CN101547751A - Process for producing metal-film-coated substrate, metal-film-coated substrate, process for producing metallic-pattern material, and metallic-pattern material - Google Patents

Abstract

The present invention discloses a metal-film-coated substrate in which the metal film has excellent adhesion to the substrate and which has a small dependence on temperature and humidity; and a process for producing the substrate. Also provided are: a metallic-pattern material which comprises a substrate and a metallic pattern having excellent adhesion to the substrate, has a small dependence on temperature and humidity, and has excellent insulation reliability in the regions not covered by the metallic pattern; and a process for producing the material. The process for producing a metal-film-coated substrate is characterized by comprising: a step (a1) in which a polymer layer is formed on a substrate, the polymer layer being made of a polymer which has a non-dissociable functional group interacting with a plating catalyst or a precursor therefor and capable of multidentate coordination and which is directly and chemically bonded to the substrate; a step (a2) in which a plating catalyst or precursor therefor capable of multidentate coordination is imparted to the polymer layer; and a step (a4) in which the plating catalyst or precursor therefor capable of multidentate coordination is plated. It may be characterized by further including, after the step (a2), the following step (a3). Step (a3) in which a metal different from the plating catalyst or precursor therefor capable of multidentate coordination is incorporated into the polymer layer.

Description

The substrate of the manufacture method of the substrate of band metal film, band metal film, the manufacture method and the metallic pattern material of metallic pattern material

Technical field

The present invention relates to substrate and metallic pattern material, particularly relate to the substrate of the band metal film that uses as metal wiring plate, printing distributing board and the manufacture method of metallic pattern material with metal film.

Background technology

Up to now, the metal wiring substrate of the distribution that is formed by metallic pattern on the surface of insulating properties substrate is widely used in electronic unit and the semiconductor element.

Manufacture method as this metallic pattern material is mainly used " null method (subtractive method) ".Described null method is on the metal film that substrate surface forms, and the photosensitive layer that exposes with the active ray irradiation is set, and this photosensitive layer is carried out the image exposure, develop afterwards, form image against corrosion, then, with this metal film etching, form metallic pattern, peel off the method for resist layer at last.

The metallic pattern that this method obtains, concavo-convex by being provided with at substrate surface, produced the effect of fixator, thus demonstrate substrate and metal film between adaptation.Therefore, when using as metal wiring, existence is by the problem of the concavo-convex high frequency waves character difference that causes of the substrate interface portion of the metallic pattern that obtains.In addition,, also must handle substrate surface,, also have the problem that needs complicated step for the metallic pattern of the adaptation excellence that obtains metal film and substrate by strong acid such as chromic acid for substrate surface is carried out concavo-convex processing.

In order to address this problem, following method has been proposed: on substrate surface, carry out plasma treatment, at the substrate surface polymerization initiating group that induces one, make monomer polymerization from this polymerization initiating group, generate surface grafting polymerization thing with polar group at substrate surface, by this surface treatment, can not make substrate surface become coarse, and the adaptation that has improved substrate and metal film is (for example, with reference to Advanced Materials 2000,20 volumes, the 1481-1494 page or leaf).Yet when using this method, graft polymers has polar group, particularly during dissociation group, can be easy to generate the absorption or the disengaging of moisture, thereby have the metal film of formation or the problem of substrate easy deformation because temperature and humidity changes.

In addition, when the metallic pattern that utilizes this method to obtain is used as the distribution of metal wiring substrate, at the residual graft polymers of substrate interface part with polar group, disassociation property group, keep easily moisture or ion etc., so may go wrong aspect the anti-ion transport of the dependence of temperature, humidity, wiring closet and the change of shape.Particularly, present situation is, when using in fine distributions such as printing distributing board, between distribution (metallic pattern) high insulating properties must be arranged, and need further improve the reliability of the insulation of wiring closet.

Summary of the invention

The problem that invention will solve

The purpose of the present invention of considering above-mentioned prior art problems and proposing is to be to provide the metal film that has with the adaptation excellence of substrate, and to the substrate and the manufacture method thereof of temperature, band metal film that the humidity dependence is low.

In addition, second purpose of the present invention is to provide the metallic pattern that has with the adaptation excellence of substrate, and temperature, humidity dependence are low, and do not form the metallic pattern material and the manufacture method thereof of insulating reliability excellence in the zone of metallic pattern.Solve the means of problem

The inventor has carried out conscientious research based on the problems referred to above, and discovery can realize above-mentioned purpose by the method shown in following.

＜1〉manufacture method of the substrate of band metal film, wherein, has (a1) forms polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (a2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (a4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; Perhaps

After (a2) operation, also have following (a3) operation,

(a3) but make this polymeric layer contain the operation of the metal different with plating catalyst that should the multiposition coordination or its precursor.

＜2〉according to＜1〉manufacture method of the substrate of the band metal film put down in writing wherein, is nitrogen-containing functional group, oxygen-containing functional group or sulfur-bearing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

＜3〉according to＜1〉or＜manufacture method of 2〉the band metal film put down in writing substrate, wherein, be nitrogen-containing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

＜4〉according to＜1 〉～manufacture method of＜3〉each band metal film of putting down in writing substrate, wherein, but the plating catalyst of aforementioned multiposition coordination or its precursor are palladium or palladium ion.

＜5〉according to＜1 〉～manufacture method of＜4〉each band metal film of putting down in writing substrate, wherein, but aforementioned plating catalyst or the different metal of its precursor with the multiposition coordination is silver, copper, nickel, cobalt, tin, chromium or zinc.

＜6〉be with＜1 〉～substrate of the band metal film that the manufacture method of＜5〉each band metal film of putting down in writing substrate obtains.

＜7〉manufacture method of metallic pattern material, wherein, has (b1) forms polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (b2) on this polymeric layer, give the plating catalyst of adding multiposition coordination or the operation of its precursor; But (b4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; (b5) plated film that forms is etched to the operation of diagram shape; Perhaps

After (b2) operation, also have following (b3) operation,

But (b3) make this polymeric layer contain the operation of the metal different with the plating catalyst that is somebody's turn to do the multiposition coordination or its precursor.

＜8〉manufacture method of metallic pattern material, wherein, has (c1) forms polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (c2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (c4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; Perhaps

After (c2) operation, also have following (c3) operation,

But (c3) make this polymeric layer contain the operation of the metal different with the plating catalyst that is somebody's turn to do the multiposition coordination or its precursor.

＜9〉according to＜7〉or＜8〉the metallic pattern material put down in writing manufacture method, wherein, but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination is nitrogen-containing functional group, oxygen-containing functional group or sulfur-bearing functional group.

＜10〉according to＜7 〉～＜9〉the metallic pattern material put down in writing manufacture method, wherein, be nitrogen-containing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

＜11〉according to＜7 〉～＜10〉each metallic pattern material of putting down in writing manufacture method, wherein, but the plating catalyst of aforementioned multiposition coordination or its precursor are palladium or palladium ion.

＜12〉according to＜7 〉～＜11〉each metallic pattern material of putting down in writing manufacture method, wherein, but aforementioned plating catalyst or the different metal of its precursor with the multiposition coordination is silver, copper, nickel, cobalt, tin, chromium or zinc.

＜13〉be with＜7 〉～metallic pattern material that＜12〉each metallic pattern material of putting down in writing manufacture method obtains.The invention effect

According to the present invention, can provide to have with the excellent metal film of the adaptation of substrate, and the substrate and the manufacture method thereof of temperature, band metal film that the humidity dependence is low.

In addition,, can also provide to have with the excellent metallic pattern of the adaptation of substrate, and temperature, humidity dependence are low, do not form the metallic pattern material and the manufacture method thereof of insulating reliability excellence in the zone of metallic pattern according to the present invention.

Implement best mode of the present invention

Hereinafter, the present invention is described in detail.At first, the manufacture method to the substrate of band metal film of the present invention describes.

The manufacture method of the substrate of＜band metal film 〉

The manufacture method of the substrate of band metal film of the present invention, wherein, have: the operation that (a1) on substrate, forms polymeric layer, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (a2) operation of giving plating catalyst or its precursor of multiposition coordination on to this polymeric layer; But (a3) make this polymeric layer contain the operation of the metal different with the plating catalyst that is somebody's turn to do the multiposition coordination or its precursor; But (a4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated.

Below, each operation is described.

[(a1) operation]

In (a1) operation, on substrate, form polymeric layer, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and constitute with the polymer of this substrate direct chemical combination (below, also only be called " interaction group " sometimes).

(a1) operation is preferably (a1-1) and is manufactured on the substrate operation that forms the polymerization trigger layer that contains polymerization initiator on the base material; (a1-2) form polymer and this polymerization trigger layer direct chemical operation in conjunction with the formation polymeric layer on this polymerization trigger layer, this polymer has the interaction group.

In addition, above-mentioned (a1-2) operation is preferably by after the polymer with polymerizable group and interaction group is contacted, give energy, make the operation of this polymer and aforesaid base plate surface whole (polymerization trigger layer surface is whole) direct chemical combination.

(surface grafting)

The method that general use is called surface grafting polymerization forms the polymeric layer on the substrate.Described glycerol polymerization is to give active seed to the macromolecular compound chain, carries out polymerization with the another kind of monomer of initiated polymerization more thus, the method for synthetic grafting (graft) polymer.Particularly, when the macromolecular compound that active seed is provided forms the surface of solids, be also referred to as surface grafting polymerization.

As suitable surface grafting polymerization method of the present invention, can use any one of known method of document record.For example, compile in new macromolecule experiment 10, macromolecule association, 1994, be total to upright publish (Co., Ltd.) and issue, among the P135, put down in writing photo-grafting polymerization, plasma irradiation glycerol polymerization method as the surface grafting polymerization method.In addition, in the adsorption technology brief guide, NTS (Co., Ltd.), prison is repaiied in the bamboo, and 1999.2 distribution among P203, the P695, have been put down in writing irradiating gamma-ray, electron beam isoradial glycerol polymerization method.

Can use the method for JP63-92658A, JP10-296895A and JP11-119413A record as the concrete grammar of photo-grafting polymerization.

When forming polymeric layer of the present invention, except above-mentioned surface grafting method, can also use following method: at the end of macromolecular compound chain, give trialkoxysilyl, NCO, amino, hydroxyl, carboxyl isoreactivity functional group, the method that the coupling reaction of the functional group that exists by itself and substrate surface combines.

From generating the viewpoint of more graft polymers, in these methods, preferably use the photo-grafting polymerization to form polymeric layer.

[substrate]

" substrate " of the present invention is the substrate with following function, and its surface can form polymer direct chemical bonding state, but this polymer has the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor; Also can be the substrate that substrate itself has this surface nature, but also can be the intermediate layer (for example, polymerization trigger layer described later) that another approach is set that this intermediate layer can have the substrate of this character on this base material.

(base material, substrate)

The stable plate object of base material preferred size that uses among the present invention, comprise for example paper, lamination plastics (polyethylene for example, polypropylene, polystyrene etc.) paper, metallic plate (for example, aluminium, zinc, copper etc.), plastic sheeting (for example, cellulose diacetate, Triafol T, cellulose propionate, the butyric acid cellulose, acetic acid butyric acid cellulose, celluloid, PET, polyethylene, polystyrene, polypropylene, Merlon, the polyvinyl acetal, polyimides, epoxy resin, di maleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene (PTFE) etc.), lamination or evaporation the paper of above-mentioned metal or plastic sheeting etc.As the base material that uses among the present invention, be preferably epoxy resin or polyimide resin.

In addition, when these substrate surfaces have the function that can form polymer direct chemical bonding state, also can be with the using of this base material itself as substrate, but described polymer has the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor.

Can also use the base material of the polyimides that in skeleton, has polymerization initiation position of paragraph numbering [0028]～[0088] record that comprises JP2005-281350A as substrate of the present invention.

In addition, the substrate (substrate of band metal film of the present invention) of the band metal film that is obtained by the manufacture method of the substrate of band metal film of the present invention forms figure by etching, goes for semiconductor packages, various electric wiring substrates etc.When in this purposes, using, preferably use the substrate that contains insulative resin shown in following, specifically the substrate that forms by insulative resin or on base material, have the substrate of the layer that insulative resin forms.

At the substrate that obtains forming, by when layer that insulative resin forms, can use known insulating resin composition by insulative resin.In these insulating resin compositions, adding on the main resin, can also use together with various additives according to purpose.For example, can also choose following several method:, add polyfunctional acrylate monomer based on the purpose of the intensity that improves insulating barrier; Based on the intensity that improves insulating barrier, improve the purpose of electrical property, can also add inorganic or organic filler etc.

In addition, " insulative resin " of the present invention is meant the resin that has insulating properties that can usage degree in known dielectric film or insulating barrier, might not be insulator completely,, just can be applicable to the present invention so long as have the resin of the insulating properties of suitable purpose.

As the object lesson of insulative resin, for example can be heat-curing resin, thermoplastic resin or their mixture.For example, as heat-curing resin, can list epoxy resin, phenolic resins, polyimide resin, mylar, di maleimide resin, polyolefin resin, isocyanates resinoid etc.

As epoxy resin, can list for example cresol novolak epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolac epoxy resins, alkylphenol novolac epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, phenols and have the epoxides, triglycidyl group chlorinated isocyanurates, alicyclic epoxy resin etc. of condensation product of the aromatic aldehyde of phenolic hydroxyl group.They can use separately, also can will use together more than 2 kinds.By epoxy resin, can form excellent materials such as hear resistance.

As polyolefin resin, can list copolymer of for example polyethylene, polystyrene, polypropylene, polyisobutene, polybutadiene, polyisoprene, cycloolefin resinoid, these resins etc.

As thermoplastic resin, can list for example phenoxy resin, polyether sulfone, polysulfones, PPSU, polyphenylene sulfide, polyphenylene ether, PEI etc.

As other thermoplastic resin, can list 1,2-two (vinyl phenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or the modified resin of itself and poly (phenylene ether) resin (a day plumage is realized etc., Journal ofApplied Polymer Science Vol.92, record among the 1252-1258 (2004)), liquid-crystalline polymer (the ベ Network ス that makes as Network ラ レ (Larry, storehouse)-(Bie Kusita)) particularly, etc., fluororesin (PTFE) etc.

Thermoplastic resin and heat-curing resin can be distinguished use separately, also can use together more than 2 kinds.This can be according to the shortcoming that remedies separately, shows the purpose of more excellent effect and carries out.For example, polyphenylene ether thermoplastic resins such as (PPE) is low to the tolerance of heat, changes so can carry out alloy (alloy) with heat-curing resin etc.For example, as the alloying of PPE and epoxy resin, triallyl isocyanate or import the PPE resin of polymerism functional group and the alloying of other heat-curing resin and using.In addition, isocyanates is the resin of dielectricity excellence in the heat-curing resin, and it uses seldom separately, as the modified resin use of epoxy resin, maleimide resin, thermoplastic resin etc.Their details is put down in writing among the P35 No. 2002/9, " electronic technology ".In addition, contain epoxy resin and/or phenol resin, contain phenoxy resin and/or polyether sulfone (PES), use in order to improve dielectricity as heat-curing resin as heat-curing resin.

In insulating resin composition, also can to contain in order carrying out crosslinked and to have the compound of two keys of polymerism, can contain acrylate, methacrylate compound particularly, particularly preferred polyfunctional compound.In addition, compound as two keys with polymerism, also can use heat-curing resin or thermoplastic resin, for example epoxy resin, phenolic resins, polyimide resin, vistanex, fluororesin etc., use methacrylic acid or acrylic acid etc., the part of resin is carried out the resin that (methyl) propylene acidification reaction forms.

Character such as the mechanical strength of filming for fortified resin, hear resistance, against weather, anti-flammability, water proofing property, electrical property can also be used the compound (composite) of resin and other composition in insulating resin composition of the present invention.As the material of compoundization use, can enumerate paper delivery, glass fibre, silica particle, phenolic resins, polyimide resin, dimaleimide cyanate resin, fluororesin, polyphenylene ether resin etc.

In addition, in this insulating resin composition, as required can also blending one or two or more kinds the filler that uses in resin material at distributing board, for example inorganic fillers such as silica, aluminium oxide, clay, talcum, aluminium hydroxide, calcium carbonate, organic fillers such as cured epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic acid polymer.

In addition, in this insulating resin composition, can also further add as required one or two or more kinds colouring agent, fire retardant, give various additives such as adhesiveness reagent, silane coupler, antioxidant, ultra-violet absorber.

When adding these materials in insulating resin composition, no matter which material in these materials with respect to resin, all preferably adds 1～200 quality %, more preferably adds 10～80 quality %.This addition is not strengthened the effect of above-mentioned character when less than 1 quality %, in addition, when surpassing 200 quality %, character such as the distinctive intensity of resin descend.

As the substrate that uses in this purposes, the dielectric constant (capacitivity) that is preferably particularly in 1GHz is the substrate that the insulative resin below 3.5 forms, or has the substrate of the layer that is formed by this insulative resin on base material.In addition, also preferred dielectric loss tangent in 1GHz is the substrate that the insulative resin below 0.01 forms, or has the substrate of the layer that is formed by this insulative resin on base material.

The dielectric constant of insulative resin and dielectric loss tangent can be measured by conventional method.For example, method according to record in " No. the 18th time electronic equipment is installed association's disquisition conference main idea collection,, P189 in 2004 ", use emptying aperture resonator perturbation method (for example, wafer thin is made with ε r, tan δ analyzer, キ-コ system (the triumphant wood of drawing together) Co., Ltd.) to measure.

Based on this reason, in the present invention, from the viewpoint of dielectric constant and dielectric loss tangent, it also is useful selecting dielectric resin material.As dielectric constant be below 3.5, dielectric loss tangent is the insulative resin below 0.01, can list liquid crystal polymer, polyimide resin, fluororesin, poly (phenylene ether) resin, isocyanate resin, two (diphenylene) ethane resin etc., comprise their modified resin in addition.

Be applicable to the substrate of manufacture method of the substrate of band metal film of the present invention, concave-convex surface is preferably below the 500nm, more preferably below the 100nm, more preferably below the 50nm, most preferably below the 20nm.The concave-convex surface of this substrate (when intermediate layer or polymerization trigger layer are set, the concave-convex surface of this layer) is more little, and the substrate of the band metal film of gained is when being used for distribution etc., and the electric loss during the high frequency transmission of electricity is just few more, so preferred.

In the present invention, on substrate surface, give active seed, with its surface grafting method, under the situation of this surface grafting method of use as a dot generation graft polymers, when generating graft polymers, preferably use the substrate that on base material, forms the polymerization trigger layer that contains polymerization initiator.By using this substrate, can produce active site effectively, generate more graft polymers.

Below, polymerization trigger layer of the present invention is described.

(polymerization trigger layer)

Polymerization trigger layer as among the present invention can list the layer that comprises macromolecular compound and polymerization initiator, and the layer that comprises polymerizable compound and polymerization initiator.

Polymerization trigger layer among the present invention is, neccessary composition is dissolved in the solvent that can dissolve, and is arranged on the substrate surface by methods such as coatings, penetrates by heating or illumination film is solidified to form.

As the compound that uses in the polymerization trigger layer among the present invention so long as and the adaptation of base material good, and energize by irradiation active ray etc., produce the compound of active seed, just can, be not particularly limited use.Particularly, can use the hydrophobicity condensate that mixed polyfunctional monomer or in molecule, had polymerizable group and the material of polymerization initiator.

Can list dienes list polymers such as polybutadiene, polyisoprene, polyprene particularly as this hydrophobic polymer that has polymerizable group in molecule, (methyl) acrylic acid allyl ester, methacrylic acid 2-allyloxy ethyl ester etc. contains single polymers of allylic monomer;

Contain dienes monomers such as butadiene, isoprene, pentadiene or contain allylic monomer as binary or multiple copolymers such as the styrene of construction unit, (methyl) acrylate, (methyl) acrylonitrile;

Unsaturated polyester (UP), unsaturated polyester epoxides, unsaturated polyester acid amides, unsaturated polyester acrylic acid, high density polyethylene (HDPE) etc. have the linear polymeric of carbon-to-carbon double bond or three-dimensional macromolecule etc. in molecule.

In addition, in this manual, when referring to " acrylic, methylpropenyl " two kinds or any one, also note is made " (methyl) acrylic " sometimes.

In the polymerism layer, the content of these polymer compounds is preferably the scope of 10～100 quality % with solid component meter, is preferably the scope of 10～80 quality % especially.

Containing in the polymerization trigger layer energizes shows the polymerization initiator of polymerization energy of initiation.Polymerization initiator used herein can be according to purpose, suitably selects to use the energy by appointment, and for example irradiation of the irradiation of active ray, heating, electron beam etc. can show the known thermal polymerization, Photoepolymerizationinitiater initiater of polymerization energy of initiation etc.Wherein, from the viewpoint that is fit to make, suitable is to utilize photopolymerization, therefore, preferably uses Photoepolymerizationinitiater initiater.

Photoepolymerizationinitiater initiater is so long as have activity to the active ray that shines, can carry out surface grafting polymerization from the polymerization trigger layer that contains this Photoepolymerizationinitiater initiater, just there is no particular limitation, can use for example radical polymerization initiator, anionic polymerization initiator, cationic polymerization initiators etc., but from reactive viewpoint, preferred radical polymerization initiator.

As this Photoepolymerizationinitiater initiater, can list particularly and for example resemble right-tert-butyl group trichloroacetophenone, 2,2 '-diethoxy acetophenone, the 2-hydroxy-2-methyl-such acetophenones of 1-phenyl third-1-ketone; Resemble benzophenone, 4,4 '-two (dimethylamino) benzophenone, 2-chloro thioxanthone, 2-methyl thioxanthones, 2-ethyl thioxanthones, the such ketone of 2-isopropyl thioxanthone; Resemble styrax, styrax methyl ether, benzoin isobutyl propyl group ether, the such styrax ethers of benzoin isobutyl butyl ether; Resemble such benzyl ketals class of benzyl dimethyl ketal, hydroxycyclohexylphenylketone etc.

In the polymerization trigger layer, the content of polymerization initiator calculates with solid constituent, is preferably the scope of 0.1～70 quality %, more preferably the scope of 1～40 quality %.

The solvent that uses when being coated with above-mentioned polymerizable compound and polymerization initiator, as long as can dissolve these compositions, just there is no particular limitation.From easy drying, operation viewpoint, the preferred not too high solvent of boiling point, particularly, can select boiling point is the solvent of 40 ℃～150 ℃ of degree.

Particularly, can list acetone, MEK, cyclohexane, ethyl acetate, oxolane, toluene, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propane diols list ethylether, pentanedione, cyclohexanone, methyl alcohol, ethanol, 1-methoxyl group-2-propyl alcohol, 3-methoxypropanol, diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propane diols list ethylether acetic acid esters, 3-methoxy propyl yl acetate etc.

These solvents can separately or mix the back to be used.And that the concentration of the solid constituent in the coating solution is suitable is 2～50 quality %.

From showing enough polymerization energy of initiation and keeping the viewpoint that film character prevents that film from peeling off, in quality after the drying, the coating weight when forming the polymerization trigger layer on base material is preferably 0.1～20g/m ², 0.5～15g/m more preferably ²

In the present invention, as mentioned above, wait the above-mentioned polymerization trigger layer formation of configuration composition on base material by coating, remove and desolvate, film forming forms the polymerization trigger layer, and at this moment, preferably heating and/or illumination are penetrated film is solidified.Particularly, preferably behind heat drying, carry out illumination and penetrate, prepare cured film, and polymerizable compound is cured to a certain degree in advance, this be for can effectively be suppressed at generate graft polymers on the polymerization trigger layer after, graft polymers and polymerization trigger layer come off together.

Heating-up temperature and time can select can abundant drying coated solvent condition, but from the aspect that is fit to make, preferred temperature is below 100 ℃, be in 30 minutes drying time, and more preferably baking temperature is that 40～80 ℃, drying time are 10 minutes heating conditions with interior scope.

Behind the heat drying, penetrate, can use the light source that in generation graft polymers reaction described later, uses according to the illumination that hope is carried out.In the operation of the production graft polymers that and then carries out, the active site of the polymerization trigger layer that produces from energizing and the viewpoint that does not hinder the generation of graft polymers, the preferred light irradiation, the polymerization initiator that exists in the polymerization trigger layer is when solidifying polymerizable compound, even radical polymerization, illumination penetrate also can full consumption not fall.Illumination is penetrated the time according to the intensity of light source and different, is preferably usually in 30 minutes.As the target that this preparation is solidified, the film residual rate that can list behind the solvent wash is below 80%, and the initator residual rate of preparation after solidifying is more than 1%.

In addition, containing beyond the polymerization trigger layer of above-mentioned polymerizable compound and polymerization initiator, the use polymerization initiating group that also preferred JP2004-161995A put down in writing forms the polymerization trigger layer of the polymer of side group on side chain.This polymer specifically, be the polymer that has the functional group's (polymerization initiating group) that contains the polymerization energy of initiation and crosslinkable groups on the side chain (below, be called polymerization initiated polymerization thing), by this polymer, can have the polymerization initiating group that is combined on the polymer chain, and this polymer chain can form the polymerization trigger layer of solid form by cross-linking reaction.

The polymerization trigger layer of Xing Chenging also is suitable as the application's polymerization trigger layer like this.

Polymerization initiated polymerization thing used herein can list the polymerization initiated polymerization thing that [0011] of JP2004-161995A～[0158] section is put down in writing.Can list the material shown in following as the particularly preferred material of polymerization initiated polymerization thing.

[changing 1]

[changing 2]

The film forming of-polymerization trigger layer-

The polymerization trigger layer that uses polymerization initiated polymerization thing of the present invention to form can be by being dissolved into above-mentioned polymerization initiated polymerization thing in the suitable solvent, the preparation coating fluid, by coating etc. this coating fluid is configured on the base material, removes and desolvate, carry out the cross-linking reaction film forming.Just, by carrying out this cross-linking reaction, with the immobilization of polymerization initiated polymerization thing.In fixing by this cross-linking reaction, have the method for using polymerization initiated polymerization thing self-condensation reaction and and the method used together of crosslinking agent, preferably use crosslinking agent.As the method for the self-condensation reaction that uses polymerization initiated polymerization thing, for example can list in crosslinkable groups and during for-NCO, utilize heating to carry out the method for the character of self-condensation reaction.By carrying out this self-condensation reaction, can form cross-linked structure.

In addition, as the crosslinking agent that uses in the method for using together with crosslinking agent, can use existing known those crosslinking agents of record in " the crosslinking agent handbook " of letter two writings under the mountain.

Preferred combination as crosslinkable groups in the polymerization initiated polymerization thing and crosslinking agent, can list (crosslinkable groups, crosslinking agent)=(COOH, the amine of multivalence), (COOH, the aziridine of multivalence), (COOH, the isocyanates of multivalence), (COOH, the epoxides of multivalence), (NH ₂, the isocyanates of multivalence), (NH ₂, aldehydes), (NCO, the amine of multivalence), (NCO, the isocyanates of multivalence), (NCO, the alcohol of multivalence), (NCO, the epoxides of multivalence), (OH, the alcohol of multivalence), (OH, the halide of multivalence), (OH, the amine of multivalence), (OH, acid anhydrides).Wherein, after crosslinked, generate urethane bonds, can form high-intensity crosslinked viewpoint and set out, the combination of more preferably (functional group, crosslinking agent)=(OH, the isocyanates of multivalence).

As the object lesson of the crosslinking agent among the present invention, can list the material of following structure.

[changing 3]

This crosslinking agent can add in the coating fluid that contains above-mentioned polymerization initiated polymerization thing when polymerization trigger layer film forming.Afterwards, the heat when filming heat drying carries out cross-linking reaction, can form firm cross-linked structure.In more detail, carry out cross-linking reaction, form cross-linked structure by the addition reaction shown in the dehydration shown in the following e * 1. and the e * 2..Be preferably more than 50 ℃ as the temperature conditions in these reactions, below 300 ℃; More preferably more than 80 ℃, below 200 ℃.

[changing 4]

In addition, addition as the crosslinking agent in the coating fluid, can change according to the amount that imports the crosslinkable groups in the polymerization initiated polymerization thing, from crosslinking degree and residual unreacted crosslinked composition viewpoint to the influence of polymerisation, molal quantity with respect to crosslinkable groups, usually the addition of crosslinking agent is preferably 0.01～50 equivalent, more preferably 0.01～10 equivalent, more preferably 0.5～3 equivalent.

In addition, just there is no particular limitation so long as dissolve the solvent of above-mentioned polymerization initiated polymerization thing for the solvent that uses during coating polymerization trigger layer.From the easy degree of drying, the viewpoint of operation, the preferred not too high solvent of boiling point, selecting boiling point particularly is the solvent of 40 ℃～150 ℃ of degree.

Can list acetone particularly; MEK; cyclohexane; ethyl acetate; oxolane; toluene; the glycol monomethyl methyl ether; ethylene glycol monomethyl ether; ethylene glycol dimethyl ether; propylene glycol monomethyl ether; propane diols list ethylether; pentanedione; cyclohexanone; methyl alcohol; ethanol; 1-methoxyl group-2-propyl alcohol; the 3-methoxypropanol; the diglycol monotertiary methyl ether; carbiphene; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; propylene glycol monomethyl ether; propane diols list ethylether acetic acid esters; 3-methoxy propyl yl acetate etc.

These solvents can be used alone or as a mixture.And that the concentration of the solid constituent in the coating solution is suitable is 2～50 weight %.

From the viewpoint of the energy of initiation and the property of thin film of surface grafting polymerization, the coating weight of using the polymerization trigger layer that polymerization initiated polymerization thing forms is preferably 0.1～20g/m in dried weight ², 1～15g/m more preferably ²

In addition, in the present invention, when foregoing use has the substrate of the layer that is formed by insulative resin on base material, preferably in the layer that this insulative resin constituted, contain known polymerization initiator, form the polymerization trigger layer of insulating properties.There is no particular limitation as the polymerization initiator that contains in this insulating properties polymerization trigger layer, can use for example aforesaid thermal polymerization, Photoepolymerizationinitiater initiater (radical polymerization initiator, anionic polymerization initiator, cationic polymerization initiators) and JP9-77891A, JP10-45927A put down in writing has the macromolecular compound of active carbonyl group at side chain, also have at side chain and have the functional group that contains the polymerization energy of initiation and the polymer (polymerization initiated polymerization thing) of crosslinkable groups etc.

The amount of the polymerization initiator that in insulating properties polymerization trigger layer, contains usually with insulating barrier in solid component meter, be preferably 0.1～50 quality % degree, more preferably 1.0～30.0 quality % degree.

(generation of graft polymers)

As the generation scheme of the graft polymers in (a1) operation as previously mentioned, can use the method for the coupling reaction between the reactive functional groups that end or side chain had that has utilized functional group that substrate surface exists and macromolecular compound, and the photo-grafting polymerization.

In the present invention, be preferably as follows scheme [(a1-2) operation]: use the substrate that on base material, has formed the polymerization trigger layer, on this polymerization trigger layer, form polymer and this polymerization trigger layer direct chemical in conjunction with the polymeric layer that is constituted, but this polymer has the non-disassociation functional group (interaction group) that forms interactional multiposition coordination with electrolytic catalyst or its precursor.Following proposal more preferably: by after the polymer with polymerizable group and interaction group is contacted, energize, thereby this polymer direct chemical is combined on the aforesaid base plate surface whole (polymerization trigger layer surface is whole).Just, make compound directly contact polymerization trigger layer surface with polymerizable group and interaction group, perhaps make and contain this compound compositions contact polymerization trigger layer surface, direct Cheng Jian of active seed simultaneously by generating on this polymerization trigger layer surface.

Though can being impregnated in the liquid composition that contains the compound with polymerizable group and interaction group by the substrate that will form the polymerization trigger layer, above-mentioned contact carries out, but, viewpoint from operability and manufacturing efficient, as described later, also can form to contain the layer that the compound compositions with polymerizable group and interaction group is a principal component at substrate surface (polymerization trigger layer surface) by rubbing method.

In the present invention, but use when generating graft polymers by the surface grafting polymerization method, have polymerizable group and can describe with the compound that plating catalyst or its precursor form the non-disassociation functional group (interaction group) of interactional multiposition coordination.

In the present invention, interaction group in the described compound with polymerizable group and interaction group (but forming the non-disassociation functional group of interactional multiposition configuration with plating catalyst or its precursor) is functional group's generation proton that can not dissociate, and by the interaction of molecular separating force and the functional group of plating catalyst or its precursor coordination.

As this interaction group, preferred nitrogen-containing functional group, oxygen-containing functional group, sulfur-bearing functional group etc., what exemplify out particularly has, imide, pyridine radicals, tertiary amine groups, ammonium, pyrrolidone-base, amidino groups, the group that contains triazine ring structure, the group that contains the cyamelide structure, nitro, nitroso, azo group, two azo groups, azido, cyano group, cyanate ester based nitrogen-containing functional groups such as (R-O-CN), ether, carbonyl, ester group, the group that contains the N-oxide structure, the group that contains the S-oxide structure, the oxygen-containing functional groups such as group that contain the N-hydroxyl structure, thioether group, sulphur oxygen base (thioxy), sulfoxide group, sulfuryl, sulfinyl group, the group that contains sulphur oxygen base imines (sulphoxy imine) structure, the group that contains the sulfosalt structure, the sulfur-bearing functional groups such as group of containing the sulphonic acid ester structure, phosphorous functional group such as phosphino-, chloride, the group of halogen atoms such as bromine and unsaturated ethylene thiazolinyl etc.In addition, so long as atom by adjacency or atomic group between relation demonstrate the scheme of non-disassociation, can also use imidazole radicals, urea base, ghiourea group.

Wherein, from the polarity height, to the high aspect of energy of adsorption of electrolytic catalyst etc., especially preferably contain ether (more specifically with-O-(CH ₂) _nStructure shown in the-O-(n is 1～5 integer)) material of pyridine radicals, cyano group, ether, thioether group.

Even having with plating catalyst or its precursor, this functional group forms interactional function, but because it does not have the polar group (hydrophilic radical) of disassociation property, so temperature, the humidity dependence of the polymeric layer that is formed by the graft polymers with this functional group are low.

In the present invention, compound with polymerizable group and interaction group can be any one form of monomer, macromonomer, polymer, wherein, from the viewpoint of the easiness of the formation of polymeric layer and control, preferably use polymer (polymer) with polymerizable group and interaction group.

Polymer as polymerizable group and interaction group, be preferably in use and have on the homopolymers or copolymer that the monomer of polymerization interaction group obtains, import the polymer that vinyl addition polymerization unsaturated groups (polymerizable group) such as vinyl as polymerizable group, pi-allyl, (methyl) acrylic form; This polymer with polymerizable group and interaction group is the polymer that has polymerizable group at least on main chain end or side chain, preferably has the polymer of polymerizable group at side chain.

In addition; polymerizable group among the present invention is by energizing; have between the compound of polymerizable group and interaction group; or the functional group that combines with substrate of the compound with polymerizable group and interaction group; except above-mentioned vinyl addition polymerization unsaturated group, can also list vinyl, ethyleneoxy, pi-allyl, acryloyl group, methacryl, oxetanyl, epoxy radicals, NCO, the functional group that contains reactive hydrogen, the active group in the azo-compound etc.

The monomer that uses when obtaining aforementioned polymer with polymerizable group and interaction group with interaction group, can list vinylpyridine class, N-vinyl pyrrolidone etc., they can use a kind separately, also can will use together more than 2 kinds.

Concerning polymer with polymerizable group and interaction group, from with the interactional viewpoint of the formation of plating catalyst or its precursor, from the unit of monomer with interaction group in polymer with polymerizable group and interaction group, the scope that preferably contains 50～95 moles of % more preferably contains the scope of 40～80 moles of %.

In addition, when obtaining having the polymer of polymerizable group and interaction group, except use has the monomer of above-mentioned interaction group, can also use other monomer synthetic.As other monomer, can use general polymerizable monomer, can list dienes monomer, propylene base class monomer etc.

This polymer with polymerizable group and interaction group can followingly synthesize.

As synthetic method, can list i) make monomer and have the method for the monomer copolymerization of polymerizable group with interaction group; Ii) make monomer with interaction group and monomer copolymerization, introduce the method for two keys then by processing such as alkali with two key precursors; Iii) make polymer with interaction group and monomer reaction, import the method for two keys (importing polymerizable group) with polymerizable group.From synthetic adaptive viewpoint, preferably ii) make monomer with interaction group and monomer copolymerization with two key precursors, introduce the method for two keys then by processing such as alkali; Iii) make polymer with interaction group and monomer reaction, import the method for polymerizable group with polymerizable group.

The monomer with interaction group that uses during as synthetic polymer with polymerizable group and interaction group can use the monomer identical with the monomer with above-mentioned interaction group.Monomer can use a kind separately, also can will use together more than 2 kinds.

As with the monomer with polymerizable group of monomer copolymerization with interaction group, can list (methyl) acrylic acid allyl ester, methacrylic acid 2-allyloxy ethyl ester etc.

In addition, as monomer, can list methacrylic acid 2-(3-chloro-1-oxopropoxy) ethyl ester, methacrylic acid 2-(3-bromo-1-oxopropoxy) ethyl ester etc. with two key precursors.

In addition, as utilizing and having carboxyl, amino or functional group reactionses such as their salt, hydroxyl and epoxy radicals in the polymer of interaction group, the monomer with polymerizable group that uses when introducing unsaturated group comprises (methyl) acrylic acid, (methyl) acrylic acid glycidyl esters, allyl glycidyl ether, 2-NCO ethyl (methyl) acrylate etc.

The mean molecule quantity of the polymer with polymerizable group and interaction group among the present invention is preferably more than 1000, below 700,000; More preferably more than 2000, below 300,000.

In addition, preferably use 10 more than the unit as the degree of polymerization of the polymer with polymerizable group and interaction group among the present invention, more preferably 20 unit are above.In addition, also be preferably 7000 below the unit, more preferably 3000 below the unit, more preferably 2000 below the unit, be preferably 1000 especially below the unit.

Below, expression is fit to the object lesson of the polymer with polymerizable group and interaction group of use in the present invention, but the present invention is not limited to these examples.

[changing 5]

The compound with polymerizable group and interaction group among the present invention except having polymerizable group and interaction group, does not damage in the scope of effect of the present invention at the water absorption rate of the polymeric layer that forms, and can also have polar group.By having polar group, after forming metal film, when for example protective layer being set, can improve the closing force of polymeric layer and protective layer contact area by the aftermentioned operation.

The solvent that in the compound compositions that comprises polymer with above-mentioned polymerizable group and interaction group etc., uses with polymerizable group and interaction group, as long as can dissolve as the compound with polymerizable group and interaction group of composition principal component etc., just there is no particular limitation.Also can in solvent, add surfactant again.

As operable solvent, can list for example methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerine, the such alcohols solvent of propylene glycol monomethyl ether, the acid that acetic acid is such, acetone, the such ketones solvent of cyclohexanone, amide solvent that formamide, dimethylacetylamide are such etc.

In addition, in the present invention, in the time will having comprised compound compositions and be applied on substrate or the polymerization trigger layer with polymerizable group and interaction group, can selective solvent so that the solvent absorptivity of substrate or polymerization trigger layer is 5～25%.This solvent absorptivity can be by being impregnated into substrate or the base material that formed the polymerization trigger layer in the solvent, and the mass change when taking out after 1000 minutes is tried to achieve.

In addition, in the time will having comprised compound compositions and be applied on substrate or the polymerization trigger layer with polymerizable group and interaction group, can selective solvent so that the swelling ratio of substrate or polymerization trigger layer is 10～45%.This swelling ratio can be by being impregnated into substrate or the base material that formed the polymerization trigger layer in the solvent, and the varied in thickness when taking out after 1000 minutes is tried to achieve.

Can add the surfactant in the solvent as required to so long as can be dissolved into getting final product in the solvent, as this surfactant, can list for example such anion surfactant and the such cationic surfactant of chlorination dodecyl trimethyl ammonium of dodecyl sodium sulfonate, (as commercially available product for example is エ マ Le ゲ Application 910 (the solid grace 910 in Emma Shandong) to the polyoxyethylene groups nonylphenyl ether, flower king (Co., Ltd.) manufacturing etc.), polyoxyethylene groups sorbitan monolaurate (as commercially available product commodity by name " Star イ-Application 20 (kind grace 20) " etc. for example), the nonionic surfactant that the polyoxyethylene groups lauryl ether is such.

In having comprised compound compositions, can also add polymerization inhibitor as required with polymerizable group and interaction group.As operable polymerization inhibitor, can use quinhydrones, di-tert-butyl hydroquinone, 2,5-two (1,1,3,3-tetramethyl butyl) hydroquinones such as quinhydrones, phenols such as p methoxy phenol, phenol, the benzoquinones class, TEMPO (2,2,6,6-tetramethyl-1-piperidines oxygen base free radical), the radical type of 4-hydroxyl TEMPO etc., nitroso amine, the pyrocatechol of phenothiazines, N-nitroso phenyl hydroxylamine, its ammonium salt etc.

In addition, in having comprised compound compositions, can add curing agent and/or curing accelerator as required, to promote the curing of polymerization trigger layer with polymerizable group and interaction group.For example, when in the polymerization trigger layer, containing epoxide, as curing agent and/or curing accelerator, can the listing aliphatic polyamines, alicyclic polyamine, aromatic series polyamine, polyamide, acid anhydrides, phenol, phenol phenolic resins, polymercaptan, have compound bearing active hydrogen more than 2 etc. of polyaddition type; Catalytic type can list aliphatic tertiary amine, aromatic nitrile base, imidazolium compounds, lewis acid complex compound etc.

In addition, as passing through heat, light, moisture, pressure, acid, beginning such as alkali solidified material, can list for example diethylenetriamines, trien, tetren, diethylamino propyl group amine, polyamide-based amine, methylene diamine, IPD, the N-aminoethylpiperazine, 3,9-two (3-aminopropyl)-2,4,8,10-four oxo spiral shells (5,5)-the hendecane adduct, two (4-amino-3-methylcyclohexyl) methane, two (4-aminocyclohexyl) methane, m-xylene diamine, diaminodiphenyl-methane, m-phenylenediamine, diamino diphenyl sulfone, the dicyano diamides, adipic dihydrazide (ジ ヒ ラ ジ De), phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl norbornene dioic anhydride, dodecyl succinic anhydride, chlorendic anhydride, PMA, benzophenone tetracid acid anhydride, ethylene glycol bisthioglycolate (trihemellitic acid acid anhydride) (Ethylene glycol bis (trimellitic anhydride)), methylcyclohexene tetracid acid anhydride, the trihemellitic acid acid anhydride, poly-azelaic acid acid anhydride, the phenol novolaks, the xyxylene novolaks, bisphenol-A phenolic varnish, the triphenyl methane novolaks, the xenyl novolaks, bicyclopentadiene phenol novolaks, terpenes phenol novolaks, polymercaptan, polysulfide, 2,4,6-three (dimethylaminomethyl) phenol, 2,4,6-three (dimethylaminomethyl) phenol-three-2 ethyl hexanoic acid salt, benzyl dimethyl amine, 2-(dimethylaminomethyl) phenol glyoxal ethyline, 2-ethyl-4-methylimidazole 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 2,4-dicyano-6-(glyoxal ethyline base-(1))-ethyl-S-triazine, BF ₃Single ethylamine complex compound, lewis acid complex compound, organic acid hydrazides, diaminourea Malaysia acyl cyanide, melamine derivative, imdazole derivatives, polyamine salt, amine group with imine moiety, aromatic series two diazo salts, diallyl salt compounded of iodine, triallyl sulfonium salt, triallyl selenium salt, ketimine compound etc.

From the viewpoints such as adaptation of coating and the substrate or the plated film of solution, these curing agent and/or effect promoter are preferably added 0～50 quality % degree of removing the residual nonvolatile component of desolvating to.In addition, curing agent and/or curing accelerator also can add in the polymerization trigger layer, in this case, add the amount of polymerization trigger layer to and the total amount of adding in the polymeric layer preferably satisfies above-mentioned scope.

In addition, can also further add plasticizer, rubber constituent (for example, CTBN), fire retardant (for example, phosphorus type flame retardant), diluent and thixotropy reagent, pigment, defrother, levelling agent, coupling agent etc.In addition, these additives also can add in the polymerization trigger layer as required.

By using these compounds and various additive suitably to mix the composition of formation with polymerizable group and interaction group, can be with the rerum natura of the polymeric layer that forms, can the most suitable setting such as thermal coefficient of expansion, vitrifying transition temperature, poplar formula spring rate, Poisson ratio, rupture stress, yield stress, heat decomposition temperature etc.Particularly, rupture stress, yield stress, heat decomposition temperature are high more good more.

Mensuration hear resistances such as the polymeric layer of gained can be tested by temperature cycles, temperature time variance experiment, anti-stream experiment, for example, thermal decomposition can followingly be estimated: the environment that is exposed to 200 ℃ if quality reduces below 20%, then has enough hear resistances in the time of following 1 hour.

When contact had comprised the compound compositions with polymerizable group and interaction group, from forming enough interactional viewpoints with plating catalyst or its precursor, its coating weight converted with solid constituent, is preferably 0.1～10g/m ², be preferably 0.5～5g/m especially ²

In addition, coating has comprised the compound compositions with polymerizable group and interaction group on substrate, make its drying, when formation has comprised the layer of the compound with polymerizable group and interaction group, can be between coating and drying, placed 30 minutes～1 hour down at 30～80 ℃, remove residual solvent.

(giving of energy)

As the method that substrate surface is energized, can use for example radiation irradiation such as heating or exposure.Can be for example illumination such as UV lamp, visible rays penetrate, with heating such as hot plate etc.As light source mercury vapor lamp, metal halide lamp, xenon lamp, chemistry lamp, carbon arc lamp etc. are for example arranged.As radioactive ray electron beam, X ray, ion beam, far infrared etc. are arranged.In addition, can also use g ray, i ray, far ultraviolet, high density energy bundle (laser beam).

First-class direct document image, the high brightness flash exposure of passing through infrared laser scan exposure, xenon gaseous discharge lamp etc. and infrared lamp exposure etc. are write down in suitable can listing by heat as concrete scheme commonly used.

As output and the light source and different of needed time of energy according to the graft polymers of target, normally 10 seconds～5 hours are provided.

In addition, when exposure is energized, in order easily to carry out glycerol polymerization, also have, for the decomposition of the graft polymers that suppresses to generate, this exposure power is preferably 10mJ/cm ²～5000mJ/cm ², 50mJ/cm more preferably ²～3000mJ/cm ²Scope.

In addition, as compound with polymerizable group and interaction group, mean molecule quantity is 20,000 or more, the degree of polymerization is the polymer more than 200 unit if use, then owing to can under low-yield exposure, easily carrying out glycerol polymerization, so the graft polymers that can further suppress to generate decomposes.

(a1) operation by as above illustrating can form on substrate by the polymeric layer that graft polymers constituted (graft polymer layer) with interaction group.

The polymeric layer of gained adds in the alkaline solution of pH12 for example, stirs 1 hour time marquis, and being decomposed into below 50% of polymerizable group position in this case, can be washed this polymeric layer with high alkalinity solution.

[(a2) operation]

In (a2) operation, to above-mentioned (a1) but the polymeric layer that forms in the operation gives plating catalyst or its precursor of multiposition coordination.In this operation, constitute the interaction group that graft polymers had of polymeric layer, according to its function, adhere to plating catalyst or its precursor that (absorption) is given.

Here, can list those that play plating catalyst or electrode effect in aftermentioned (a4) electroplating work procedure as plating catalyst or its precursor.For this reason, plating catalyst or its precursor decide according to the kind of the plating in (a4) electroplating work procedure.

In addition, here, the plating catalyst that uses in this operation or its precursor are preferably plated by electroless plating catalyst or its precursor.

(plated by electroless plating catalyst)

The plating catalyst that uses among the present invention just can use arbitrarily so long as can the multiposition coordination, and can list particularly can the multiposition coordination, have the self catalyzed reduction reaction catalysis can metal etc.Can list Pd, Ag, Cu, Ni, Al, Fe, Co etc. particularly.Wherein, but can high aspect from the kind of the functional group of multiposition coordination, catalysis, preferred especially Pd.

(plated by electroless plating catalyst precarsor)

The plated by electroless plating catalyst precarsor that uses in this operation just can use so long as can form the material of plated by electroless plating catalyst by chemical reaction with being not particularly limited.Mainly can use the metal ion of the metal that lists as above-mentioned plated by electroless plating catalyst.Form 0 valency metal as the metal ion of plated by electroless plating catalyst precarsor by reduction reaction as the plated by electroless plating catalyst.Metal ion as the plated by electroless plating catalyst precarsor also can be after being provided to polymeric layer, be impregnated into before the plated by electroless plating bath, change 0 valency metal into by other reduction reaction, form the plated by electroless plating catalyst, by reducing agent in the plated by electroless plating bath, change metal (plated by electroless plating catalyst) in also plated by electroless plating catalyst precarsor direct impregnation can being bathed to plated by electroless plating.

In fact, the metal ion as the plated by electroless plating precursor is to use slaine to be provided on the polymeric layer.So long as be dissolved in the suitable solvent, dissociate into the slaine of metal ion and alkali (anion) as employed slaine, just there is no particular limitation, can list M (NO ₃) _n, MCl _n, M _2/n(SO ₄), M _3/n(PO ₄) (M represents the metallic atom of n valency) etc.The material that is fit to use above-mentioned slaine disassociation formation as metal ion.Can list Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, Pd ion as concrete example, but from the kind and the catalysis of the functional group of multiposition coordination can be high viewpoint, catalysis can aspect preferred Pd ion.

To can be as the metal of plated by electroless plating catalyst or as the method that the slaine of plated by electroless plating catalyst precarsor is provided to polymeric layer: metal is distributed to the dispersion liquid that forms in the suitable dispersant prepares dispersion liquid, perhaps slaine is with suitable dissolution with solvents, prepare the metal ion solution that contains disassociation, this dispersion liquid or solution are coated on the polymeric layer, and the substrate that perhaps will form polymeric layer is impregnated in this dispersion liquid or the solution.By contact plated by electroless plating catalyst or its precursor, thereby utilize the effect of the such molecular separating force of Van der Waals force, perhaps utilize the coordinate bond of lone electron pair, on plated by electroless plating catalyst or its precursor adsorption interaction group in the polymeric layer.

From making this viewpoint of fully adsorbing, the concentration of metal concentration in the dispersion liquid of contact or solution metal ion is preferably the scope of 0.001～50 quality %, the more preferably scope of 0.005～30 quality %.In addition, as being preferably 30 seconds time of contact～24 hours degree, more preferably 1 minute～1 hour degree.

(other catalyst)

In the present invention, in (a4) described later operation,, can use 0 valency metal as not being to carry out plated by electroless plating but the catalyst that uses when directly carrying out metallide to polymeric layer.As this 0 valency metal, can list Pd, Ag, Cu, Ni, Al, Fe, Co etc., particularly can high aspect, preferably Pd, Ag, Cu from absorption (adhesion) property, catalysis to the interaction group.

The function of the electrode when this catalyst plays as the metallide in (a4) operation.

In addition, be provided to the method for polymeric layer, can use the method identical with the method that above-mentioned plated by electroless plating catalyst or its precursor are provided as catalyst with other.

Through (a2) operation of above-mentioned explanation, form between interaction group that can be in polymeric layer and plating catalyst or its precursor and interact.

[(a3) operation]

In (a3) operation, but make polymeric layer contain the metal different (below, be also referred to as " dissimilar metal " sometimes) with the plating catalyst of multiposition coordination or its precursor.

This operation can be at (a2) but give in the operation plating catalyst of multiposition coordination or its precursor the polymeric layer that has been given carry out, in addition, carry out when also can in (a1) operation, form polymeric layer.Just, under latter event, in (a1) operation, use when having comprised compound compositions formation polymeric layer with polymerizable group and interaction group, by in said composition, containing dissimilar metal in advance, can in the polymeric layer that forms, contain dissimilar metal.

In addition, this dissimilar metal also can contain in polymeric layer with the form of metal ion.

The dissimilar metal that uses among the present invention so long as with (a2) but the plating catalyst of the multiposition coordination of using in the operation or the different metal of its precursor, can use arbitrarily, preferably with polymeric layer in the interaction group form to interact in (absorption), also play metal as the function of plated by electroless plating catalyst or electrode.Therefore, the dissimilar metal that (a3) uses in the operation is preferably according to the kind decision of the plating in aftermentioned (a4) operation.

Particularly, the dissimilar metal that uses in this operation is preferably silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), tin (Sn), chromium (Cr) or zinc (Zn), wherein, to the good aspect of the adaptability of plated by electroless plating, more preferably silver, copper or nickel.

As these dissimilar metals being given (a2) but given the method for the polymeric layer of the plating catalyst of multiposition coordination or its precursor in the operation, can be: this dissimilar metal is distributed in the suitable dispersant forms dispersion liquid, the preparation dispersion liquid; Perhaps use suitable dissolution with solvents, preparation contains the metal ion solution of disassociation, and to polymeric layer, the substrate that perhaps will form polymeric layer is impregnated in this dispersion liquid or the solution with this dispersion liquid or solution coat.The dissimilar metal that is given utilizes the effect of the such molecular separating force of Van der Waals force, perhaps utilizes the coordinate bond of lone electron pair (non-share electron pair), is adsorbed onto on the interaction group in the polymeric layer.

From the viewpoint that this absorption is fully carried out, the concentration of metal concentration in the dispersion liquid of contact or solution metal ion is preferably the scope of 0.001～50 quality %, the more preferably scope of 0.005～30 quality %.In addition, as be preferably 30 seconds time of contact～about 24 hours, about more preferably 1 minute～1 hour.

In addition, this operation has comprised when containing the method for dissimilar metal in the compound compositions with polymerizable group and interaction group using, solid constituent amount with respect to said composition, the interior dissimilar metal of scope that preferably contains 0.001～100 quality %, the more preferably scope of 0.005～50 quality %.

(a3) operation through above-mentioned except having added plating catalyst or its precursor, also contains dissimilar metal in polymeric layer.

[(a4) operation]

By the polymeric layer that has given plated by electroless plating catalyst or its precursor is electroplated, form plated film in (a4) operation.The plated film that forms has excellent electric conductivity, adaptation.

The kind of the plating of carrying out in this operation can list plated by electroless plating, metallide etc., in aforementioned (a2) operation with (a3) in the operation, can basis and polymeric layer between form interactional plating catalyst or its precursor and dissimilar metal function select.

Just, in this operation, can carry out metallide, also can carry out plated by electroless plating the polymeric layer that has given plating catalyst or its precursor.

Wherein, in the present invention, plated by electroless plating is preferably carried out in the formation and the adaptation aspect of the hybrid structure that shows from improve polymeric layer.In addition, in order to obtain the electrodeposited coating of desired thickness, more preferably behind plated by electroless plating, carry out the scheme of metallide again.

Below, the plating that is adapted at carrying out in this operation is described.

(plated by electroless plating)

Described plated by electroless plating is meant to use to have dissolved as plating wants the metal ion solution separated out, by the operation of chemical reaction precipitating metal.

Plated by electroless plating in this operation for example is to have given the substrate of plated by electroless plating catalyst and dissimilar metal, washing, remove remaining plated by electroless plating catalyst (metal) after, be impregnated into that plated by electroless plating carries out in bathing.Can use known usually plated by electroless plating to bathe as the plated by electroless plating bath of using.

In addition, the substrate of plated by electroless plating catalyst precarsor and dissimilar metal ion will have been given, with plated by electroless plating catalyst precarsor and dissimilar metal ionic adsorption or be impregnated into the state of polymeric layer, when being impregnated in the plated by electroless plating bath, substrate is washed, after removing remaining precursor (slaine etc.), be impregnated in the plated by electroless plating bath.In this case, in bathing, plated by electroless plating carries out the reduction and the back to back plated by electroless plating of plated by electroless plating catalyst precarsor and dissimilar metal ion.Bathe and above-mentioned same as plated by electroless plating used herein, also can use known usually plated by electroless plating to bathe.

In addition, the plated by electroless plating catalyst precarsor also can carry out following reduction with the dissimilar metal ion: different with the scheme of above-mentioned use plated by electroless plating liquid, prepare catalyst activation liquid (reducing solution) in addition, carry out in another operation before plated by electroless plating.Catalyst activation liquid is the solution that has dissolved reducing agent, and this reducing agent is reduced to 0 valency metal with plated by electroless plating catalyst precarsor (mainly being metal ion) and dissimilar metal ion, and this solution can be 0.1%～50%, is preferably 1%～30%.As reducing agent, can use sodium borohydride, the such boron class reducing agent of dimethyamine borane, reducing agents such as formaldehyde, hypophosphorous acid.

The composition of bathing as common plated by electroless plating mainly comprise 1. electroplate with metal ion, 2. reducing agent, 3. mainly contain the additive (stabilizing agent) that improves metal ion stability.In this electroplating bath, except these compositions, can also contain the known additives such as stabilizing agent of electroplating bath.

The kind of the metal that uses in bathing as plated by electroless plating, known have copper, tin, lead, nickel, gold, palladium, a rhodium.Wherein, from the viewpoint of electric conductivity, special preferably copper, gold.

In addition, also have reducing agent, the additive of suitable above-mentioned metal.For example, the plated by electroless plating of copper is bathed and is contained CuSO ₄As mantoquita, contain HCOH as reducing agent, contain chelating agents such as copper ion stabilizing agent EDTA and Rochelle salt, trialkanolamine as additive etc.In addition, in the electroplating bath that when the plated by electroless plating of CoNiP, uses, contain cobaltous sulfate, nickelous sulfate, contain sodium hypophosphite, contain sodium malonate, natrium malicum, sodium succinate as complexing agent as reducing agent as its slaine.In addition, the plated by electroless plating of palladium is bathed and is contained Pd (DH ₃) ₄) Cl ₂As metal ion, contain NH ₃, H ₂NNH ₂As reducing agent, contain EDTA as stabilizing agent.In these electroplating baths, can add mentioned component composition in addition.

The thickness of the plated by electroless plating plated film of Xing Chenging can wait by the temperature of the concentration of metal ions of electroplating bath, the time that is impregnated into electroplating bath or electroplating bath and control like this, but viewpoint from electric conductivity, be preferably more than the 0.1 μ m, more preferably more than the 0.3 μ m.

In addition, as the time that is impregnated into electroplating bath be preferably 1 minute～about 6 hours, about more preferably 1 minute～3 hours.

As above the electroplating film that obtains with plated by electroless plating is observed section by SEM, and the particulate that can confirm plated by electroless plating catalyst, dissimilar metal and have plated metal to constitute closely is dispersed in the polymeric layer, and then separates out plated metal on polymeric layer.The interface of substrate and plated film is the state that polymer and particulate mix, so the interface of substrate (organic principle) and inorganic matter (catalyst metals or plated metal) level and smooth (for example, concavo-convex difference is that 500nm is following), adaptation is good.

(metallide)

In this operation, be in (a2) operation, to have given plating catalyst or its precursor and the dissimilar metal that (a3) contains in the polymeric layer in the operation has under the situation of electrode function, to having given the polymeric layer of this catalyst or its precursor, carry out metallide.

In addition, can also be behind aforementioned plated by electroless plating, as electrode, can carry out metallide with the plated film that forms.Thus, will with the plated by electroless plating film of substrate adaptation excellence as matrix, form new metal film easily thereon with any thickness.Like this,, carry out metallide, can form the metal film that is fit to purpose thickness, so metal film of the present invention is fit for various uses by behind plated by electroless plating.

Method as the metallide among the present invention can be used existing known method.In addition, the metal that uses in the metallide as this operation can be enumerated copper, chromium, lead, nickel, gold, silver, tin, zinc etc., from the viewpoint of electric conductivity, and preferably copper, gold, silver, more preferably copper.

In addition, the thickness of the metal film that obtains by metallide is according to purposes and different, can wait and controls by regulating the metal concentration that contains in the electroplating bath or current density.In addition, when in common electric distribution etc., using, be preferably more than the 0.5 μ m from the viewpoint thickness of electric conductivity, more preferably more than the 3 μ m.

In the present invention, from the metal or the slaine of aforementioned plating catalyst, plating catalyst precursor, and/or the metal of in polymeric layer, separating out by plated by electroless plating, in this layer, form the microstructure of fragment shape, thereby further improve the adaptation of metal film and polymeric layer.

Be present in amount of metal in the polymeric layer when take a picture taking the substrate section by metallurgical microscopes, occupying in the ratio from the most surperficial metal to the zone of the degree of depth 0.5 μ m of polymeric layer is 5～50 area %, when the arithmetic average roughness Ra of polymeric layer and metal interface (JIS B0633-2001) is 0.05 μ m～0.5 μ m, show stronger closing force.

The manufacture method of＜metallic pattern material (1) 〉

The 1st kind of scheme of the manufacture method of metallic pattern material of the present invention is characterised in that to have: the operation that (b1) forms polymeric layer on substrate, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymeric layer of this substrate direct chemical combination constitute; But (b2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (b3) on this polymeric layer, give the operation of the metal different with the plating catalyst that is somebody's turn to do the multiposition coordination or its precursor; But (b4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; And the operation that (b5) plated film that forms is etched to diagram shape.

Below, in the manufacture method (1) of metallic pattern material (b1) operation～(b5) operation describes.

[(b1) operation]

In (b1) operation, on substrate, form polymeric layer, but this polymeric layer is by having the non-disassociation functional group (interaction group) that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymeric layer of this substrate direct chemical combination constitute.

(a1) operation in (b1) operation in the manufacture method of this metallic pattern material (1) and the manufacture method of the substrate of aforementioned band metal film is identical, and preferred scheme is also identical.

[(b2) operation]

In (b2) operation, to (b1) but the polymeric layer that forms in the operation gives plating catalyst or its precursor of multiposition coordination.

(a2) operation in (b2) operation in the manufacture method of this metallic pattern material (1) and the manufacture method of the substrate of aforementioned band metal film is identical, and preferred scheme is also identical.

[(b3) operation]

In (b3) operation, but polymeric layer is contained and the plating catalyst or the different metal (dissimilar metal) of its precursor that are somebody's turn to do the multiposition coordination.

(a3) operation in (b3) operation in the manufacture method of this metallic pattern material (1) and the manufacture method of the substrate of aforementioned band metal film is identical, and preferred scheme is also identical.

[(b4) operation]

In (b4) operation, to above-mentioned (b2) but the plating catalyst or its precursor that are administered to the multiposition coordination of polymeric layer in the operation are electroplated.

(a4) operation in (b4) operation in the manufacture method of this metallic pattern material (1) and the manufacture method of the substrate of aforementioned band metal film is identical, and preferred scheme is also identical.

[(b5) operation]

In (b5) operation, the plated film that forms in above-mentioned (b4) operation is etched to diagram shape.Just, in this operation,, thereby form desirable metallic pattern with unwanted partially-etched the removing of the plated film of whole formation of substrate surface.

Can use arbitrary method to form this metallic pattern, particularly, can use general known null method, semi-additive process.

Described null method is on the plated film that forms the dry film resist layer to be set, and by graph exposure, development, forms the figure identical with metallic pattern, and the dry film resist pattern as mask, is removed plated film with etching solution, forms the method for metallic pattern.Material arbitrarily can be used as the dry film resist layer, feminine gender, the positive, aqueous, membranaceous material can be used.In addition,, the method for using when making printed wiring board can be used arbitrarily, wet etching, dry ecthing etc. can be selected to use arbitrarily as engraving method.Aspect Job Operations, wet etching apparatus etc. are simple, so preferred.Can use for example aqueous solution of copper chloride, iron chloride etc. as etching solution.

In addition, described semi-additive process is on the plated film that forms the dry film resist layer to be set, form and the identical figure of nonmetal figure portion by graph exposure, development, carry out metallide with the dry film resist pattern as mask, after removing the dry film resist pattern, carry out fast-etching, remove the plated film of diagram shape, form the method for metallic pattern.Dry film resist layer, etching solution etc. can use and the null method identical materials.In addition, electrolytic plating method can use the method for aforementioned record.

Through above-mentioned operation, can make metallic pattern material with desirable metallic pattern.

The manufacture method of＜metallic pattern material (2) 〉

The 2nd kind of scheme of the manufacture method of metallic pattern material of the present invention is characterised in that to have: the operation that (c1) forms the diagram shape polymeric layer on substrate, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (c2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; (c3) but the operation of the metal different with the plating catalyst that contains at this polymeric layer and should the multiposition coordination or its precursor; But (c4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated.

Just, the manufacture method of aforementioned metal graphic material (1) is that the front that spreads all over substrate forms polymeric layer, removes the plated film that forms on this polymeric layer, thereby forms the scheme of desirable metallic pattern; And the manufacture method of metallic pattern material (2) is the polymeric layer that forms diagram shape on substrate, the scheme of the metallic pattern that the polymeric layer of formation and this diagram shape adapts.

Below, in the manufacture method (2) of metallic pattern material (c1) operation～(c4) operation describes.

[(c1) operation]

In (c1) operation, on substrate, form the diagram shape polymeric layer, but this polymeric layer by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute.

(c1) operation in the manufacture method of this metallic pattern material (2) is to be that benchmark carries out with the method that illustrates in (a1) operation in the manufacture method of the substrate of aforementioned band metal, in the manufacture method of the substrate of being with metal film, be that whole face at substrate all forms polymeric layer, and in this programme, form the polymeric layer of diagram shape.

More specifically, in (a1) operation of manufacture method of the substrate of band metal film, when using the surface grafting polymerization method, provide energy by whole face to substrate, form polymeric layer, and in (c1) operation, be in forming the polymeric layer process, the energy of diagram shape is provided, forms the polymeric layer of diagram shape.

The item that illustrates in (a1) operation of manufacture method (1) of the substrate of aforementioned band metal can be similarly used in the detailed description of the relevant item of the substrate (base material and the intermediate layer that can form on base material, polymerization trigger layer) that (c1) operation is used, each key element that constitutes polymeric layer etc.

(providing of energy)

In (c1) operation, the method for energy of diagram shape is provided, and there is no particular limitation, so long as the method that can produce the energy of active site at substrate surface of diagram shape can be provided, just can use arbitrarily.

As the method that the diagram shape energy is provided, electron beams such as the illumination that can be for example infrared laser, ultraviolet lamp, visible rays etc. is penetrated, irradiating gamma-ray, by thermal head heat record etc., but from the viewpoint of the simplification of cost, device, the method for preferably shining active ray.Comprise for example mercury vapor lamp, metal halide lamp, xenon lamp, chemistry lamp, carbon arc lamp etc. as these light sources.Comprise electron beam, X ray, ion beam, far infrared etc. as radioactive ray.In addition, can also use g ray, i ray, far ultraviolet, high density energy bundle (laser beam).

In addition, as concrete scheme commonly used suitable can list by heat write down first-class direct recording geometry, by the infrared laser scan exposure, by high brightness flash exposure such as xenon gaseous discharge lamp and infrared lamp exposure etc.

When the active ray of illumination pattern shape, can also use scan exposure, use any one of graph exposure of graphic arts film based on numerical data.

Like this, by the energy of diagram shape is provided, the active site that substrate surface can be produced and have polymerizable group and overlaps with the compound of interaction group is providing the zone generation graft polymers of energy.

[(c2) operation, (c3) operation and (c4) operation]

(c2) operation in the manufacture method of metallic pattern material (2), (c3) operation and (c4) operation respectively with the manufacture method of the substrate of aforementioned band metal film in (a2) operation, (a3) operation identical with (a4) operation, preferred scheme is also identical.

Through above operation, can make the metallic pattern material that has with the corresponding metallic pattern of figure of polymeric layer.

The substrate and the metallic pattern material of＜band metal film 〉

The substrate of band metal film of the present invention, metallic pattern material are substrate and the materials that the manufacture method by the manufacture method of the substrate of aforementioned band metal film of the present invention, metallic pattern material obtains.

The substrate of the band metal film of formation gained, the polymeric layer of metallic pattern material are as previously mentioned, form interaction with plating catalyst or its precursor, it is non-disassociation, possess hydrophilic property is than the low functional group of disassociation property group, so the hydrophily of polymeric layer itself is also low, temperature, humidity dependence are also low.As a result, can prevent that the metal film (plated film) and the substrate that form from deforming on this polymeric layer.

In addition, even this polymeric layer remains in the metallic pattern material (the metallic pattern material that the manufacture method (1) by metallic pattern material of the present invention obtains) in the zone that does not form metallic pattern, but because the hydrophily in this non-formation zone is low, insulating reliability is also excellent.

On the other hand, the metallic pattern material that the manufacture method (2) by metallic pattern material of the present invention obtains is owing to be the state that does not have polymeric layer in the zone that forms metallic pattern, so the insulating reliability excellence.

It is whole of the substrate of (more preferably below the 100nm) below the 500nm or substrate, the material that the part is provided with metal film (plated film) formation that the substrate of band metal film of the present invention, metallic pattern material are preferably at concave-convex surface.In addition, the adaptation of substrate and metal film (metallic pattern) is preferably more than the 0.2kN/m.Just, it is level and smooth to have a substrate surface, and the feature of the adaptation excellence of substrate and metal film (metallic pattern).

In addition, the concavo-convex of substrate surface is that relative substrate surface vertically cuts off substrate, observes the value that its section is measured by SEM.

In more detail, the Rz that measures according to JIS B0601, just " in given side, from the mean value of the Z data that are up to the 5th big summit and poor from the mean value of the little the lowest point of minimum to the 5 " is preferably below the 500nm.

In addition, the value of the adaptation of substrate and metal film is with epoxy adhesive (ア ラ Le ダ イ ト (I throws by Shandong paddy one), チ バ ガ イ ギ-(very clinging to loud, high-pitched sound one gives) made), with copper coin (thickness: 0.1mm) bond to the surface of metal film, after under 140 ℃ the temperature dry 4 hours, carry out 90 degree based on JIS C6481 and peel off experiment, perhaps directly strip the end of metal film itself, carry out 90 degree based on JIS C6481 and peel off the resulting value of experiment.

The substrate of the band metal film that the manufacture method of the substrate by band metal film of the present invention obtains, for example can be used as anti electromagnetic wave film etc., perhaps pass through metal film (plated film) etching is formed figure, and be used for various uses such as semiconductor chip, various electric distributing board, FPC, COF, TAB, antenna, multi-layered wiring board, motherboard.

In addition, the metallic pattern material that obtains of manufacture method (1) and (2) by the metallic pattern material also can be used for above-mentioned various uses.

Embodiment

Below, the present invention is described in detail by embodiment, but the present invention is not subjected to their any qualification.In addition, if there is no particular limitation, " % " and " part " is quality criteria.

[embodiment 1]

[manufacturing of substrate]

On glass epoxy substrate, epoxies dielectric film GX-13 (thickness 45 μ m) heating, the pressurization that to make as aginomoto fine chemistry (the monosodium glutamate Off ア イ Application テ Network ノ) company of electric insulation layer, pass through vacuum laminator, bonding under the pressure of 0.2MPa, 100 ℃～110 ℃ condition, obtain base material A.

Then, by spin-coating method coating thickness on base material A is the insulating properties composition of 3 microns the polymerization initiator that contains following composition, places 1 hour down at 30 ℃, except that after desolvating, drying is 30 minutes under 170 ℃, forms polymerization trigger layer (the polymerization trigger layer of insulating properties).

(the insulating properties composition that contains polymerization initiator)

Stir on one side, on one side with 20 mass parts bisphenol A type epoxy resin (epoxide equivalents 185, エ ピ コ-ト 828 (a Chinese mugwort mouth throws 828) that oiling シ エ Le エ Port キ シ (Xi Ailu cuts open the gram west) (Co., Ltd.) makes), 45 mass parts line style phenol formaldehyde (PF) epoxy resin (epoxide equivalents 215, the エ ピ Network ロ Application N-673 that big Japanese イ Application キ (Yin Ke) chemical industry (Co., Ltd.) is made (a Chinese mugwort storehouse dragon N-673)), 30 mass parts novolac resin (phenolic hydroxyl group equivalents 105, the Off エ ノ ラ イ ト that big Japanese イ Application キ (Yin Ke) chemical industry (Co., Ltd.) is made (method Chinese mugwort slave throws the Rye)), heating for dissolving in 20 parts of ethyl diethylene glycol (DEG) acetic acid esters and 20 parts of solvent naphthas, behind the cool to room temperature, toward the cyclohexanone varnish (YL6747H30 of oiling シ エ Le エ Port キ シ (it is western that Xi Ailu cuts open gram) (Co., Ltd.) manufacturing that wherein adds the phenoxy resin that 30 mass parts form by aforementioned エ ピ コ-ト 828 (a Chinese mugwort mouth throws 828) and bisphenol S, nonvolatile component 30 quality %, weight average molecular weight 47000), 0.8 mass parts 2-phenyl-4,5-two (hydroxymethyl) imidazoles, 2 mass parts micro mist bitstones, 0.5 the silicone based defrother of mass parts, again in this mixture, add 10 parts by the synthetic polymerization initiated polymerization thing P of following method, obtain containing the insulating properties composition of polymerization initiator.

(polymerization initiated polymerization thing P's is synthetic)

In the there-necked flask of 300ml, add 30g propylene glycol monomethyl ether (MFG), be heated to 75 degree.In 2.5 hours to wherein dripping 8.1g bromination [2-(acryloxy) ethyl] (4-benzoyl benzyl) Dimethyl Ammonium, the methacrylic acid 2-hydroxyethyl ester of 9.9g, 13.5g methacrylic acid isopropyl esters, 0.43g dimethyl-2, the solution of the MFG of 2 '-azo two (2 Methylpropionic acid ester) and 30g.Afterwards, reaction temperature is elevated to 80 degree, reacted again 2 hours, obtain having the polymer P of polymerization initiating radical.

After forming above-mentioned this polymerization trigger layer, under 180 ℃, carry out solidifying in 30 minutes and handle.Thus, obtain substrate Al.The concave-convex surface (Rz) of this substrate Al is 0.1 μ m.

[formation of polymeric layer]

(polymer 1 synthetic) with polymerizable group and interaction group

At first, following synthetic polymer 1 with polymerizable group and interaction group.

In the there-necked flask of 1000ml, add 20gN, the N-dimethylacetylamide flows down at nitrogen, is heated to 75 ℃.Divide the acrylic acid 2-hydroxyethyl ester, the 4-vinylpridine (monomer) of 31.1g and the N that contains the 20g of 0.85gV-601 (with the pure medicine manufacturing of light) that dripped 8.6g in 2.5 hours, the solution of N-dimethylacetylamide with interaction group.After dripping, be heated to 80 ℃, stirred again 3 hours.Afterwards, with the reaction solution cool to room temperature.

Add 0.37g two amyl hydroquinone, 0.47g dibutyl tin laurate, the カ レ Application ズ AOI (Ka Lanzi AOI) (Showa Denko K. K's manufacturing) of 23.3g, the N of 25g in above-mentioned reaction solution, the N-dimethylacetylamide was 55 ℃ of reactions 4 hours.Afterwards, in reactant liquor, add 20.0g methyl alcohol, reacted again 2 hours.After reaction finished, precipitation was crossed filter solid, washing, and drying obtains the polymer 1 (following structure) that 15g has polymerizable group and interaction group.

In addition, " カ レ Application ズ AOI (Ka Lanzi AOI) " is a kind of monomer with polymerizable group, and it has NCO.

[changing 6]

(generation of graft polymers)

9.6 mass parts are had polymer 1,76.0 mass parts isopropyl alcohols, 33.9 mass parts methyl alcohol and the 4.8 mass parts N of polymerizable group and interaction group, and the N-dimethylacetylamide mixes, the preparation coating solution.

Then, by spin-coating method, the coating solution for preparing is applied on the polymerization trigger layer of aforesaid base plate A, so that thickness is 1.0 μ m, after under 80 ℃ dry 30 minutes, use the UV exposure machine (model: UVF-502S of three motor manufacturings forever, lamp: UXM-501MD), with 1.5mW/cm ²Irradiation energy (measuring the energy that the ultraviolet ray accumulation quantometer UIT150-with ウ シ オ (Ouchy Europe) motor manufacturing is shone by optical sensor UVD-S254), shone for 660 seconds, all generate graft polymers at the whole face of the polymerization trigger layer of substrate A1.

Afterwards, the substrate A1 that has generated graft polymers was flooded 5 minutes in the methyl alcohol of stirring, clean with distilled water then.

Thus, obtain having the substrate A2 of polymeric layer.

[providing of plating catalyst]

The substrate A2 that will have polymeric layer floods after 10 minutes in the palladium chloride aqueous solution of 0.2 quality %, is impregnated in the distilled water to clean.

Then, in 1L water, add treatment fluid MRD2A, the MRD2C of 60mL of the last village industry manufacturing of 18mL, make substrate A2 dipping in the catalyst activation liquid (reducing solution) of preparation like this be impregnated in the distilled water clean after 5 minutes with polymeric layer.

[providing of dissimilar metal]

Then, the substrate A2 that will have polymeric layer floods after 10 minutes in the silver nitrate aqueous solution of 1 quality %, is impregnated in the distilled water to clean.

[plated by electroless plating]

To the above-mentioned substrate A2 that obtains with the polymeric layer that has added plating catalyst, use the plated by electroless plating of following composition to bathe, under 60 ℃, carry out 5 minutes plated by electroless plating.The thickness of the non-electrolytic copper plated film of gained is 0.3 μ m.

(composition that plated by electroless plating is bathed)

Distilled water 1709g

Copper sulphate 18.1g

Ethylene diaminetetraacetic acid 2 sodium salt 54.0g

Polyoxygenated ethylidene glycol (molecular weight 1000) 0.18g

2,2 '-bipyridyl 1.8mg

10% ethylene amine aqueous solution 7.1g

37% formalin 9.8g

The pH of above electroplating bath composition can be adjusted to 12.5 (60 ℃) with NaOH and sulfuric acid.

[metallide]

Then, the plated by electroless plating film as power supply layer, is used the cathode copper electroplating bath of following composition, at 3A/dm ²Condition under, metallide 30 minutes.The thickness of the electrolytic copper plated film of gained is 18 μ m.Thus, obtain substrate A3. with metal film

(composition that metallide is bathed)

Copper sulphate 38g

Sulfuric acid 95g

Hydrochloric acid 1mL

カ Star パ-グ リ-system PCM (Ka Paguli wood PCM) (manufacturing of メ Le テ Star Network ス (Mai Lutaikusi) Co., Ltd) 3mL

Water 500g

(adaptation evaluation)

To the plated film of the substrate A3 of the band metal film of the wide gained of 5mm, (エ of Co., Ltd.-ア Application De デ-(Ai Ang struggle against Di) manufacturing RTM-100), with the hot strength of 10mm/min, measures 90 ° of peel strengths, is 0.65kN/mm to use cupping machine.

(insulating reliability test)

In the coated surface of the substrate A3 of the band metal film of gained, correspondingly form resist layer when as the residual zone of metallic pattern (wiring graph), there is not the plated film in the zone of resist layer, by by FeCl ₃The etching solution that/HCl constitutes is removed.Afterwards, remove resist layer, be formed for measuring the comb shape distribution of the wiring closet insulating reliability of line and gap=100 μ m/100 μ m by the alkali stripper that constitutes by 3%NaOH solution.

With this comb shape distribution, in the HAST testing machine (AMI-150S-25) that ESPEC makes, in 125 ℃-85% relative humidity (unsaturation), apply under voltage 10V, 2 atmospheric pressure, when placing 200 hours, do not find the not good problem of insulation of wiring closet.

Like this, even place down hot and humid, also find the problem that insulation is not good, so can know that the water imbibition of the polymeric layer that constitutes this comb shape distribution is low, temperature, humidity dependence are low.Just, can know that the water imbibition of polymeric layer of the substrate A3 that constitute to form the band metal film before the comb shape distribution is also low, temperature, humidity dependence are low.

[embodiment 2]

Except the dissimilar metal aqueous solution that uses among the embodiment 1 being changed into the 1wt% nickelous sulfate 6 hydrate aqueous solution and embodiment 1 similarly obtain substrate with metal film.By the method identical with embodiment 1, measure 90 ° of peel strengths of substrate of the band metal film of gained, be 0.64kN/m.

In addition and embodiment 1 similarly carry out insulating reliability test, do not find that the insulation of wiring closet is bad.

[embodiment 3]

Except in embodiment 1, the methyl alcohol of 33.9 mass parts that formation is contained the coating solution of polymer 1 with polymerizable group and interaction group, change into beyond the ethanolic solution of 1% trifluoroacetic acid silver of 33.9 mass parts and embodiment 1 similarly obtains substrate with metal film.By the method identical with embodiment 1, measure 90 ° of peel strengths of substrate of the band metal film of gained, be 0.68kN/m.

In addition and embodiment 1 similarly carry out insulating reliability test, do not find that the insulation of wiring closet is bad.

[embodiment 4]

Except in embodiment 1, remove beyond the operation of adding dissimilar metal and embodiment 1 similarly obtains substrate with metal film.By the method identical with embodiment 1, measure 90 ° of peel strengths of substrate of the band metal film of gained, be 0.60kN/m.

In addition and embodiment 1 similarly carry out insulating reliability test, do not find that the insulation of wiring closet is bad.

Can know from The above results,, on level and smooth substrate, can form adaptation metal film well, and not form the insulating reliability excellence in the zone of metallic pattern according to the present invention.Therefore, the substrate of the band metal film that the application of the invention obtains (metallic pattern material) can obtain the printing distributing board of the reliability excellence of electricity.

Claims (13)

1, the manufacture method of the substrate of band metal film, wherein, has (a1) forms polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (a2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (a4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; Perhaps

After (a2) operation, also has following (a3) operation;

(a3) but make this polymeric layer contain the operation of the metal different with plating catalyst that should the multiposition coordination or its precursor.

2, the manufacture method of the substrate of the band metal film put down in writing of claim 1 wherein, is nitrogen-containing functional group, oxygen-containing functional group or sulfur-bearing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

3, the manufacture method of the substrate of the band metal film put down in writing of claim 1 or 2 wherein, is a nitrogen-containing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

4, the manufacture method of the substrate of each band metal film of being put down in writing of claim 1～3, wherein, but the plating catalyst of aforementioned multiposition coordination or its precursor are palladium or palladium ion.

5, the manufacture method of the substrate of each band metal film of being put down in writing of claim 1～4, wherein, but aforementioned plating catalyst or the different metal of its precursor with the multiposition coordination is silver, copper, nickel, cobalt, tin, chromium or zinc.

6, the substrate of the band metal film that the manufacture method of the substrate of each band metal film of being put down in writing obtains with claim 1～5.

7, the manufacture method of metallic pattern material, wherein, has (b1) forms polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (b2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (b4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; (b5) plated film that forms is etched to the operation of diagram shape; Perhaps

After (b2) operation, also has following (b3) operation;

(b3) but make this polymeric layer contain the operation of the metal different with plating catalyst that should the multiposition coordination or its precursor.

8, the manufacture method of metallic pattern material, wherein, has (c1) forms the diagram shape polymeric layer on substrate operation, but this polymeric layer is by having the non-disassociation functional group that forms interactional multiposition coordination with plating catalyst or its precursor, and and the polymer of this substrate direct chemical combination constitute; But (c2) on this polymeric layer, give the operation of plating catalyst or its precursor of multiposition coordination; But (c4) operation that plating catalyst or its precursor of this multiposition coordination are electroplated; Perhaps

After (c2) operation, also have following (c3) operation,

(c3) but make this polymeric layer contain the operation of the metal different with plating catalyst that should the multiposition coordination or its precursor.

9, the manufacture method of the metallic pattern material put down in writing of claim 7 or 8 wherein, is nitrogen-containing functional group, oxygen-containing functional group or sulfur-bearing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

10, the manufacture method of each metallic pattern material of being put down in writing of claim 7～9 wherein, is a nitrogen-containing functional group but aforementioned and plating catalyst or its precursor form the non-disassociation functional group of interactional multiposition coordination.

11, the manufacture method of each metallic pattern material of being put down in writing of claim 7～10, wherein, but the plating catalyst of aforementioned multiposition coordination or its precursor are palladium or palladium ion.

12, the manufacture method of each metallic pattern material of being put down in writing of claim 7～11, wherein, but aforementioned plating catalyst or the different metal of its precursor with the multiposition coordination is silver, copper, nickel, cobalt, tin, chromium or zinc.

13, the metallic pattern material that the manufacture method of each metallic pattern material of being put down in writing obtains with claim 7～12.