tetracarboxylic dianhydrides etc..As above-mentioned tetrabasic carboxylic acid or its acid anhydrides, preferred tetrabasic carboxylic acid among these Dianhydride, more preferably aromatic tetracarboxylic acid's dianhydride, further preferred pyromellitic acid anhydride.Above-mentioned tetrabasic carboxylic acid or its acid anhydrides can be single Solely using one kind, or can be used in combination.

As above-mentioned diamine compound, can include (such as) 2,2- bis- (p- aminophenyl) -6, it is 6 '-dibenzo azoles, p- Double [4- (4- amino-benzene oxygens) phenyl] propane of phenylenediamine, m- phenylenediamine, 4,4 '-diamino-diphenyl propane, 2,2-, 4,4 '- Diamino diphenyl sulfone, 4,4 '-diaminodiphenyl ether, benzidine, 4,4 "-diaminourea-p- terphenyl, p- double (2- methyl -4- Ammonia amyl group) virtue such as benzene, 1,5- diaminonaphthalenes, 2,4 di amino toluene, meta-xylene -2,5- diamines, m- xylylene diamine Fragrant race's diamines；Aliphatic diamines such as piperazine, methylene diamine, ethylenediamine, tetra-methylenedimine etc..As above-mentioned two amine compounds Thing, these central optimization aromatic diamines, more preferably 4,4 '-diaminodiphenyl ether.Above-mentioned diamine compound can individually make With one kind, or can be used in combination.

In above-mentioned polycondensation reaction above-mentioned tetrabasic carboxylic acid or the lower limit of the mol ratio of its acid anhydrides and diamine compound for (such as) 4.8:5.2.On the other hand, the upper limit of above-mentioned mol ratio for (such as) 5.2:4.8.Above-mentioned mol ratio be less than above-mentioned lower limit or In the case that person exceedes the above-mentioned upper limit, then there is the worry of polyimide molecule amount reduction.

Can be polar solvent, or non-polar solven as above-mentioned reaction dissolvent.As above-mentioned polar solvent, Can include (such as) ketone solvent such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone；Methyl acetate, ethyl acetate, acetic acid The ester solvents such as butyl ester, diethy-aceto oxalate；Diethyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, four The ether solvents such as hydrogen furans；The halogenated hydrocarbon solvents such as dichloromethane, chlorobenzene；The phenol solvent such as cresols, chlorophenol；The tertiary amine solvents such as pyridine；N- N-methyl-2-2-pyrrolidone N, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), tetramethylurea, Hexaethyl Phosphoric triamide, gamma-butyrolacton etc..As above-mentioned non-polar solven, can include (such as) hexane, heptane, benzene, toluene, diformazan The hydrocarbon solvents such as benzene.As above-mentioned reaction dissolvent, more preferably preferred polar solvent among these, METHYLPYRROLIDONE.It is above-mentioned One kind can be used alone in reaction dissolvent, or can be used in combination.

As the method for above-mentioned polycondensation reaction, can include (such as) have by room temperature (less than more than 15 DEG C 25 DEG C) Stirring and (blend step) and (add the step of heated while being stirred the step of mix reaction solution Hot step) method.The lower limit of above-mentioned incorporation time for (such as) 30 minutes.On the other hand, the upper limit of above-mentioned incorporation time is (such as) 2 hours.In addition, the lower limit of above-mentioned heating-up temperature for (such as) 40 DEG C.On the other hand, the upper limit of above-mentioned heating-up temperature is (such as) 90 DEG C.In addition, the lower limit of above-mentioned heat time for (such as) 1 hour.On the other hand, the upper limit of above-mentioned heat time is (such as) 40 hours.In addition, above-mentioned blend step and heating stepses are preferably carried out under the inert atmospheres such as nitrogen atmosphere.

Polyamidoimide is the resin for having amido link (amide groups) and imide bond in intramolecular.Polyamidoimide Can by (such as) tricarboxylic acid anhydride and polyhydric isocyanate compound is reacted to obtain in organic solvent.

Polyesterimide is the resin for having ester bond (ester group) and imide bond in intramolecular.Polyesterimide can pass through (such as) imidodicarboxylic acid of the reaction product as tricarboxylic acid anhydride and diamines is obtained with polyol reaction.As polyester acyl Imines, can include (such as) " EH402-45 " of the big society that refines day.

Polyester is the resin for having ester bond in intramolecular.Polyester can be by making polybasic carboxylic acid be obtained with polyol reaction .It should be noted that polyester can also be (such as) modified poly ester such as alkyd resin.

Epoxy resin is the resin that intramolecular has epoxy radicals.Epoxy resin can by (such as) make bisphenol compound with There is epihalohydrin etc. epoxy radicals and the compound of halogen atom to react to obtain.

Phenoxy resin refers to (poly- in the molecular weight obtained by bisphenol compound and epihalohydrin reaction among epoxy resin It is right) larger material.As the phenoxy resin, can include (such as) bisphenol A-type as obtained by bisphenol-A and epihalohydrin Phenoxy resin, bisphenol S type phenoxy resin etc. as obtained by bisphenol S and epihalohydrin.As phenoxy resin, among these It is preferred that bisphenol A-type phenoxy resin (Li such as East are melted into " YP-50 " of society).

Melmac is the resin using melamine and formaldehyde as raw material.Melmac can be by by trimerization Cyanamide and formaldehyde is condensed in the basic conditions, is obtained again as the further polycondensation of melamine methylol by obtained by such as heating .

Polyvinyl chloride is the resin that intramolecular has chlorine atom.Polyvinyl chloride can be obtained by the addition polymerization of vinyl chloride .

As alkene and the copolymer of polar monomer, can include (such as) alkene and vinegar of ethene, propylene, 1- butylene etc. Vinyl acetate, (methyl) acrylic acid, the copolymer etc. of ethyl acrylate isopolarity monomer.

As the resin without polar group, can include (such as) polyolefin etc..Polyolefin is to contain alkene conduct The resin of monomer.As polyolefin, can include (such as) polyethylene (Alathon), polypropylene (Noblen), poly- Butene-1 (1- chevrons), ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene -4-methyl-1-pentene copolymerization Thing, ethene -1- hexene copolymers, ethylene-l-octane copolymer, propene-1-butene copolymer, propylene-ethylene -1- butenes Thing, propylene -4 methyl 1 pentene copolymer etc..

As synthetic resin, preferably there is the resin of polar group, more preferably polyimides, polyester, polyester among these Acid imide, polyamidoimide, phenoxy resin or combinations thereof, further preferred polyesterimide and phenoxy resin Hybrid resin and polyimides.If synthetic resin is the hybrid resin of polyesterimide and phenoxy resin, polyester acyl is sub- The lower limit of the mass ratio of amine and phenoxy resin for (such as) 10:90, preferably 30:70, more preferably 60:40, it is further excellent Elect 70 as:30.On the other hand, the upper limit of above-mentioned ratio for (such as) 99:1, preferably 90:10, more preferably 80:20.Upper Ratio is stated less than above-mentioned lower limit or above-mentioned ratio more than in the case of the above-mentioned upper limit, then has and is difficult to improve formed resin Layer and the worry of the adaptation of metal level.

The lower limit of the content of synthetic resin in the solid constituent of the resin combination is preferably 80 weight %, more preferably 90 mass %, more preferably 95 mass %, particularly preferably 98 mass %.On the other hand, the solid of the resin combination The upper limit of the content of synthetic resin in composition is preferably 99.9 mass %, more preferably 99.5 mass %.In synthetic resin In the case that content is less than above-mentioned lower limit, then mechanical strength for the resin bed that can have been formed etc. becomes insufficient worry.Phase Instead, in the case where the content of synthetic resin exceedes the above-mentioned upper limit, then having the content of other compositions such as additive becomes not It is sufficiently worried.

(additive)

Additive improves the adaptation of the resin bed formed by the resin combination and metal level, and additive passes through The energy level for the lowest unoccupied molecular orbital for having used the semiempirical molecular orbital calculating of AM1 methods and having calculated is below -0.2eV.Additive can So that one kind is used alone, or can be used in combination.

The energy level for the lowest unoccupied molecular orbital for calculating and calculating for the semiempirical molecular orbital by using AM1 methods, it is logical Cross used Molecular Orbital Calculation software (such as MOPAC6 built in " Winmostar " of " Network ロスア PVC リティ societies ") with The calculating of electronic state on the basis of vacuum level and try to achieve.It should be noted that due to the relation of computational accuracy, above-mentioned energy level May not be consistent with measured value, although also there is the situation that symbol is changed into positive sign, value is smaller, then mean more to be easy to be changed into it is cloudy from Son, that is to say, that other molecules of metal level etc. are more easy to be cationized.

The energy level for the lowest unoccupied molecular orbital that the semiempirical molecular orbital by using AM1 methods of additive is calculated and calculated Lower limit is preferably -2.0eV, more preferably -1.7eV, more preferably -1.5eV.On the other hand, above-mentioned lowest unoccupied molecular orbital The upper limit of energy level is -0.2eV, is preferably -0.5eV, more preferably -0.6eV, more preferably -1.0eV, particularly preferably - 1.2eV.In the case where the energy level of above-mentioned lowest unoccupied molecular orbital is less than above-mentioned lower limit, meet that the species of the additive of characteristic is limited System, meeting the selection of the additive of purposes may become difficult.On the contrary, the energy level in above-mentioned lowest unoccupied molecular orbital exceedes on above-mentioned In the case of limit, then the dissolution for having the metal ingredient for coming from metal level when forming resin bed becomes insufficient worry.

The energy level for the highest occupied orbital that the semiempirical molecular orbital by using AM1 methods of additive is calculated and calculated Lower limit be preferably -10eV, more preferably -9.6eV, more preferably -9.5eV.On the other hand, above-mentioned highest occupied orbital Energy level the upper limit be preferably -8.0eV, more preferably -8.5eV, more preferably -8.6eV.In above-mentioned highest occupied orbital Energy level be less than above-mentioned lower limit in the case of, then the insufficient worry of the resin bed and the adaptation of metal level that have been formed.Phase Instead, above-mentioned highest occupied orbital energy level exceed the above-mentioned upper limit in the case of, meet characteristic additive species by Limitation, meeting the selection of the additive of purposes may become difficult.Here, " highest occupied orbital " is referred to occupied by electronics Molecular orbit among energy level highest track.The value of " energy level of highest occupied orbital " is smaller, then it represents that is more difficult to turn into sun Ion.

The semiempirical molecular orbital by using AM1 methods of additive calculate and the lowest unoccupied molecular orbital energy level that calculates with most The poor lower limit of high occupied orbital energy level is preferably 7.2eV, more preferably 7.8eV.On the other hand, the energy of above-mentioned lowest unoccupied molecular orbital Level and the poor upper limit of the energy level of highest occupied orbital are preferably 9.0eV, more preferably 8.9eV.In above-mentioned lowest unoccupied molecular orbital In the case that the difference of energy level and the energy level of highest occupied orbital is less than above-mentioned lower limit, meet that the species of the additive of characteristic is limited System, meeting the selection of the additive of purposes may become difficult.On the contrary, the energy level and highest in above-mentioned lowest unoccupied molecular orbital are occupied In the case that the difference of the energy level of track exceedes the above-mentioned upper limit, then the resin bed and the adaptation of metal level formed is insufficient It is worried.Here, " energy level of lowest unoccupied molecular orbital and the energy level of highest occupied orbital " refers to that the energy level of lowest unoccupied molecular orbital subtracts most Value obtained by the energy level of high occupied orbital.

The lower limit of the reduction potential of above-mentioned additive is preferably -1.20V, more preferably -1.10V.On the other hand, it is above-mentioned to go back The upper limit of former current potential is preferably -0.30V, more preferably -0.40V.In the case where above-mentioned reduction potential is less than above-mentioned lower limit, then The dissolution for having the metal ingredient for coming from metal level when forming resin bed becomes insufficient worry.On the contrary, gone back above-mentioned In the case that former current potential exceedes the above-mentioned upper limit, then meet that the species of the additive of characteristic is restricted, meet the additive of purposes Selection may become difficult, or the stability of additive itself may be deteriorated according to occasion.

Above-mentioned additive generally comprises hetero atom.As the hetero atom contained by the additive, can include (such as) nitrogen is former Son, sulphur atom, oxygen atom, bromine atoms, combinations thereof etc., among these preferably nitrogen-atoms, sulphur atom, oxygen atom or they Combination, more preferably nitrogen-atoms, sulphur atom or combinations thereof.Here, " hetero atom " refer to except carbon atom and hydrogen atom with Outer atom.

Additive include it is heteroatomic in the case of, the lower limit of heteroatomic number is preferably 3 contained by additive, more preferably For 4.On the other hand, there is no particular limitation for the upper limit of heteroatomic number contained by additive, can be (such as) 8.Adding In the case that heteroatomic number contained by agent is less than above-mentioned lower limit, then the energy level for being difficult to make lowest unoccupied molecular orbital is in above-mentioned particular range It is interior.

As comprising heteroatomic additive, can include (such as) there is the compound comprising heteroatomic group, take Generation or non-substituted heterocyclic compound etc..It is used as heterocyclic compound or monocyclic heterocyclic compound or polycyclic Heterocyclic compound, it is preferred that being monocyclic heterocyclic compound.

As comprising heteroatomic group, can include (such as)

The group of the nitrogen atom of amino, cyano group, nitro, cyano group, amide groups, imide, NCO etc.；

The group of the sulfur atom-containing of mercapto, thioether group, sulfo group etc.；

The group containing oxygen atom of hydroxyl, ether, ester group, carboxyl, carbonyl, epoxy radicals etc.；

The halogen atoms such as bromine atoms；

Group of the halogen atom-containings such as haloalkyl etc..Among these, nitrogen atom is more preferably containing heteroatomic group Group, sulfur atom-containing group and group containing oxygen atom, more preferably amino, mercapto, cyano group, nitro or it Combination, particularly preferably amino, mercapto or combinations thereof.

As non-substituted heterocyclic compound, can include (such as)

Aza-cyclopentane (azolidine), piperidine (azinane), imidazolidine, pyrroles, pyridine, imidazoline, The nitrogen-containing heterocycle compounds such as imidazoles, pyrazoles, triazole, azophenlyene；

The sulfur heterocyclic compounds such as tiacyclopentane (thiolane), thia hexamethylene (thiane), thiophene, thiazole；

The Oxygenic heterocyclic compounds such as tetrahydrofuran (oxolane), oxinane (oxane), furans, pyrans；

Thiazole, thiadiazoles, oxazoles, benzothiazole, Fen Evil thiophenes (phenoxathiin) etc. include two or more hetero atoms Heterocyclic compound etc..Among these, as non-substituted heterocyclic compound, preferably comprise nitrogen-atoms, sulphur atom or they The heterocyclic compound of combination, more preferably comprising at least two miscellaneous in the group being made up of nitrogen-atoms and sulphur atom The heterocyclic compound of atom, further preferably comprising at least two in the group being made up of nitrogen-atoms and sulphur atom Heteroatomic unsaturated heterocyclic compound, particularly preferably thiadiazoles, imidazoles and thiazole.

As substituted heterocyclic compound, can include (such as) above-mentioned non-substituted heterocyclic compound substituted by substituent Compound obtained by part or all of hydrogen atom possessed by thing etc..As above-mentioned substituent, can include (such as) bag Containing above-mentioned heteroatomic group, alkyl etc..As alkyl, can include (such as) methyl, ethyl, propyl group, butyl etc., these are worked as In preferred methyl.

As substituted heterocyclic compound, can include (such as) the 5- methyl isophthalic acids that are represented by following formula (A1), 3,4- thiophenes two Azoles -2- mercaptan, the 2,5- dimercapto -1,3,4- thiadiazoles represented by following formula (A2), the 2- amino -5- mercaptos represented by following formula (A3) Base -1,3,4- thiadiazoles, the 2- amino -1,3,4- thiadiazoles represented by following formula (A4), 2- amino -4 represented by following formula (A5), 5- dicyano -1H- imidazoles, the 2- amino -5- nitrothiazoles represented by following formula (A6) etc..

[chemical formula 1]

As additive, preferably substituted or non-substituted heterocyclic compound, more preferably with amino, mercapto or it Combination heterocyclic compound, more preferably 5- methyl isophthalic acids, 3,4- thiadiazoles -2- mercaptan, 2,5- dimercaptos -1,3,4- Thiadiazoles, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, 2- amino -1,3,4- thiadiazoles, 2- amino -4,5- dicyano -1H- miaows Azoles and 2- amino -5- nitrothiazoles.

The lower limit of the molecular weight of additive is preferably 50, more preferably 80, more preferably 90.On the other hand, add The upper limit of the molecular weight of agent is preferably 2,000, more preferably 1,000, more preferably 500, particularly preferably 200.Adding Add the molecular weight of the agent sorrow insufficient less than the resin bed and the adaptation of metal level in the case of above-mentioned lower limit, then formed Consider.On the contrary, in the case where the molecular weight of additive exceedes the above-mentioned upper limit, then there is additive in the resin bed formed Scattered insufficient worry.

Relative to the synthetic resin of 100 mass parts, the lower limit of the content of additive is preferably 0.1 matter in the resin combination Measure part, more preferably more preferably 0.5 mass parts, 0.7 mass parts.On the other hand, relative to the synthesis tree of 100 mass parts Fat, the upper limit of the content of additive is preferably 10 mass parts in the resin combination, more preferably 3 mass parts, further preferably For 1.5 mass parts.It is close less than the resin bed and metal level in the case of above-mentioned lower limit, then formed in the content of additive The insufficient worry of conjunction property.On the contrary, additive content exceed the above-mentioned upper limit in the case of, then have the resin combination with The worry that the adaptation of metal level declines on the contrary, or the worry for thering is manufacturing cost to rise.

[other any conditions]

As other any conditions, can include (such as) solvent, curing agent, pigment, dyestuff, inorganic filler, organic fill out Material, lubricant, fire retardant, flame retardant, antioxidant, levelling agent etc..

Solvent improves the coating of the resin combination.As solvent, if its for can dissolve or scattered synthetic resin, Additive and the as needed solvent of other any conditions that contains, there is no particular limitation, can include (such as) Reaction dissolvent illustrated in the polymerisation of above-mentioned polyimide precursor etc..Among these, solvent is preferably N- methyl -2- Pyrrolidones and cresols.It should be noted that in the reaction dissolvent being dissolved or dispersed in synthetic resin used in polymerisation In the case of, solvent that can also be using above-mentioned reaction dissolvent as the resin combination.One kind can be used alone in solvent, or It can be used in combination.

In the case where the resin combination includes solvent, the lower limit of the solid component concentration of the resin combination is preferably 5 mass %, more preferably 10 mass %.In addition, the upper limit of the solid component concentration of the resin combination is preferably 80 mass %, More preferably 60 mass %.In the case where the solid component concentration of the resin combination is less than above-mentioned lower limit, then has and be difficult to shape The worry of resin layer.On the other hand, in the case where the solid component concentration of the resin combination exceedes the above-mentioned upper limit, then have The worry that coating declines.

Curing agent makes and the resin bed formed to solidify by the resin combination.As curing agent, can be set according to synthesis Species of fat etc. and suitably selected, and can include (such as) isocyanates system curing agent, melamine compound, silicon Alkane coupling agent, titanate coupling agent etc..One kind can be used alone in curing agent, or can be used in combination.

As isocyanates system curing agent, can include (such as)

The aromatic diisocyanates such as toluene di-isocyanate(TDI) (TDI), PPDI, naphthalene diisocyanate；

Hexamethylene diisocyanate (HDI), 2,2,4- trimethylhexane diisocyanates, lysine diisocyanate etc. Carbon number is 3 to 12 aliphatic diisocyanate；

1,4- cyclohexane diisocyanates (CDI), IPDI (IPDI), 4,4 '-dicyclohexyl methyl hydride Diisocyanate (hydrogenation MDI), methylcyclohexane diisocyanate, isopropylidene dicyclohexyl -4,4 '-diisocyanate, 1, 3- bis- (isocyanatomethyl) hexamethylene (hydrogenation XDI), double (isocyanatomethyl)-two rings of hydrogenation TDI, 2,5- The ester ring type two that the carbon numbers such as double (isocyanatomethyl)-two ring [2.2.1] heptane of [2.2.1] heptane, 2,6- are 5 to 18 Isocyanates；

Xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI) etc. have aromatic rings Aliphatic diisocyanate；

Isocyanic acid will be blocked obtained by isocyanate-terminated contained by these diisocyanate cpds using blocking agent Ester etc..

As melamine compound, can include (such as) methyl melamine, butylated melamines, methylolation Melamine, butylated melamine etc..Melamine compound is applicable to such situation, i.e. the resin combination bag It is contained in the synthetic resin for the group that there is hydroxyl, carboxyl, epoxy radicals etc. can be reacted with amine for end.

In addition, in the case where the resin combination includes the synthetic resin with hydroxyl, metatitanic acid 4 third can also be used The Titanium alkoxides such as ester, tetraisopropyl titanate, tetramethoxy titanate ester, butyl titanate, four own ester of metatitanic acid are as curing agent.

In the case where the resin combination includes curing agent, relative to the synthetic resin of 100 mass parts, curing agent contains The lower limit of amount for (such as) 1 mass parts.On the other hand, relative to the synthetic resin of 100 mass parts, the upper limit of the content of curing agent For (such as) 20 mass parts.

[manufacture method of resin combination]

As the manufacture method of the resin combination, there is no particular limitation, and can include (such as) possess and will synthesize The step of resin, additive and other contained as needed any conditions mixing (blend step) and by the mixture Method of the step of stirring (whipping step) etc..As the lower limit of the mixing time in above-mentioned whipping step, do not limit particularly It is fixed, and for (such as) 30 minutes.On the other hand, the upper limit as mixing time, there is no particular limitation, and for (such as) 2 small When.

As the method that synthetic resin etc. is added additives in above-mentioned blend step, there is no particular limitation, can Think the method that additive is directly appended to synthetic resin etc., or add the additive for being dissolved in organic solvent in advance It is added to the method for synthetic resin etc..Here, in order that the resin bed and the adaptation of metal level that are formed by the resin combination have Imitate and each position is equably improved, preferably equably mix synthetic resin and additive in the manufacture of the resin combination. From this viewpoint, as the adding method of additive, will preferably be dissolved in advance good with synthetic resin compatibility The method that the additive of organic solvent is added to synthetic resin etc..In addition, in synthetic resin dissolving in the case of organic solvents, As the organic solvent of advance solubilising additive, it is preferably the organic solvent identical solvent with dissolving above-mentioned synthetic resin. In the case where additive is dissolved into organic solvent in advance, as the lower limit of the concentration of above-mentioned additive, do not limit particularly It is fixed, preferably 0.1 mass %, more preferably 1 mass %.On the other hand, as above-mentioned additive concentration the upper limit, without spy Other restriction, and preferably 50 mass %, more preferably 20 mass %.

[advantage]

The resin combination can be readily selected the additive for meeting purposes, and the resin combination can be easily Improve the adaptation of formed resin bed and metal level.Therefore, the resin combination can be suitable for varnish, adhesive, bottom Paint coating etc..

[resin combination]

Synthetic resin and additive, the reduction potential of above-mentioned additive are included according to the resin combination of the second embodiment For below more than -1.20V -0.30V.The resin combination can be similar with the resin combination of the first embodiment, difference It is in using the material of reduction potential within the above range as additive.It should be noted that above-mentioned lowest unoccupied molecular orbital Energy level is low and reduction potential high (absolute value is small) is the index for representing to be easy to receive electronics to be reduced jointly.On however, The energy level for stating lowest unoccupied molecular orbital is value of the molecule isolated in vacuum under absolute zero, and therefore, it is with representing molten in solution The precondition of the reduction potential of the value of agent chemoattractant molecule aggregation at room temperature is different, additionally due to the relation of computational accuracy, its May not be consistent with measured value.Therefore, the energy level of above-mentioned lowest unoccupied molecular orbital and reduction potential are not perfectly correlated.

The lower limit of the reduction potential of above-mentioned additive is -1.20V, is preferably -1.10V.On the other hand, above-mentioned reduction potential The upper limit be -0.30V, be preferably -0.40V.In the case where above-mentioned reduction potential is less than above-mentioned lower limit, then has and forming resin The dissolution for the metal ingredient for coming from metal level during layer becomes insufficient worry.On the contrary, exceed in above-mentioned reduction potential upper In the case of stating the upper limit, then meet that the species of the additive of characteristic is restricted, meeting the selection of the additive of purposes may become Must be difficult, or the stability of additive itself may be deteriorated according to occasion.

The energy level for the lowest unoccupied molecular orbital that the semiempirical molecular orbital by using AM1 methods of additive is calculated and calculated Lower limit is preferably -2.0eV, more preferably -1.7eV, more preferably -1.5eV.On the other hand, above-mentioned lowest unoccupied molecular orbital The upper limit of energy level is preferably -0.2eV, more preferably -0.5eV, more preferably -0.6eV, particularly preferably -1.0eV, more Particularly preferably -1.2eV.In the case where the energy level of above-mentioned lowest unoccupied molecular orbital is less than above-mentioned lower limit, then meet the addition of characteristic The species of agent is restricted, and meeting the selection of the additive of purposes may become difficult.On the contrary, in above-mentioned lowest unoccupied molecular orbital In the case that energy level exceedes the above-mentioned upper limit, then the dissolution for having the metal ingredient for coming from metal level when forming resin bed becomes not It is sufficiently worried.

[advantage]

The resin combination can be readily selected the additive for meeting purposes, and the resin combination can be easily Improve the adaptation of resin bed that it is formed and metal level.Therefore, the resin combination can be suitable for varnish, adhesive, Primer base etc..

<3rd embodiment>

[laminate structure]

Fig. 1 laminate structure 1 includes the conductor 2 as metal level and the resin bed 3 on the coated surface of conductor 2. That is the laminate structure 1 includes metal level and the resin bed 3 being directly layered on the layer on surface of metal.The stacking knot Structure body 1 may be adapted to be used as insulated electric conductor.

(conductor)

As the main component of conductor 2, copper, iron, aluminium, silver, gold and their alloy etc. can be enumerated, these are central excellent Select copper.By the way that copper to be used as to the main component of conductor 2, can improve conductor 2 and resin bed 3 adaptation and cost with leading Electrical balance.

There is no particular limitation for the cross sectional shape of conductor 2, can include (such as) circular, square, rectangle etc..In addition, lead There is no particular limitation for the cross-sectional sizes of body 2, makes the cross sectional shape of conductor 2 in the case of circular, the lower limit of average diameter For (such as) 0.2mm.On the other hand, the upper limit of average diameter for (such as) 3.0mm.In addition, it is in the cross sectional shape for making conductor 2 In the case of square, the lower limit of the average length on one side for (such as) 0.05mm.On the other hand, the upper limit of the average length on one side For (such as) 5.0mm.

As shown in Fig. 2 conductor 2 has the usually oxide layer 2a of face side and than more in the inner part non-oxygen of oxide layer 2 Change layer 2b.Oxide layer 2a is formed by the oxide of the metal of the main component as conductor 2.Oxide layer 2a average thickness There is no particular limitation for lower limit, its for (such as) 1nm.On the other hand, the upper limit of oxide layer 2a average thickness for (such as) 100nm。

(resin bed)

Resin bed 3 is formed by the resin combination.For the resin combination, have been carried out illustrating due to above-mentioned, because And the description thereof will be omitted herein.Metallic particles 4 is dispersed with the near interface of resin bed 3 and conductor 2.Resin bed 3 substantially contains The region of metallic particles 4 is that the average distance apart from the surface of conductor 2 is interface adjacent domain 5 within 800nm.Resin bed 3 is made Played a role for the insulating barrier and/or protective layer of conductor 2.Resin bed 3 can be individual layer or multilayer.Resin bed 3 There is no particular limitation for the lower limit of average thickness, its for (such as) 20 μm.On the other hand, the upper limit of the average thickness of resin bed 3 There is no particular limitation, its for (such as) 100 μm.As the resin combination, the tree according to the first embodiment can be used Oil/fat composition and according to both resin combinations of the second embodiment.

(metallic particles)

Metallic particles 4 is dispersed in resin bed 3.Metallic particles 4 is by from the dissolution of conductor 2 and being diffused into the gold of resin bed 3 The particle for belonging to the precipitation of composition and being formed.Therefore, the metal of the main component of the main component of metallic particles 4 and conductor 2 or its Oxide is substantially the same.It should be noted that as above-mentioned metal ingredient, it can be the material from oxide layer 2a dissolutions, It can be the material from oxidation free layer 2b dissolutions.In addition, the surface of metallic particles 4 can also be oxidized.

There is no particular limitation for the lower limit of the average grain diameter of metallic particles 4, and it is preferably 1nm, more preferably 5nm.It is another Aspect, there is no particular limitation for the upper limit of the average grain diameter of metallic particles 4, and it is preferably 50nm, more preferably 30nm.By making The average grain diameter of metallic particles 4 within the above range, can further improve the adaptation of conductor 2 and resin bed 3.If metal The average grain diameter of grain 4 is less than above-mentioned lower limit, then chemical crosslinking of resin and other effects can become not as caused by above-mentioned metallic particles 4 Fully, thus the worry that reduces of the adaptation that has conductor 2 and resin bed 3.On the contrary, if the average grain diameter of metallic particles 4 exceedes The above-mentioned upper limit, then there is the worry reduced with the adaptation of conductor 2 because the inequality of the density of resin bed 3 homogenizes etc..Need Bright, " average grain diameter " of metallic particles 4 is the value that determines by the following method.That is, to expose conductor 2 and resin bed 3 Mode cut the laminate structure 1, after cut surface is mechanically polished, carry out ion beam processing.Use scanning electron microscopy Mirror (such as) above-mentioned cut surface is taken pictures under 50,000 times, obtain the image of rectangular area, the rectangular area has In a thickness direction apart from resin bed 3 and the interface 800nm of conductor 2 side, and vertical with above-mentioned side 2 among resin bed 3, 290nm side.The particle of any more than 10 is taken in the images, using the average value of their own most long width as metal The average grain diameter of particle 4.It should be noted that smaller due to the area of above-mentioned cut surface and the feelings of above-mentioned zone can not be ensured Under condition, then have what is be in contact with the interface of resin bed 3 and conductor 2 using the image of such rectangular area, the rectangular area Side, and area is maximum.

The content of metallic particles 4 is preferably to become bigger closer to the interface of resin bed 3 and conductor 2, more lean in resin bed 3 Nearly outer surface becomes smaller mode and enters line tilt in a thickness direction.By this way, metallic particles in resin bed 3 is passed through 4 content enters line tilt in a thickness direction in a manner of becoming bigger closer to the interface of resin bed 3 and conductor 2, can be with The adaptation of conductor 2 and resin bed 3 is further improved, and becomes prone to play the spy needed for insulating properties, flexibility (adaptability) of operation etc. Property.Furthermore it is possible to further improve resin bed 3 caused by above-mentioned metallic particles 4 and the resin bed 3 of the near interface of conductor 2 The discontinuity alleviation effects of the physical characteristics such as thermal coefficient of expansion, Young's modulus.

Relative to the content of whole metallic particles 4 contained by resin bed 3, metallic particles 4 in interface adjacent domain 5 Content lower limit is preferably 90 volume %, more preferably 99 volume %.If the content of the metallic particles 4 in interface adjacent domain 5 is small In above-mentioned lower limit, then the adaptation of conductor 2 and resin bed 3 becomes insufficient, and resin bed 3 is distributed to additionally, due to metallic particles 4 Proximity, thus have the worry of the reductions such as insulating properties, flexibility (adaptability) of operation.It should be noted that metallic particles 4 3/2 is asked again after the area ratio/occupancy ratio of metallic particles 4 in the cross-sectional image that " content " is shot for measure by SEM The value of power.

The lower limit of the content of metallic particles 4 in interface adjacent domain 5 is preferably 0.005 volume %, and more preferably 0.01 Volume %.On the other hand, the upper limit of the content of the metallic particles 4 in interface adjacent domain 5 is preferably 1 volume %, more preferably 0.2 volume %.By making the content of the metallic particles 4 in interface adjacent domain 5 further to improve conductor in above range 2 and the adaptation of resin bed 3.If the content of the metallic particles 4 in interface adjacent domain 5 is less than above-mentioned lower limit, by above-mentioned gold Chemical crosslinking of resin and other effects becomes insufficient caused by metal particles 4, the sorrow that the adaptation for having conductor 2 and resin bed 3 reduces Consider.On the contrary, if the content of the metallic particles 4 in interface adjacent domain 5 exceedes the above-mentioned upper limit, because the inequality of density homogenizes Or resin component reduction and worry that the adaptation that has conductor 2 and resin bed 3 reduces.

[manufacture method of laminate structure]

The manufacture method of Fig. 1 laminate structure 1 is used as the conductor 2 of metal level including the use of resin combination to be coated to The step of surface (coated step).The resin combination can use according to the resin combination of the first embodiment and according to Both resin combinations of second embodiment.

(coated step)

In this step, using resin combination with the surface of coated conductor 2.As using the resin combination to be coated to The method on the surface of conductor 2, can include (such as) there is the table that the resin combination is coated on to the conductor 2 as metal level The step of face (application step) and method of (heating stepses) the etc. the step of resin combination being coated with is heated.

(application step)

In this step, resin combination is coated on to the surface of conductor 2.Conductor is coated on as by the resin combination The method on 2 surface, can include (such as) resin combination is turned into varnish shape, then by including storing the clear of the varnish The apparatus for coating of paint bath and coating die is come method for being coated etc..According to this method, by the way that conductor 2 is immersed in into varnish So that varnish is attached to the surface of conductor 2 in groove, coating die is then passed to, so that varnish coating is substantially homogeneous Thickness.

It should be noted that conductor 2 can also be surface-treated before this step.Side as the surface treatment Method, can include (such as) by the surface treating agent coats containing above-mentioned additive and solvent available for the resin combination In the surface of conductor 2 and then the method being dried etc..By this way, by using above-mentioned surface conditioning agent so as to right Conductor 2 is surface-treated, and can more reliably be improved by the closely sealed of the resin bed 3 that the resin combination is formed and conductor 2 Property.Can make the content of the above-mentioned additive in above-mentioned surface conditioning agent for (such as) more than 0.1 mass % 10 is below mass %.

(heating stepses)

In this step, the resin combination being coated with is heated.By the heating, promote conductor 2 it is main into The dissolution of the metal divided and the diffusion to coating layer (resin bed 3), are formed by upper as a result, promoting in resin bed 3 The metallic particles stated the precipitation of the metal ingredient of diffusion and come.If in addition, the resin combination includes polyimide precursor, Polyimides is formd by the dehydration closed-loop of the polyimide precursor.

As heating means, can include (such as) heating furnace of long tubular is set on the direct of travel of conductor 2, then Method of indirectly heat conductor 2 etc..As the method for indirectly heat, there is no particular limitation, can include (such as) hot blast adds The known method such as heat, infrared heating, high-frequency heating.The lower limit of above-mentioned heating-up temperature is preferably 200 DEG C.The opposing party Face, the upper limit of above-mentioned heating-up temperature is preferably 400 DEG C.If above-mentioned heating-up temperature is less than above-mentioned lower limit, when having due to heating Between increase and cause productivity reduce worry.On the contrary, if above-mentioned heating-up temperature exceedes the above-mentioned upper limit, have conductor 2 or The worry of the reductions such as the mechanical strength of resin bed 3.The lower limit of above-mentioned heat time is preferably 5 minutes.On the other hand, above-mentioned heating The upper limit of time is preferably 1 hour.If the above-mentioned heat time is less than above-mentioned lower limit, the formation for having resin bed 3 is insufficient It is worried.On the contrary, if the above-mentioned heat time exceedes the above-mentioned upper limit, insulation characterisitic, resin bed 3 and the conductor 2 of resin bed 3 are had Adaptation or productivity reduce worry.

In the manufacture method of the laminate structure 1, coated step is generally repeated several times.Thus, by be repeated several times by Step is covered, so as to easily make resin bed 3 reach expectation thickness., can be according to repetition in the case where being repeated several times coated step Number be adjusted so that the aperture of coating die becomes larger.In addition, when obtaining certain thickness resin bed 3, Resin component contained in varnish can be changed, so as to form the resin bed 3 being made up of the different multilayer of main component.Need It is bright, as the lower limit of the number of repetition of each layer of coated step, can properly select, its for (such as) 2 times.The opposing party Face, as the upper limit of above-mentioned number of repetition, can properly select, its for (such as) 20 times.

In the laminate structure 1, the excellent adhesion of conductor 2 and resin bed 3.In addition, the manufacture of the laminate structure 1 Method can to easily and reliably provide the laminate structure 1.

<4th embodiment>

[laminate structure]

Fig. 3 laminate structure 11 includes the conductive pattern 6 as metal level, is layered in the one side of the conductive pattern 6 Basement membrane 7, be directly layered in the another aspect of conductive pattern 6 as the resin bed 13 of bond layer, across resin bed 13 And it is layered in the cover layer 8 in the another aspect of conductive pattern 6.That is, the laminate structure 11 include metal level and The resin bed 13 being directly layered on the layer on surface of metal.The laminate structure 11 can be suitable for use as flexible printed circuit board etc..

(conductive pattern)

Conductive pattern 6 constitutes the loop of the laminate structure 11.As the main component of conductive pattern 6, can include With the main component identical material of above-mentioned conductor 2 etc..Oxide layer and ratio oxidation of the conductive pattern 6 generally with superficial layer The oxidation free layer of layer more in the inner part.For the oxide layer and oxidation free layer, due to their oxygen with Fig. 2 laminate structure 1 It is identical to change layer 2a and oxidation free layer 2b, thus the description thereof will be omitted herein.

The lower limit of the average thickness of conductive pattern 6 for (such as) 2 μm.On the other hand, the average thickness of conductive pattern 6 is upper Be limited to (such as) 100 μm.If the average thickness of conductive pattern 6 is less than above-mentioned lower limit, the intensity and conduction of conductive pattern 6 are had Property reduce worry.On the contrary, if the average thickness of conductive pattern 6 exceedes the above-mentioned upper limit, the laminate structure 11 is had Average thickness becomes worry too much.

(basement membrane and cover layer)

As basement membrane 7 and cover layer 8, there is no particular limitation, can use known dielectric film.Basement membrane 7 and cover The lower limit of the average thickness of epiphragma 8 for (such as) 3 μm.On the other hand, the upper limit of above-mentioned average thickness for (such as) 200 μm.

(resin bed)

Resin bed 13 plays a role as the bond layer for being bonded conductive pattern 6 and cover layer 8.Resin bed 13 is by the tree Oil/fat composition and formed.In resin bed 13 metallic particles 4 is dispersed with the near interface of conductive pattern 6.For the resin group Compound and metallic particles 4, due to being illustrated above-mentioned, thus the description thereof will be omitted herein.The resin combination can use According to the resin combination of the first embodiment and according to both resin combinations of the second embodiment.

The lower limit of the average thickness of resin bed 13 is preferably 5 μm, more preferably 10 μm.On the other hand, resin bed 13 is flat The upper limit of equal thickness is preferably 100 μm, more preferably 75 μm.If the average thickness of resin bed 13 is less than above-mentioned lower limit, have The worry insufficient with the adhesive strength of conductive pattern 6 of cover layer 8.On the contrary, if the average thickness of resin bed 13 is more than above-mentioned The upper limit, then when manufacturing the laminate structure 11, the residual solvent in using periods such as reflow ovens welding due to resin bed 13 Gasification allows to that space can be formed, worried caused by peel strength decline or the poor grade of outward appearance so as to have.

[manufacture method of laminate structure]

The manufacture method of Fig. 3 laminate structure 11 is including the use of resin combination to be coated to the conductive pattern as metal level The step of surface of case 6 (coated step).The resin combination can use according to the resin combination of the first embodiment with And according to both resin combinations of the second embodiment.

(coated step)

In this step, using resin combination to be coated to the surface of conductive pattern 6.As using the resin combination with The method on the surface of coated conductive pattern 6, can include (such as) there is in the one side of conductive pattern 6 stacking by the resin group Compound and (Stacking steps) and (the heating the step of resin combination being laminated is heated the step of resin bed 13 formed Step) method etc..

(Stacking steps)

In this step, will be layered in by the resin combination and the resin bed 13 formed in the one side of conductive pattern 6. As the method being layered in resin bed 13 in the one side of conductive pattern 6, can include (such as) as method, this method bag Include the first cascade structure and bag for preparing the basement membrane 7 for including conductive pattern 6 and being layered in the one side of the conductive pattern 6 Include resin bed 13 and the step of the second laminate structure of the cover layer 8 that is layered in the one side of the resin bed 13；And pass through The conductive pattern 6 of first cascade structure is set to be arranged oppositely and be laminated with the phase of resin bed 13 of the second laminate structure, from And on conductive pattern 6 directly be laminated resin bed 13 the step of.First cascade structure can by (such as) on the upper strata of basement membrane 7 Folded metal film, the method that the metal film is etched is obtained again.In addition, the second laminate structure can by (such as) Method that the resin combination is coated with cover layer 8 etc. and obtain.It should be noted that as in this step in conductive pattern The method of resin bed 13 is laminated on 6, is not limited to the above method, or (such as) stack gradually basement membrane 7, conductive pattern 6, Method of resin bed 13 and cover layer 8 etc..

(heating stepses)

In this step, the resin combination being layered in the one side of conductive pattern 6 is heated.By the heating, promote The dissolution of the metal of the main component of conductive pattern 6 and the diffusion to resin bed 13 are entered, as a result, promoting in resin Layer 13 is formed by the precipitation of the metal ingredient of above-mentioned diffusion and next metallic particles 4.If gather in addition, the resin combination includes Acid imide presoma, then polyimides is formd by the dehydration closed-loop of the polyimide precursor.

As heating means, can include (such as) by heating furnace and the method to the indirectly heat of laminate structure 11 Deng.As the method for indirectly heat, can include and the 3rd embodiment identical method.The lower limit of above-mentioned heating-up temperature is preferred For 200 DEG C.On the other hand, the upper limit of above-mentioned heating-up temperature is preferably 400 DEG C.If above-mentioned heating-up temperature is less than above-mentioned lower limit, Have due to the worry that the heat time increases and causes productivity to reduce.On the contrary, if above-mentioned heating-up temperature exceedes the above-mentioned upper limit, Then have the worry of the reductions such as the mechanical strength of conductive pattern 6 or resin bed 13.The lower limit of above-mentioned heat time is preferably 30 points Clock.On the other hand, the upper limit of above-mentioned heat time is preferably 2 hours.If the above-mentioned heat time is less than above-mentioned lower limit, tree is had Lipid layer 3 forms insufficient worry.On the contrary, if the above-mentioned heat time exceedes the above-mentioned upper limit, productivity reduction is had It is worried.In addition, atmosphere during heating is preferably under inert gas atmosphere.

In heating stepses, before above-mentioned heating is carried out, it is possibility to have the tree that will be layered in the one side of conductive pattern 6 The pre-dried step of oil/fat composition (pre-drying step).As pre-dried method, can include (such as) in nitrogen atmosphere etc. Method heated under inert atmosphere with the temperature below above-mentioned heating-up temperature etc..The lower limit of pre-dried heating-up temperature is (such as) 40 DEG C.On the other hand, the upper limit of above-mentioned heating-up temperature for (such as) 150 DEG C.In addition, under the pre-dried heat time Be limited to (such as) 20 minutes.On the other hand, the upper limit of above-mentioned heat time for (such as) 120 minutes.It should be noted that pre- In drying steps, it can also on the way change heating-up temperature.By pre-drying step so that the volatility of the resin combination into Divide volatilization in advance, so as to suppress generation of the bubble of resin bed 13 etc..

In the laminate structure 11, due to the excellent adhesion of conductive pattern 6 and resin bed 13, thus even if bending to It is variously-shaped to be also difficult to splitting occurs.

[other embodiments]

Embodiments disclosed herein should be considered in all respects as illustrative and not restrictive.The present invention Scope be not limited to the composition of the embodiment above, but shown by the scope of claims, and the present invention Scope is intended to all modifications being included in the implication and scope being equal with the scope of claim.

As the manufacture method of the resin combination, it is not limited to the manufacture method of the embodiment above, can also arrange Enumerate (such as) additive is added to the method for polymeric reaction solution before the polymerization of synthetic resin or in polymerization process；Use Method that synthetic resin and additive are kneaded by the kneading machines such as open roller, kneader, twin shaft mixing extruder etc..

In the laminate structure, as long as resin bed is layered at least a portion surface of metal level.In addition, In the laminate structure, also other layers can be further laminated in the outside of resin bed.If the laminate structure further comprises Other layers, then other layers can be the resin bed to be formed by the resin combination, or be set by others Oil/fat composition and the resin bed formed, or metal level.

In the laminate structure, metal level can also not have electric conductivity.In addition, the shape of metal level is not special Limit, it is variously-shaped that tabular, foil-like etc. can be included.If metal level is shaped as foil-like, the lower limit of average thickness is (example Such as) 10 μm.On the other hand, the upper limit of above-mentioned average thickness for (such as) 100 μm.

As the manufacture method of the laminate structure, it is not limited to the manufacture method of the embodiment above, can also arrange Enumerate (such as) using extruder and by the method for the resin combination extrusion molding on the surface of metal level；Use rod coating Machine, wing etc. and the resin combination is coated on to the method on the surface of metal level；And including by the resin combination The step of being shaped to sheet, the resin combination of sheet is configured to step on the surface of metal level and by pressurization plus Heat and method the step of be bonded the resin combination etc..

In the case where the laminate structure is flexible printed circuit board, only shape is not limited to as the embodiment above Into one layer of conductive pattern, or two-face printing circuit board or multilayer board formed with more than 2 layers of conductive pattern. In addition, the laminate structure as flexible printed circuit board includes the conductive pattern as metal level, is layered in the conductive pattern Basement membrane in the one side of case and the only resin bed being directly layered on the another side of above-mentioned conductive pattern, it can not include covering Epiphragma.In this case, the manufacture method as the laminate structure, can include (such as) it is included in above-mentioned first cascade The step of formation of structure has the step of resin combination is coated with the face of conductive pattern and heats the resin combination Method etc..

It should be noted that metal level is carried out at surface by using the surface conditioning agent illustrated in the 3rd embodiment Reason, so as to improve the resin bed formed by other resin combinations beyond the resin combination and above-mentioned metal level Adaptation.

[embodiment]

Hereinafter, although by embodiment and further to the resin combination according to one embodiment of the invention, layer Lamination structural body and its manufacture method are specifically described, but the present invention is not limited to following Production Example.

It should be noted that the reduction potential of additive used in the present embodiment is measured by the following method. That is, the previously prepared tetrabutyl ammonium tetrafluoroborate that 10mg sample is dissolved in 5ml under an inert atmosphere is 0.1mol/L acetonitrile solution, then carry out bubbling argon in atmosphere, argon gas stream and it is following under the conditions of determine cyclic voltammetric Figure.

Device name：" the potentiostat/galvanostat PGSTAT302 " of " オートラボ societies "

Sweep speed：The 0.1V/ seconds

Working electrode：Platinum electrode

To electrode：Platinum electrode

Reference electrode：Silver/silver chloride electrode (saturation KCl solution)

The electric current when positive voltage direction and negative voltage side scan up is read out from the cyclic voltammogram obtained by the measure Spike potential, and with the oxidation-reduction potential (Fc/Fc of ferrocene⁺) on the basis of above-mentioned current peak current potential is corrected, will Reduction potential of the average value of reduction side spike potential during each self-scanning as sample.

[resin combination No.1 to No.11 manufacture]

By the 4 of 94.3g, 4 '-diaminodiphenyl ether is dissolved into after 803g METHYLPYRROLIDONE, is added 102.7g pyromellitic acid anhydride.Then, under nitrogen atmosphere, above-mentioned reaction solution is stirred 1 hour at 25 DEG C, risen thereafter Temperature stirs 20 hours to 60 DEG C.After stirring, above-mentioned solution is cooled down, and as polyimide precursor solution.It is poly- to this Additive shown in acid imide precursor solution addition 2g table 1 below, is stirred for 1 hour, so as to manufacture resin combination No.1 to No.10.In addition, the material of additive will not be added as resin combination to above-mentioned polyimide precursor solution No.11。

[resin combination No.12 to No.18 manufacture]

Polyesterimide varnish (" EH402-45 " of the society that refines big day) is diluted using cresols, becomes polyester Acid imide content is 30 mass % polyesterimide solution.With 75:25:1 solid constituent ratio mixes the polyesterimide Solution, bisphenol A-type phenoxy resin (East are melted into " YP-50 " of society) and table 1 below shown in additive, and stir 1 hour, So as to manufacture resin combination No.12 to No.17.In addition, with 75:25 solid constituent ratio mixed polyester imide solution And bisphenol A-type phenoxy resin, and stir 1 hour, so as to manufacture resin combination No.18.

Title for the additive of resin combination No.1 to No.10 and resin combination No.12 to No.17 preparation And structural formula is as follows.

Additive (A1)：5- methyl isophthalic acids, 3,4- thiadiazoles -2- mercaptan

Additive (A2)：2,5- dimercapto -1,3,4- thiadiazoles

Additive (A3)：2- amino -5- sulfydryl -1,3,4- thiadiazoles

Additive (A4)：2- amino -1,3,4- thiadiazoles

Additive (A5)：2- amino -4,5- dicyano -1H- imidazoles

Additive (A6)：2- amino -5- nitrothiazoles

Additive (B1)：1,2,4- triazole -3- mercaptan

Additive (B2)：3- amino -5- sulfydryl -1,2,4- triazoles

Additive (B3)：Thiazolamine

Additive (B4)：2- sulfydryl -1- methylimidazoles

[chemical formula 2]

[chemical formula 3]

[laminate structure No.1 to No.18 manufacture]

Resin combination No.1 to No.18 is coated on to the gloss for the electrolytic copper foil that average thickness is 35 μm using wing On face, then in nitrogen atmosphere, 30 minutes predrying is carried out at 50 DEG C, and 60 points are further carried out at 120 DEG C Clock it is predrying.Then, by carrying out the heating of 60 minutes at 300 DEG C, so as to manufacture the stacking knot of resin bed and copper foil Structure body No.1 to No.18.

For laminate structure No.1 to No.18, metal level and tree are evaluated by 180 ° of disbonded tests as follows The adaptation of lipid layer.These evaluation results are shown in Table 1.In addition, table 1 shows the additive calculated by the following method in the lump Lowest unoccupied molecular orbital energy level.It should be noted that in table 1, "-" represents that the composition is not used." lumo energy " represents most The energy level of low-altitude track." HOMO energy levels " represents the energy level of highest occupied orbital." phr " represents to synthesize relative to 100 mass parts The mass parts of resin." EI/Ph " represents the hybrid resin of polyesterimide and phenoxy resin.

(180 ° of disbonded tests)

Laminate structure No.1 2 cut channels that cut-out length is about 2cm to No.18 are spaced in about 0.5mm, use tweezer Son starts one end of the resin bed between 2 cut channels, uses thermomechanical the testing machine (" TMA of " セイコー Electricity societies "：Heat Mechanical analysis ") the 180 of resin bed ° of disbonded tests are carried out, so as to determining peel strength (N/cm).Laminate structure No.1 is extremely No.11 peel strength in no heat treatment (normality), carry out the heating of 30 minutes in 160 DEG C under air after, with And in 160 DEG C be measured under the conditions of each after the heating of 60 minutes under air.In addition, laminate structure No.12 to No.18 peel strength is measured under conditions of no heat treatment (normality).It is 8 (N/cm) by peel strength Situation above is judged as well, and the situation less than 8 (N/cm) is judged as into difference.

The semiempirical molecular orbital of AM1 methods of lowest unoccupied molecular orbital calculate and calculate by using to(for) additive and most The energy level of high occupied orbital, it is by using Molecular Orbital Calculation software (" Winmostar " of " Network ロスア PVC リティ societies " Built-in MOPAC6) electronic state calculating and try to achieve.

[table 1]

As shown in table 1, for the resin combination by the energy level containing lowest unoccupied molecular orbital for below -0.2eV additive No.1 to No.6 and No.12 to No.15 and the laminate structure formed, it has obtained good result in terms of peel strength. In addition, even if the laminate structure formed by resin combination No.1 to No.6 remains in that well after the heat treatment Peel strength.On the other hand, for by the resin combination No.11 and No.18 without additive and containing lowest unoccupied molecular orbital The stepped construction that energy level is more than the resin combination No.7 to No.10 and No.16 to No.17 of -0.2eV additive and formed Body, it does not obtain good result in terms of peel strength.

In addition, as shown in table 1, for by the resin containing the additive that reduction potential is below more than -1.20V -0.30V Composition No.1 to No.6 and No.12 to No.15 and the laminate structure formed, it has been obtained well in terms of peel strength Result.In addition, even if the laminate structure formed by resin combination No.1 to No.6 remains in that after the heat treatment Good peel strength.On the other hand, for by the resin combination No.11 and No.18 without additive and containing also The stepped construction that former current potential is less than the resin combination No.7 to No.10 and No.16 to No.17 of -1.20V additive and formed Body, it does not obtain good result in terms of peel strength.

Industrial applicibility

As described above, the readily selected addition for meeting purposes of resin combination according to one embodiment of the invention Agent, and it is easy to improve the adaptation of formed resin bed and metal level.According to the stacking of another embodiment of the present invention The resin bed of structure and the excellent adhesion of metal level.According to the laminate structure of another embodiment again of the present invention Manufacture method can to easily and reliably provide the laminate structure of the excellent adhesion of resin bed and metal level.

Symbol description

1st, 11 laminate structure

2 conductors

2a oxide layers

2b oxidation free layers

3rd, 13 resin bed

4 metallic particles

5 interface adjacent domains

6 conductive patterns

7 basement membranes

8 cover layers

Claims

1. a kind of resin combination, it includes synthetic resin and additive, in the resin combination,

The energy level for the lowest unoccupied molecular orbital that the semiempirical molecular orbital by using AM1 methods of the additive is calculated and calculated For below -0.2eV.

2. resin combination according to claim 1, wherein, it is described to add relative to the synthetic resin of 100 mass parts Add the content of agent for more than 0.1 mass parts 10 mass parts below.

3. resin combination according to claim 1 or 2, wherein, the additive is substituted or non-substituted jeterocyclic chemistry Compound.

4. resin combination according to claim 3, wherein, the heterocyclic compound have amino, mercapto or they Combination.

5. resin combination according to any one of claim 1 to 4, wherein, the synthetic resin, which includes, has polarity The resin of group.

6. resin combination according to claim 5, wherein, the resin with polar group is polyimides, gathered Ester acid imide, polyester, polyamidoimide, phenoxy resin or combinations thereof.

7. a kind of resin combination, it includes synthetic resin and additive, in the resin combination,

The reduction potential of the additive is below more than -1.20V -0.30V.

8. a kind of laminate structure, it includes metal level and the resin being layered at least a portion surface of the metal level Layer,

The resin bed is formed by the resin combination comprising synthetic resin and additive,

9. laminate structure according to claim 8, wherein, the main component of the metal level is copper.

10. a kind of laminate structure, it includes metal level and the resin being layered at least a portion surface of the metal level Layer,

The reduction potential of the additive is below more than -1.20V -0.30V.

11. a kind of manufacture method of laminate structure, the laminate structure includes metal level and is layered in the metal level Resin bed at least a portion surface,

The step of manufacture method includes being coated at least a portion surface of the metal level using resin combination,

The resin combination includes synthetic resin and additive,

12. a kind of manufacture method of laminate structure, the laminate structure includes metal level and is layered in the metal level Resin bed at least a portion surface,

The resin combination includes synthetic resin and additive,

The reduction potential of the additive is below more than -1.20V -0.30V.