CN1111567A - Copper clad laminate, multilayer printed circuit board and their processing method - Google Patents

Abstract

To provide a copper clad laminate having a bonded part wherein copper foils or copper foil and an insulating layer are strongly bonded, without providing roughing treatment or black treatment on the copper foil, by designing such a configuration that the copper foil has a metal layer on the side to be bonded with the insulating layer and the metal layer and insulating layer are cross-linked with each other by chemical bonds through sulfur atoms. Further, there is provided a multilayer printed circuit board which has a bonded side ensuring a powerful adhesion of the circuit copper foil and insulating layer, by designing such a configuration that the alternating metal layers and insulating layers are cross-linked with each other by chemical bonds through sulfur atoms. The bonding intensity of the bonding layer can be improved by the processing of the copper clad laminate and the multilayered printed circuit board immersed in an aqua solution containing hydrochloric acid or salts thereof to be treated.

Description

Copper clad laminate, multilayer printed circuit board and their processing method

The present invention relates to be used for the film of printed circuit or the copper clad laminate that substrate is used, multilayer board, and processing method.According to Purinto Kairo Gijutsu Binran(" printed circuit handbook ", the 2nd edition, Nikkan Kogyo Shinbun Co., Ltd. publish), copper clad laminate comprises: (1) is by Copper Foil and paper-based phenolic resin, paper substrate epoxy resin, the paper substrate mylar, glass cloth basic ring epoxy resins, glass fabricbase polyimide resin, the laminate of glass fabricbase BMI-cyanate resin or glass fabricbase fluoroplastics system, (2) by Copper Foil and flooded the fabric laminate of epoxy resin or low-k resin virtue acid amides and (3) by glass cloth basic ring epoxy layer and the compound copper clad laminate formed as the paper or the non-woven glass fabricbase epoxy resin of core material.Described laminate is hard copper clad laminate, in addition, also is useful on the another kind of copper clad laminate of flexible printed circuit board, and the latter sticks with glue the agent bonding and makes usually by a slice soft plastic film and Copper Foil.Polyester film and polyimide film are used as this plastic foil.

Copper Foil can be divided into two classes: electrodeposited copper foil and roll-in Copper Foil.And they can be divided into many classes according to classification, for example corresponding to the classification of used resin Copper Foil, according to the thickness of Copper Foil and the classification of engineering properties.

So far the Copper Foil of coating binder has been used for the copper clad laminate of phenolic resins copper clad laminate and flexible printed circuit board.In addition, under the situation of epoxy resin copper clad laminate and polyimide resin copper clad laminate, resin material has been used as directly bonding insulating barrier.The electric conductor of printed circuit board (PCB) greatly reduces at interval in recent years, and this is because the density of electronics equipment increases, and weight and volume reduces event.This tendency has caused producing following requirement: to restrain bubble in the fusion weld dipping and produce when printed circuit board (PCB) immerses, eliminate any problem that produces in the drilling operation, and when needs are electroplated to the corrosion resistance of electroplating chemical product.Proposed to have the requirement of so very harsh performance and littler circuit profile aspect.These require conversely the adhesion strength between this class insulating barrier of strong request Copper Foil and synthetic resin matrix again.In order to ensure adhesion strength, under the situation of electrodeposited copper foil, bonding surface at the protuberance of the electrodeposited copper foil convex-concave structure that is referred to as former paper tinsel or end paper tinsel provides usually with molecule (being called hacking), produces the grappling effect of improving intensity to guarantee to see from the microcosmic viewpoint; And, the barrier layer and the antirust processing of formation also are provided.This hacking is handled and has been guaranteed that the adhesion strength between copper foil surface and the insulating barrier is in realistic scale.Yet on the other hand, at first, in the circuit forming process, not etched in predetermined etching period in the convex-concave structure that copper foil surface forms, and on stromal surface, be left residual copper, therefore it just becomes and makes electrical vitiable reason, and just needs quite long etching period in order to remove this remaining copper.This causes that the facet etch degree increases, and makes to be difficult to form a kind of high-quality circuit.For this purpose, the light etching of desirability in recent years, its limit is by trading off with adhesion strength and reaching.Secondly because the convex-concave structure of Copper Foil causes that high frequency waveforms is disturbed, further light etching has proposed requirement to degree.

Traditionally, epoxy resin and butyraldehyde-phenolic resin base adhesive has been used as the adhesive of Copper Foil and synthetic resin matrix (dielectric substrate).Be based on hydrogen bond and utilize the fine grain grappling effect that forms at copper foil surface with the bonding of Copper Foil, this kind situation does not belong to chemical bonding; Thereby enough adhesion strengths have only the wet look (smooth surface) when Copper Foil to be subjected to the hacking processing, comprise when blackout is handled just guaranteed.

As mentioned above, according to prior art, in the laminate that comprises Copper Foil and insulating barrier, adhesion strength is to be used for increasing by the grappling that the particulate on the ledge of the end paper tinsel that sticks to Copper Foil (former paper tinsel) provides.Therefore, in (1) etching in the circuit forming process, need the more time to remove ledge and the particulate that is embedded in the insulating barrier (for example synthetic resin matrix), and the etching of Copper Foil generating plane; Be restricted so reduce little line width, and for the limit that on Copper Foil, forms little circuit, the limit of width fixed on 0.1mm in industrial consideration.(2) handle the number of times that has caused the process that increases and reduce productivity ratio by the hacking that provides particulate to carry out; Thereby be difficult to reduce the Copper Foil production cost.(3) the hacking condition is difficult to control, makes to be difficult to guarantee to obtain uniform product quality.(4) in addition, for guaranteeing the brute force bonding between prepreg and Copper Foil, blackout is handled and is necessitated, to keep the adhesion strength of Copper Foil protuberance in the multilayer of multilayer circuit board forms.

On the other hand, the bonding between elastomeric material and metal or elastomeric material and the laminate is disclosed in U.S.P.No.4,446,198, the open No.51-57783 of Japan Patent, Japanese patent publication NO.60-14836, No.56-19820 are among open No.54-53180 of Japan Patent and the No.1-201454.Yet, do not have the example explanation on Copper Foil, to form metal level, and provide between Copper Foil and insulating barrier through crosslinked bonding by chemical bond through sulphur atom.In addition, the open No.3-111464 of Japan Patent has described and has utilized the acrylic-nitrile rubber that contains zinc oxide as the adhesive between laminate and Copper Foil, but the not mentioned metal level that forms on Copper Foil, and provides crosslinked bonding by the chemical bond through sulphur atom.

An object of the present invention is to solve the problem of prior art, the copper clad laminate that to provide with good high-frequency signal transmission performance be characteristics, this laminate with bonding cross section is characterised in that: between Copper Foil and the Copper Foil or the brute force between Copper Foil and insulating barrier bonding, do not need to form protuberance or provide the hacking of particulate or blackout to handle to protuberance.

Another object of the present invention is to provide a kind of multilayer board, and this printed circuit board (PCB) has the bonding cross section of powerful bonding between system Copper Foil of circuit and the insulating barrier, and has good high-frequency signal transmission performance.

Another object of the present invention also is a kind of processing method is provided, be used for further improving between the Copper Foil of copper clad laminate and insulating barrier or the circuit Copper Foil of multilayer board and the caking property between insulating barrier.

The present inventor is paid to go out great efforts and solves described problem.As a result, they find, Copper Foil and metal level can be by using specific metal level and use specific adhesive on Copper Foil, reach powerful adhesive bond through chemical bond is crosslinked.This discovery causes having finished the present invention.The solution of the problem of above-mentioned prior art, the bonding surface that need not the hacking Copper Foil owing to the adhesive that powerful adhesion strength occurs guaranteeing becomes possibility.

In other words, the present invention will provide the copper clad laminate of following feature, in the copper clad laminate of the wherein Copper Foil with bonding cross section and insulating barrier lamination and bonding, its paper tinsel has metal level on the adhesive surface between Copper Foil and insulating barrier, metal level and insulating barrier are crosslinked by the chemical bond through sulphur atom.Sulphur atom number in this chemical combination key is 1 to several, and the sulphur source of sulphur atom then is the such vulcanizing agent of sulphur, sulfur donor and thio-alcohol.

If copper clad laminate of the present invention has the bonding cross section, wherein adhesive surface have the Copper Foil of metal level and as the insulating barrier of adhesive layer by lamination and bonding, the restriction that it is not formed by any concrete layer.A kind of may be that insulating barrier is mutually crosslinked with Copper Foil, and wherein the bonding surface of Copper Foil has metal level, and metal matrix is lamination and is bonded on the insulating barrier of crosslinked and Copper Foil bonding.Also have and a kind ofly may be, insulating barrier is made up of the crosslinked adhesive layer that is used as synthetic resin matrix, in other words, it can be the insulating barrier as the synthetic resin substrate that is cross-linked to form by the adhesive that impregnated in substrate, and described substrate comprises has flooded the substrate that contains the adhesive with the compound that can vulcanize unsaturated bond and be selected from least one class vulcanizing agent of sulphur, sulfur donor and thio-alcohol.Should be pointed out that to form CuS at copper foil surface when not having metal level when only Copper Foil being arranged, the result significantly reduces adhesion strength.

Cyano group ester resin, epoxy resin and polyimide film contain can vulcanize unsaturated bond, or available multiple mode becomes and contains unsaturated bond.The basic molecular structure of these compounds can become to contain can vulcanize unsaturated bond.But also might by with can mix with fine other sulfide polymer that mixes of these resins, and make them contain unsaturated bond.These resins are used as the adhesive components of described matrix impregnation effectively.

In addition, also may have the film that forms coating binder on the Copper Foil of metal level, and, allow to form vulcanizable unsaturated bond in the insulation bottom surface of matrix by lamination on the surface, form Copper Foil and matrix, thereby form Copper Foil and dielectric substrate through crosslinked and copper clad laminate bonding.In addition, also may be applied to the cross-linked rubber stick and prepare, and form prepreg and the Copper Foil that the surface has metal level, thereby form Copper Foil and dielectric substrate copper clad laminate by crosslinked bonding through lamination as on the prepreg of dielectric substrate.

Dielectric substrate of the present invention is not limited to be used in as in common printed circuit or any other new copper clad laminate.Those are by also can using that hard synthetic resin matrix or mantle matrix are made.Conducting channel can be on dielectric substrate or inner formation.This conducting channel can be formed by the Copper Foil of band metal level among the present invention, also can be formed by the copper clad laminate of prior art.

In addition, copper clad laminate of the present invention also can have conventional bonding cross section except that having bonding of the present invention cross section.And laminate also can have anticorrosion layer, as stainless steel foil, and aluminium foil and nickel foil.In this case, but the adhesive of anticorrosion layer the application of the invention, through laminated bonding to insulating barrier.

If the used adhesive of the present invention is used to obtain the copper clad laminate with bonding cross section, get up by laminated bonding at bonding section Copper Foil and dielectric substrate through metal level, then this adhesive just bonds through being cross-linked to form the powerful chemical key with the metal level of Copper Foil, thereby superior bond strengths rendering is provided.In described metal matrix, except that Copper Foil, the used adhesive of the present invention demonstrates the powerful adhesion strength based on the direct chemical key when having described surface-treated metal level.

The laminated bonding condition is selected from following scope usually, but is not limited thereto: 100-250 ℃, 5-300kg/cm ²With 5-90 minute.The condition that makes a choice is at the sulfuration between the surface-treated layer of described adhesive and Copper Foil or metal matrix, and the sulfuration that itself takes place at the same time of described adhesive (these conditions can by easy experimental selection), thereby realize boning based on the brute force of mutual chemical bond.This adhesion strength is enough high.These conditions can be obtained by simple experiment, and the condition of finding out is the brute force bonding that guarantees that adhesive and metal level combine.

The present invention aspect the multilayer board of the multilayer circuit Copper Foil that forms at the Copper Foil that has by dielectric substrate inside, provides the printed circuit board (PCB) with following feature: metal level and insulating barrier crosslinked bonding the by being produced by the chemical bond through sulphur atom.

An instantiation of this multilayer board comprises the circuit Copper Foil as a pair of wiring board of base plate, they are by through having the crosslinked bonding of the compound that can vulcanize unsaturated bond, and the material that has flooded adhesive, wherein adhesive contains at least one class vulcanizing agent that is selected from sulphur, sulfur donor and mercaptan.Circuit Copper Foil and improved mechanism of the bonding between insulating barrier and copper clad laminate is identical in multilayer board.

The instantiation of dielectric substrate comprises: (1) those by the paper-based phenolic resin laminate, the paper substrate epoxy laminate, paper substrate polyester resin layer pressing plate, glass cloth basic ring epoxy layer pressing plate, glass fabricbase polyimide resin layer pressing plate, glass fabricbase fluoroplastic layer pressing plate, the hydrocyanic ester resin of glass fabricbase BMI-triazine layer pressing plate and the modification of glass fabricbase is formed, (2) those are by aromatic polyamide resin, that the polyimides that fiber or cloth strengthen or the polyimides of hydrocyanic ester resin or heat stable resin such as low-k and fluoroplastics are formed and (3) those by glass cloth basic ring epoxy layer pressing plate on the surface and paper or adhesive-bonded fabric basic ring epoxy resins be the dielectric substrate that the composite laminate of core material is formed.

In addition, also might use the matrix of silicon matrix, gallium base semiconductor sheet, glass matrix, ceramic substrate and application beryllium oxide, graphite, boron nitride and paper.

The example of metal matrix comprises iron plate (silicon steel, stainless steel), aluminum matrix and titanium matrix.

The Copper Foil of usefulness can be electrolytic deposition Copper Foil or roll-in Copper Foil in the present invention.Its thickness is unfixing, is generally 3-500 μ m, preferred 5-500 μ m, more preferably 5-150 μ m.

Should be pointed out that if Copper Foil is thinner than 3 μ m, may crease or break; It handles inconvenient.If Copper Foil is thicker than 500 μ m, copper product just may be made on the Copper Foil of electrolytic deposition, and this copper foil surface (dull surface) is characterised in that unevenness lacks uniformity.

Preferably use the following metal level of formation on the bonding surface of Copper Foil, this metal level comprises and contains the metal or metal alloy that is selected from least a element among B, Al, P, Cu, Zn, Ti, V, Cu, Mn, Fe, Co, Ni, Ag, In, Zr, Sn, Nb, Mo, Ru, Rh, Pd, Pb, Ta, W, Ir and the Pt.The example of this alloy has Cu-Zn alloy, Ni-Zn alloy, Ni-Sn alloy, Ni-Cu alloy, Pd-P alloy and Ni-P alloy.In order to ensure the adhesion strength of brute force, its compositing range is Cu with respect to the ratio of other element is 1-90 weight (wt%), more preferably 5-70wt%.Ni is 1-90wt%, more preferably 5-70wt% with respect to the ratio of other element (as Zn, Sn, Cu and P).In addition, for high-frequency applications, nonmagnetic metal is absolutely necessary, for example the alloy of other element beyond Pd and Pd and the Pd (as with the alloy of P).Pd is 1-99wt%, more preferably 60-95wt% with respect to the ratio of other element.Should be pointed out that Cu is not as independently metal level use; It only is used as a kind of alloying element.As the example of complex metal layer, the Pd-P alloy is used as and forms the bottom barrier metal layer, comprises that the metal level of Cu-Zn is used as surface metal-layer.

The method that forms these metal levels comprises plating, vapor deposition plating and sputter.Usually the viewpoint from productivity ratio is preferred with electroplating.As the example of metal level formation method, be that palladium is restored by chemical plating from the formalin solution of palladium bichloride, form metal level in the colloid catalyst of palladium bichloride and tin ion thereby perhaps palladium is immersed.

Metal layer thickness is generally 5 μ m or littler, preferred 0.01-5 μ m, and more preferably 0.01-1 μ m, but be not limited to these numerical value.

Even metal layer thickness surpasses 5 μ m, its adhesion strength is saturated and no longer increase.In addition, according to existing manufacturing process, be difficult to make the even metal level of thickness less than 0.01 μ m.Pin hole may exist, and the Copper Foil under the face may come out, and causes adhesion strength to reduce.

Copper foil surface on bonding surface can be hacking or smooth.According to copper clad laminate of the present invention, even for the Copper Foil with smooth surface (this Copper Foil does not have the grappling effect), also can guarantee powerful adhesion strength, saved the needs of Copper Foil hacking technology.For frequency applications, the present invention allows to use the Copper Foil with smooth surface.

When for example making electrodeposited copper foil, a kind of method that forms paper tinsel at the bottom of the roll-in or so-called former paper tinsel is arranged, the method be in copper sulfate solution with rotary drum do negative electrode in a continuous manner electrolytic deposition go out Copper Foil, Copper Foil is just separated in a continuous manner.In the case, from then on drum upward is called wet look or drum face (S) in isolated surface, and it has more smooth surface.Its another side then is called the dull surface (M) with convex.In next hacking treatment process, particulate is provided on convex, obtain the surface of handling through hacking.In other method, carry out the antirust processing of electrochemistry for the dull surface of Copper Foil, this processing is called as surface treatment or post processing.Used adhesive can be guaranteed the brute force bonding between Copper Foil and Copper Foil or Copper Foil and insulating barrier among the present invention, does not need hacking to handle.

When the copper foil surface unevenness is pressed JIS(Japanese Industrial Standards)-during the expressing with the average unevenness Ra of center line of B-0601 regulation, the Ra of the S face in the electrodeposited copper foil is generally 0.1-0.35 μ m, and the Ra of the M face of handling without hacking is about 0.1-2.0 μ m.On the other hand, the surface irregularity of roll-in Copper Foil on the two sides is 0.1-0.15 μ m.Copper clad laminate of the present invention has the advantage of guaranteeing enough adhesion strengths, need not use the Copper Foil with any of these surface irregularity, thereby has enlarged the range of choice of Copper Foil.When copper clad laminate was used for the high frequency waveforms signal, the surface irregularity Ra that needs Copper Foil to have was 0.35 μ m or lower, from the preferred 0.2 μ m or lower of the viewpoint of skin effect.In the case, can guarantee enough adhesion strengths.

Containing the adhesive that has the compound that can vulcanize unsaturated bond and be selected from least one class vulcanizing agent in sulphur, sulfur donor and the thio-alcohol is used among the present invention as the adhesive through crosslinked bonding.

Described adhesive layer thickness is 5-1000 μ m preferably.When adhesive layer thickness was lower than 5 μ m, adhesion strength and insulating properties all can reduce.Even adhesive layer thickness surpasses 1000 μ m, adhesion strength no longer increases, thereby uneconomical.The preferred scope of adhesive layer thickness is 10-500 μ m.

Having monomer, oligomer, polymer or the elastomer that can vulcanize unsaturated bond is used as and has the compound that can vulcanize unsaturated bond.

Oligomer, polymer or elastomeric example comprise styrene butadiene ribber (SBR), butadiene rubber (BR), the nitrile butadiene rubber (NBR) that has based on the unsaturated bond of butadiene; Have natural rubber, isoprene rubber (IR), neoprene (CR), butyl rubber (IIR) and chloro butyl rubber based on the unsaturated bond of isoprene; Have based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB) and 1,4-hexadiene (1, the ethene-alpha-olefin copolymer elastomer of unsaturated bond 4-HD), the i.e. ethene-alpha-olefin copolymer that obtains by the copolymerization of alhpa olefin and dienes, for example ethylene propylene diene terpolymers (EPDM) and ethylene butene diene terpolymer (EBDM).Especially be preferred with EBDM.Example also comprises the halo nitrile rubber, the carbon fluorubber, as 1,1-difluoroethylene-hexafluoropropylene copolymer and 1,1-difluoroethylene-five fluorine propylene copolymer, chloropropylene oxide homopolymers (CO), copolymer rubber (ECO) by chloropropylene oxide and oxirane preparation, chloropropylene oxide allyl glycidol copolymer, expoxy propane allyl glycidyl ether copolymer, expoxy propane chloropropylene oxide allyl glycidyl ether trimer, acrylic rubber (ACM), polyurethane rubber (U), silicon rubber (Q), CSM (CSM), polysulfide rubber and ethylene acrylic rubber.Other example comprises liquid rubber, for example each class I liquid I butadiene rubber and liquid atactic butadiene rubber, and the latter is with 1, the butadiene polymer that the 2-vinyl connects by the preparation of anion activated polymerization.Also may use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN etc., Ube Industries, Ltd), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbyl polymers and polynorbornene (Elfatochem system).

Example also comprises the unsaturated polyester resin based on maleic anhydride, fumaric acid, itaconic acid and citraconic acid; Based on acryloyl group, methacryl and allylic unsaturated Epocryl; Polyurethane acrylate resin, the polyether acrylate resin, the polyalcohols acrylate, the alkyd acrylate, polyester acrylate resin, spiral shell acetal acrylate, the diallyl phthalate resin, diallyl tetrabromo-phthalate resin, diethylidene glycol diene propyl carbonate resin and polyethylene polymercaptan resin.

Monomer comprises for example N, Malaysia acyl polymer amines such as N '-m-phenylene bisamide, triallyl isocyanurate and trimethyl pi-allyl chlorinated isocyanurates.

In these compounds, following compounds is considered to be used effectively from cost and as hear resistance etc. in nature: ethene-alpha-olefin copolymer, as ethylene propylene diene terpolymers (EPDM) and ethylene butene diene terpolymer (EBDM), nitrile butadiene rubber (NBR), halo cyano group rubber, neoprene (CR), styrene butadiene ribber (SBR), butyl rubber (IIR) and chloro butyl rubber.

Acrylonitrile content is that the NBR of 15-55wt% effectively uses.Effectively the rubber that uses is pressed the Mooney viscosity number of JIS-K-6300 regulation at ML ₁₊₄Be 20-100 when (100 ℃).This rubber is usually 140-180 ℃ of sulfuration 5-50 minute.

Effectively the styrene-content of the SBR that uses is 5-85wt%, and Mooney viscosity is at ML ₁₊₄Be 30-80 when (100 ℃).

The Mooney viscosity number that effective EPDM that uses presses the JIS-K-6300 regulation is 5-110, and ethylene contents is 45-85wt%, and diene content is 2.0-25wt%, but is not limited to these numerals.Diene comprises dicyclopentadiene (DCPD), 1,4-hexadiene or inferior vinyl norbornene (ENB), but be not limited to these compounds.Preferred diene component comprises DCPD and ENB.

Effectively the EBDM that uses has the Mooney viscosity number (ML of 1-50 ₁₊₄(100 ℃)), melt flow (190 ℃) 1.5-25, ethylene contents 55-95wt%, diene content 2-35wt%, but be not limited to these numerical value.Similar to the situation of EPDM, diolefin compound comprises dicyclopentadiene (DCPD), 1, the 4-hexadiene (1,4-HD) or inferior vinyl norbornene (ENB), but be not limited to these.

EPDM and EBDM with two kinds of molecular weight distribution of width all can use.

The equal tool excellent electrical properties of EPDM and EBDM; They are good especially aspect the anticorona or anticreep vestige requirement that in recent years printed circuit is proposed; They are much more excellent than conventional adhesive.The trimeric character of propylene diene is subjected to following factor affecting: molecular structure, molecular weight (Mooney viscosity), the type of the third fate and content, the ratio between ethene and propylene and their branch ratio.

When polymer EPDM that uses super high molecular weight and EBDM, its Mooney viscosity can be regulated by using adjustment oil, thereby improves processability.

Ethylene propylene copolymer (EPM) and ethylene-butylene copolymer (EBM) do not contain vulcanizable unsaturated bond, but this shortcoming can be overcome by monomer, oligomer and the copolymer that use contains certain unsaturated bond.The present invention allow this with contain the polymers compositions of the compound of unsaturated bond.

This means main in the present invention oligomer, polymer or the elastomer that uses, comprise EPM and EBM and EPDM and EBDM, can mix with diene type elastomer, polymer, oligomer or monomer,, bond thereby significantly improve to improve the adhesive property between metal level and adhesive.The mixing ratio of diene type elastomer, polymer, oligomer or monomer contains the compound that can vulcanize unsaturated bond with respect to 100 weight portions, preferred 5-50 weight portion.

Described diene type elastomer polymer or oligomer comprise butadiene acrylonitrile copolymer, natural rubber, polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, styrene-butadiene-copolymer and polychlorostyrene pentadiene.

Styrene-butadiene-copolymer (SBR) is a kind of butadiene and cinnamic copolymer of ratio at random of comprising basically.This SBR also can be used as diene polymer or oligomer.Except that butadiene and styrene, contain the methacrylic acid of a small amount of the 3rd component and the mixed polymers of this class trimer of divinylbenzene and SBR and high-load styrene resin, also can use.According to the difference of polymerization, SBR can summarize and is categorized as emulsion polymerisation SBR and polymerisation in solution SBR.In addition, according to the form of product, it can be categorized as solid SBR and SBR emulsion.They all can use.Generally, this SBR does not comprise butadiene and cinnamic block polymerization, and the latter can be used for the present invention.

Polybutadiene can use the polybutadiene and the liquid polybutadiene of general purpose; Can select for use according to concrete needs.Butadiene acrylonitrile copolymer also can use.Liquid polybutadiene comprises NISSO-PB, because the 90% oligomer skeleton that diene anion activated polymerization obtains is 1,2-ethene connecting-type, it has the derivative as the derivative of functional groups such as vinyl, carboxyl and hydroxyl or its hydrogenation material, the acrylic terminal, the Malaysia modification, epoxide modified and epoxy resin modification.Also has Nippon-Petrochemical Co., Ltd. the liquid polybutadiene of Sheng Chaning, it comprises the pi-allyl end group and has following molecular structure, promptly in butadiene unit about 65% 1,2-connects, about 14% trans 1,4-connects and 16% cis 1, and 4-connects random combining, and the imide-modified and derivative amine modification of its Malaysia modification, epoxide modified, the phenol modification, half ester, acryloyl modification.It also comprises the Co. by Idemitsu Petrochemical, Ltd. " the Poly bd " of Sheng Chaning, and derivative, the former is the liquid polybutadiene with high response polyhydroxylated molecule end, wherein about 60% is trans 1,4 connecting-type, and about 20% is cis-1,4 connecting-types and about 20% are ethene-1,2 connecting-types.Also might use by B.F.Goodrich Chemical Co. and Ube Industrids, Ltd. the HYCAR RLP(trade mark of Sheng Chaning), it is the low-molecular weight polymer of mainly being made up of butadiene, it has at the two ends of main chain rule functional group is arranged, and on main chain, contain acrylonitrile group, and at carboxyl, amido and the vinyl at molecule two ends.

In addition, liquid chloroprene rubber, liquid isoprene and liquid styrene butadiene copolymer also can use.The polybutadiene of general purpose is mainly by polymerisation in solution production, and minute quantity is then by emulsion polymerisation production, and both all can be used for the present invention.Make product by polymerisation in solution and comprise Co derivative, Ni derivative and the Ti derivative of using the Zieglar Catalyst Production, and the Li derivative relevant with alkyl lithium catalyst.Consistent therewith is that it can be divided into two classes, and a class is wherein about 90% to be cis-1,4 connecting-type, and another kind of is about 35% to be that cis-1,4 connects.Two types all can be used for the present invention.When producing,, can sneak into a certain amount of the 3rd component for improving two types mixed performance with the mixed mutually mixture of the polybutadiene of general purpose.The 3rd component is selected from styrene-butadiene-copolymer, liquid rubber and the material that is called compatilizer usually.

Have the described compound that vulcanizes unsaturated bond and comprise at least one class vulcanizing agent that is selected from sulphur, sulfur donor and thio-alcohol.The content of vulcanizing agent, with respect to 100 weight portion high molecular weight materials, preferred 0.1-30 weight portion.Should be pointed out that the metal oxide vulcanization agent, for example zinc oxide also can be used in combination.

Sulphur powder and insoluble sulphur can be used as the sulphur of sulfuration.The sulfur donor that is used to vulcanize can use and decompose the organic compound of emitting the active sulfur atom under curing temperature.These compounds are included in has one group of compound that S-S connects in the molecule, they can be by following general formula:

R ₁-（-S-）n-R ₂

R wherein ₁And R ₂Be the group that is easy to emit sulphur atom, as dialkyl amido, morpholinyl and benzothiazolyl, " n " represents the integer of 2-6.

These compounds comprise:

2-(4 '-morpholino two sulfo-s) benzothiazole (MDB),

The 5-chloro-(4 '-morpholino two sulfo-s) benzothiazole,

The 5-nitro-(4 '-morpholino two sulfo-s) benzothiazole,

The 6-chloro-(4 '-morpholino two sulfo-s) benzothiazole,

The 6-nitro-(4 '-morpholino two sulfo-s) benzothiazole,

The 7-chloro-(4 '-morpholino two sulfo-s) benzothiazole,

The 7-nitro-(4 '-morpholino two sulfo-s) benzothiazole,

The 8-chloro-(4 '-morpholino two sulfo-s) benzothiazole,

The 8-nitro-(4 '-morpholino two sulfo-s) benzothiazole,

The 2-nitro-(3 '-morpholino two sulfo-s) benzothiazole,

Tetramethylthiuram disulfide,

Tetrapropylthiuram disulfide,

Tetrabutylthiuram disulfide,

Curing four (2-ethylhexyl) thiuram,

Dipentamethylene thiuram tetrasulfide (TRA),

Curing four (3-chloropropyl) thiuram,

Curing four (3-nitro propyl group) thiuram,

Curing four (3-hydroxypropyl) thiuram and

4,4-dithiomorpholine (R).

In addition, sulfuration tetra methylthiuram (TS) also can use, although it excludes in the above-mentioned general formula.

Various types of heat-stabilised poly mercaptan can be used as the sulfur alcohol compound of sulfuration usefulness.These polymercaptans comprise 2,4, and 6-tri-thiol-1,3,5-triazines and slaine thereof are at 6 esters this substituent 2 just like aminoalkyl, that 4-dimercapto-1,3,5-triazines and slaine thereof and thioglycolic acid and polyalcohol form.Described slaine is generally a sodium salt or a sylvite.Have 2 of aminoalkyl at 6,4-dimercapto-1,3,5-triazines derivative can be easily by 2, and 4-two chloro-6-alkylamino-1,3,5-triazines and NaOH reaction make; And 2,4-two chloro-6-alkylamino-1,3,5-triazines can be reacted at low temperatures by cyanuric chloride and various amino-compound and make.In this occasion, use polynary amino-compound, as ethylene diamine, can produce the compound that comprises crosslinked many 1,3,5-triazines ring.These compounds comprise

2,4-dimercapto-6-methylamino-1,3,5-triazines,

2,4-dimercapto-6-ethylamino-1,3,5-triazines,

2,4-dimercapto-6-propyl group amino-1,3,5-triazines,

2,4-dimercapto-6-isopropyl amino-1,3,5-triazines,

2,4-dimercapto-6-butyl amino-1,3,5-triazines,

2,4-dimercapto-6-isobutylamino-1,3,5-triazines,

2,4-dimercapto-6-dimethylamino-1,3,5-triazines,

2,4-dimercapto-6-diethylamino-1,3,5-triazines,

2,4-dimercapto-6-dipropyl amino-1,3,5-triazines,

2,4-dimercapto-6-diisopropylaminoethyl-1,3,5-triazines,

2,4-dimercapto-6-dibutylamino-1,3,5-triazines,

2,4-dimercapto-6-allyl amino-1,3,5-triazines,

2,4-dimercapto-6-phenyl amino-1,3,5-triazines,

2,4-dimercapto-6-tolyl amino-1,3,5-triazines,

N, N '-two (2,4-dimercapto-1,3,5-triazines base) ethylene diamine,

2,4-dimercapto-6-hydroxyethylamino-1,3,5-triazines and 2, two (the hydroxyethylamino)-1,3,5-triazines of 4-dimercapto-6-.

In addition, 2,4-dimercapto-6-acryloyl group amino-1,3,5-triazines etc. also can effectively use.In addition, the HMW type comprise contain combine with the amino of polyallylamine resin with side chain primary amino radical 2, the polymer of 4-dimercapto-6-dibutylamino-1,3,5-triazines residue.The ester of sulfo-Glycolic acid and polyalcohol comprises glycerine three sulfo-glycolates, trimethylolpropane tris sulfo-glycolate and pentaerythrite tetrathio glycolate.

Also can use as dicumyl peroxide, α with vulcanizing agent, α '-two (tert-butyl hydroperoxide isopropyl) benzene and 2,5-dimethyl-2, these peroxide of 5-two (t-butyl peroxy) hexane, but the type of described peroxide is not limited to these compounds.The mixing ratio of peroxide contains the compound of unsaturated bond, preferably 0.01-10 weight portion with respect to 100 weight portions.Especially use the mercaptan of sulfuration usefulness with above-mentioned peroxide, can obtain preferred result.

In addition, if need, in adhesive, with the also preferred vulcanization accelerator of using of vulcanizing agent.Vulcanization accelerator comprises acylate, as cobalt naphthenate; Calcined magnesia, zinc oxide and lead and yellow-collation; Aldehyde ammonia derivative such as hexa; Aldehyde amine derivative such as n-butyraldehyde aniline; Thiourea derivative such as N, N '-rhenocure CA, trimethyl thiourea and N, N '-diethyl thiourea; Guanidine derivatives is as 1, two-o-tolyl guanidinesalt of 3-diphenylguanidine, di-o-tolyl guanidine, 1-neighbour-tolyl two guanidine derivatives and dicathecole borate; The zinc salt of thiazole such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole, the ring of 2-mercaptobenzothiazole be amine salt, 2-(N, N '-diethyl thiocarbamoyl) benzothiazole benzothiazole, and 2-(4 '-morpholino two sulfo-s); Sulfamide derivative such as N-cyclohexyl-2-[4-morpholinodithio base sulfenamide, the N-tert-butyl group-2-[4-morpholinodithio base sulfenamide, N-oxo diethylidene-2-[4-morpholinodithio base sulfenamide and N, N '-two cyclohexyls-2-[4-morpholinodithio base sulfenamide; Thiurams derivative such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, curing four (2-ethylhexyl) thiuram, tetramethylthiuram monosulfide and dipentamethylene thiuram tetrasulfide; The slaine of diethyldithiocar bamic acid such as piperidine pentamethylene dithiocarbamate, pipecoline base aminodithioformic acid pipecoline, zinc diethyl dithiocarbamate, N-ethyl-N-phenyl zinc dithiocarbamate, N-pentylidene zinc dithiocarbamate, zinc dibenzyl dithiocarbamate, zinc dibutyl dithiocarbamate, sodium diethyldithiocarbamate, NB sodium dibutyl dithiocarbamate, cupric dimethyldithio carbamate, ferric dimethyl dithiocarbamate and tellurium diethyl dithiocarbamate; Xanthates homologue such as zinc butyl xanthate and zinc isopropyl xanthate; And their mixture, but be not limited to these.The content of vulcanization accelerator is with respect to 100 weight portion adhesive, preferably 0.01-10 weight portion.

Should be pointed out that when these vulcanizing agents or vulcanization accelerator to be coated on the Copper Foil metal level, but not inject adhesive, is effective to improving adhesion strength.

In addition, if desired, also can add anti-maturing agent such as amine ketone derivatives, the secondary aromatic amine derivative, amphyl, polyphenol derivatives, benzimidizole derivatives, aminodithioformic acid slaine derivative, thiourea derivative, phosphoric acid derivatives, organic sulfur are for acid derivative and wax derivative.The content of anti-maturing agent is with respect to the preferred 0.01-5.0 weight portion of 100 weight portion adhesive.

Used adhesive can mix with the compatilizer and the modifier that comprise the polymer substance except that being used for those of adhesive among the present invention, to improve with the compatibility of synthetic resin matrix and to improve character.

For example, can use following material: phenol resin such as phenolic resin type, phenolic varnish type, alkyl phenol type, xylene resin modification with Malaysia polyimide resin modification; To tert-butyl group thiophenol resin (Sanfel BTS, Sanshin Chemical Inc. produces); Various epoxy resin such as bisphenol A-type, Bisphenol F type, phenolic varnish type, brominated bisphenol A type, bromination phenolic varnish type and alicyclic ring type; Ester cyanate type, cumarone indene copolymer, hydrogenation rosin, the maleic resin of rosin ester, rosin modification, these rosin and derivative thereof, Petropols, the Malaysia polyimide resin, mylar, the acryloyl resin, silicones contains the high polymer monomer of polymerizable functional group; Polyether rubber is the graft copolymer and the expoxy propane chloropropylene oxide allyl glycidyl ether trimer of high polymer monomer and low molecular monomer as described; Epoxy propane rubber, polysulfide rubber, the carbon fluorubber, tetrafluoride EP rubbers, CSM, second acryloyl rubber, silicon rubber, polyurethane rubber, polyisoprene, polyisobutene forms the IPN(interpenetrating polymer networks) mix monomer, as polystyrene polybutene IPN, IPN between phenol resin or epoxy resin and liquid rubber and the acryloyl rubber, cross-linked silicone rubber, second acryloyl rubber, the epoxy resin IPN such as cyanogen butadiene rubber, styrene butadiene ribber and the EP rubbers that contain elastomer latices.

The high polymer monomer that has the polymerizable functional group that can effectively utilize in the end; be those macromolecular compounds that have carboxyl, methacrylyl, dihydroxyalkyl and epoxy radicals in the end, as polystyrene, SAN, polyacrylonitrile, polymethyl methacrylate, butyl polyacrylate and polysiloxanes.Be effective to the low molecular monomer with described high polymer monomer graft copolymerization, comprise vinyl monomer such as acrylate, vinylacetate, styrene and vinylpyridine.

In addition, also can add 1wt% or the following at least one compounds and the surfactant that are selected from various silane, titanium, aluminium base coupling agent.

The mixed proportion of compatilizer or modifier with respect to whole adhesive, is generally 1-60wt%, preferably 5-50wt%, more preferably 5-30wt%.When adding compatilizer or modifier, the adhesion strength of Copper Foil and matrix causes the brute force bonding between Copper Foil and Copper Foil (circuit Copper Foil) or Copper Foil and matrix owing to the function of compatilizer increases.

Adhesive can following arbitrary type use: sheet type, aqueous solution type, emulsion-type or solvent-borne type.As needs, also can under the situation that does not influence effect of the present invention, in adhesive, add following material: asbestos, aluminium oxide, Attagel, kaolin, carbon black, graphite, SiO 2 powder, calcium silicates, diatomite, magnesia, titanium oxide, iron oxide, magnesium hydroxide, aluminium hydroxide, slate powder, selenite, the fused silica powder, boron nitride, calcium carbonate, magnesium carbonate, talcum, feldspar, molybdenum dioxide, barite, vermiculite, white powder, mica, the agalmatolite clay, gypsum and similarly inorganic filler, or as the phenolic resins microballoon, polyimide microsphere, wood chip and organic fiber powder.

In addition, carbon fiber, metallic fiber, palpus crystalline substance, boron fibre, glass fibre, ceramic fibre, polyester fiber, vinylon fiber and Fypro also can be used for adhesive.They use with silk, filament yarn, cut staple, staple fiber, Spanized yarn, cloth and adhesive-bonded fabric form.

Also can add pigment.Petroleum base paraffin oil, naphtalene oil and aromatic oil also can be used as the softening agent adding in addition.The mixture and the similar fire proofing material that also can add aluminium hydroxide, hydrated gypsum, Firebrake ZB, alunite, red phosphorus, halogenated organic compounds and antimony trioxide.

When copper clad laminate of the present invention immerses hydrochloric or its salt, as in the aqueous solution of copper chloride and iron chloride the time, the adhesion strength between Copper Foil and insulating barrier has improvement again.The preferred 0.1N-10N of the concentration of hydrochloric acid, infiltrating time preferably 0.1-10 minute.

Fig. 1 is a sectional view of representing the structure of copper clad laminate in the embodiment of the present invention;

Fig. 2 is a sectional view of representing the structure of copper clad laminate in another embodiment of the present invention;

The preferred embodiments of the invention are below described, however should with understand the present invention and be not limited to following description.

Embodiment 1

As shown in Figure 1,0.2mm the thick rubber based adhesives sheet of making by (II) described stack hereinafter 3, (I) described surface-treated metal layer 2(0.4 μ m is thick hereinafter to be clamped in band) one of 9 class Copper Foils and cover paper 4(4-1 by 7 layers of FR-1 level paper-based phenolic resin copper clad laminate (MCL437F) of being used for that Hitachi chemical Co., Ltd provides, 4-2,4-7), the face 5 of the thick electro copper foil 1 of 35 μ m is handled (surface irregularity: Ra1.5 μ m) without hacking.At 170 ℃ of temperature, 200kg/cm ²With its lamination 1 hour, be pressed into whole under the pressure, thereby obtain copper clad laminate as shown in Figure 1.The peeling strength test that the bonding of carrying out testing rubber according to JIS-C 6481 is broken, this product have 90 good degree peel strength value, 2.0-2.2kg/cm.And recording its 260 ℃ welding hear resistances is 15 seconds or longer, illustrates that this product fully satisfies required standard.

The described paper that covers was that 0.25mm is thick before being laminated into one whole, and 7 layers of this paper thickness are 1.75mm to 2mm when lamination.Yet after being laminated into one whole, this thickness becomes about 1.4mm.

The type of (I) surface-treated metal layer on the shiny surface of Copper Foil is

ⅰ) the Pd-P(weight ratio is 100: 6)

ⅱ）Ni

ⅲ）Co

ⅳ）Zn

ⅴ）Sn

ⅵ) the Ni-Cu(weight ratio is 50: 50)

ⅶ) the Zn-Cu(weight ratio is 50: 50)

ⅷ) the Zn-Cu(weight ratio is 30: 70)

ⅸ）In

The composition of (II) rubber based adhesives sheet

SRB(Japan synthetic rubber Co., Ltd, merchant's name: JRS152) ... 100 weight portions

Solid phenolic resin (Hitachi Chemical Company Ltd.'s system, merchant's name: HP180R) ... 20 weight portions

White carbon (PPG Industries Inc., merchant's name: HiSil233T) ... 50 weight portions

Zinc oxide ... 5 weight portions

Stearic acid ... 1 weight portion

Sulphur ... 1 weight portion

Embodiment 2

The copper clad laminate that embodiment 1 obtains is copper clad laminate of solidly, and the present embodiment relates to flexible two-sided copper clad laminate.Should be pointed out that embodiment 1 and 5 relates to a hard copper clad laminate, and embodiment 2,3 and 4 relates to flexible two-sided copper clad laminate.

As shown in Figure 2, on the dull surface 15 of thick electrodeposited copper foil 11-1 of 18 μ m and 11-2, form 9 class surface-treated metal layer 12-1 and the 12-2 of thick 0.5 μ m with galvanoplastic, wherein Copper Foil is not done the hacking processing.

By the described thick SER rubber based adhesives sheet 13 of 0.2mm of making of II hereinafter.Each dull surface of Copper Foil is face-to-face placement, and NBR rubber based adhesives sheet 13 is sandwiched in therebetween.This metal, rubber and rubber are at 170 ℃ of temperature, 50kg/cm ²Vulcanized simultaneously under the pressure 30 minutes, and be laminated into one whole, thereby obtain copper clad laminate shown in Figure 2.This laminate is the copper clad laminate that is used to have the printed circuit board (PCB) of rubber core material.

The composition of (II) rubber based adhesives sheet

SBR(Japan SYnthetic Rubber Co. Ltd makes, merchant's name: JRS1502) ... 100 weight portions

[the styrene 23.5 weight % of combination, Mooney viscosity ML ₁₊₄(100 ℃) 52]

White carbon (PPG Industries Inc.'s system, merchant's name: HiSil 233T) ... 50 weight portions

Zinc oxide ... 5 weight portions

Stearic acid ... 1 weight portion

Sulphur ... 2 weight portions

Dibenzothiazyl disulfide ... 1.5 weight portion

This laminate is pressed JIS-C 6481 tests, 90 degree peel strengths and 260 ℃ of welding hear resistances, break with the bonding that shows rubber.Peel strength is 2.0-2.2kg/cm, demonstrates powerful bonding strength, even also is like this on the copper-clad surface of handling without hacking.The welding hear resistance is 15 seconds or longer.

When replacing this rubber based adhesives sheet with conventional butyraldehyde base adhesive, peel strength has only 0.6kg/cm, and the welding hear resistance has only 2 seconds or shorter, has shown very big difference.

In order to make the circuit of 0.15mm width, with 30 seconds of copper chloride etching solution etching copper clad laminate.Almost do not observed facet etch on laminate, good circuit has been made in this expression.

Embodiment 3

Form with electroless plating at the wet look of the thick electrodeposited copper foil of original 35 μ m (surface irregularity: Ra0.2 μ m) go up i) and to comprise Pd-P(weight ratio 100: 6) surface-treated metal layer (0.5 μ m is thick) and ii) comprise Zn-Cu(weight ratio 30: 70 with plating formation) surface-treated metal layer (0.5 μ m is thick).The thick rubber based adhesives sheet of 0.2 μ m as described below is clipped in per two Copper Foils, and at 170 ℃ and 50kg/cm ²Pressure laminated 30 minutes makes it to be pressed into one complete, thereby obtains copper clad laminate.

The composition of (II) rubber based adhesives sheet:

NBR(Japan synthetic rubber Co., Ltd, merchant's name: T4632) ... 100 weight portions

Solid phenolic resin (Hitachi chemical Co., Ltd, merchant's name: HP180R) ... 30 weight portions

Epoxy resin (Shell Co. Ltd, trade mark EP828) ... 10 weight portions

Styrene/acrylonitrile macromonomer (Toha Gosei Co., Ltd system macromonomer, merchant's name: AN-6) ... 5 weight portions

White carbon (PPG Industries, Inc., merchant's name: HiSil 233T) ... 50 weight portions

Zinc oxide ... 5 weight portions

Stearic acid ... 1 weight portion

Sulphur ... 1.5 weight portion

Described laminate is carried out peeling strength test and 260 ℃ of welding heat-resistance tests by JIS-C 6481, to measure the bond damage situation of rubber.Peel strength is 2.2-2.8kg/cm, even for the copper-clad surface of handling without hacking, also confirms to have powerful adhesion strength.The welding hear resistance is 15 seconds or longer.

Embodiment 4

In the sheet of rubber based adhesives described in the embodiment, add following 10 types of compatilizers, to produce 10 class rubber based adhesives sheets:

1) (Japanese tempering is learned Co., Ltd, molecular weight: 300-400 to the Cumarone indene copolymer ... 10 weight portions

2) polybutadiene (Japanese Soda Co., Ltd, merchant's name: Nisso PB-3000) ... 10 weight portions

3) polyisoprene (Kuraray Co., Ltd, merchant's name: Kuraprene LIR) ... 10 weight portions

4) dicyclopentadiene resin (Japan petroleum chemistry Co., Ltd, merchant's name: Nisseki Neoresin EP-100) ... 5 weight portions

5) hydration rosin (Riken Harcules, Inc., merchant's name: ForalAX) ... 5 weight portions

6) unsaturated polyester resin (maleic anhydride-isophthalic acid-propylene-glycol-based) ... 5 weight portions

7) silicone resin (Shin-Etsu chemistry Co., Ltd, merchant's name: KE42) ... 5 weight portions

8) C ₅Foundation stone oleoresin (Japanese Zeon Co., Ltd, merchant's name: QuintonA-100) ... 5 weight portions

9) silane coupling agent (ν-sulfydryl propyl trimethoxy silicane) ... 0.5 weight portion

10) epoxide modified polystyrene graphite PMMA ... 5 weight portions

To pressing the laminate of producing with above-mentioned rubber based adhesives sheet with official's 3 same way as, press JIS-C6481 test 90 degree peel strengths and 260 ℃ of welding hear resistances, with the bond damage situation of mensuration rubber.Its peel strength is 2.0-2.2kg/cm, even for the copper-clad surface of handling without hacking, also confirms to have powerful adhesion strength.The welding hear resistance is 15 seconds or longer.

Embodiment 5

With total amount is that the composition of 163 weight portions is pressed into the thick sheet of 0.2mm, and composition is composed as follows:

100 weight portion NBR(HYCAR 1002) B.F.Goodrich chemical company

50 weight portion phenol modified resin (Durez 12687) Sumitomo Durez Co., Ltds,

5 weight portion ZnO

5 weight portion sulphur

1.5 weight portion dibenzothiazyl disulfide (DM) and

1.5 weight portion stearic acid.

This composition is adhered to (surface irregularity: Ra0.2 μ m), this Copper Foil is by three metalloid surface treatments (electrolysis is thick to tool 0.5 μ m) on the shiny surface of the thick electrodeposited copper foil of 18 μ m.

1) the Zn-Cu(weight ratio is 30: 70), 2) Ni-P(weight ratio 97: 3) and 3) Pd-P(weight ratio 96: 4).With its 160 ℃ with the covering paper and cover paper, mold pressing 30 minutes of embodiment 1 used paper substrate phenol resin copper clad laminate with the MCL E67 glass-based epoxy resin of producing by Hitachi chemical Co., Ltd.Previous field matched moulds pressure pressure 150kg/cm ², back one occasion 50kg/cm ²

Carry out 90 degree peel strength tests by JIS-C 6481, the result is 2kg/cm or more under the room temperature.260 ℃ welding hear resistance is 15 seconds or longer in addition, shows to have satisfactory result.

Embodiment 6

The composition that will have following composition is pressed into the thick sheet of 0.2mm:

40 weight portion NBR(HYCAR 1002) B.F.Goodrich chemical company

60 weight portion phenol-formaldehyde resin modifieds (Bakelite RD40-1) Sumitomo Durez Co., Ltd,

10 weight portion ZnO

1.75 weight portion sulphur

0.625 weight portion dibenzothiazyl disulfide (DM)

1.5 weight portion stearic acid

1 weight portion cobalt naphthenate

100 weight portion batts.

This composition is adhered on the shiny surface of the thick electrodeposited copper foil of 9 classes, 18 μ m (surface irregularity: Ra 0.2 μ m), these Copper Foils carry out surface treatment by embodiment 1, and with embodiment 1 used paper-based phenolic resin copper clad laminate cover the paper lamination and the bonding in aggregates, condition is 160 ℃, 150kg/cm ²With lamination 45 minutes.

Carry out 90 degree peel strength tests by JIS-C 6481, the result is 2kg/cm or higher under the room temperature.In addition, 260 ℃ welding hear resistance is 15 seconds or longer, and expression has satisfactory result.After immersing hydrochloric acid, 180 ℃ of heating 48 hours; Measure 90 degree peel strengths then after welding, the result is satisfied.

Embodiment 7

The thick adhesive film of about 0.2mm that will have following composition, be sandwiched between the shiny surface (surface irregularity: Ra 0.2 μ m) of the thick electrodeposited copper foil of 18 μ m that covers paper and handle with the thick surface metal of 0.5 μ m of used paper-based phenolic resin copper clad laminate in 7 layers of embodiment 1

The Japanese synthetic rubber of 100 parts by weight of styrene butadiene rubbers (JSR 1502) Co., Ltd

The white carbon of 50 weight portions (PPG Industries, Inc., merchant's name: HiSil 233T)

5 weight portion ZnO

1 weight portion sulphur

1 weight portion stearic acid

1 weight portion cobalt naphthenate

1.5 weight portion vulcanization accelerator (2-mercaptobenzothiazole)

Carry out 90 degree peel strength tests by JIS-C 6481, the result is 2kg/cm or higher under the room temperature.In addition, 260 ℃ of welding hear resistances are 15 seconds or longer, show satisfactory result.

Embodiment 8

With the shiny surface (surface irregularity: Ra0.2 μ m) go up formation 0.5 μ m thick Pd-P surface metal-layer (Pd and P weight ratio 94: 6) of galvanoplastic at the electrodeposited copper foil of the thick hacking of 18 μ m.So just, (Hitachi chemical Co., Ltd, merchant's name: Copper Foil MCL-E67), the shiny surface of this Copper Foil just becomes upper surface, forms conducting channel (live width 0.1mm) with etching to have made FR-4 level glass-based epoxy resin copper clad laminate.Similarly, making the band Pd-P(weight ratio of making 94: 6) shiny surface of the Copper Foil of layer arranges mutually face-to-face.The thick propylene diene trimer of 0.2mm (EPDM) base adhesive sheet with following composition is sandwiched between them then.At 160 ℃ of temperature, 50kg/cm ²With its lamination 30 minutes, make it be bonded to one whole under the pressure.

The composition of adhesive film

100 weight portion EPDM(Sumitomo chemistry Co., Ltd, Esprcne 505)

The white carbon of 100 weight portions (PPG Industries, Inc., merchant's name: HiSil 233T)

60 weight portion process oils

5 weight portion ZnO

1.0 weight portion stearic acid

2.0 weight portion two-n-zinc dibutyl dithiocarbamate

0.5 weight portion tetramethylthiuram disulfide

1.0 weight portion 2-mercaptobenzothiazole

1.5 weight portion sulphur.

Carry out 90 degree peel strength tests by 6481 pairs of described laminates of JIS-C, the result is 2.3kg/cm or higher under the room temperature.Immersing 6N hydrochloric acid is 2.3kg/cm after 1 hour; Was 1.5kg/cm 180 ℃ of heating after 48 hours.After 5 seconds, the result is 〉=2kg/cm in immersing 260 ℃ of welding agent water.90 degree peeling strength tests are 1.0kg/cm under 150 ℃ of high temperature.260 ℃ welding hear resistance is 15 seconds or longer.Compare with the Copper Foil of handling through hacking and with those situations of the alkyd resin based adhesive bonds of PVB of routine, more than all test results all better or equal at least.

Embodiment 9

At the adhesive surface of the thick silicon steel plate of 1mm, the adhesive surface of aluminum matrix and even surface (surface irregularity: on each face Ra:0.15 μ m), form the thick Pd-P(weight ratio 96=4 of the 0.4 μ m) layer of the thick electrodeposited copper foil of 18 μ m with electroless plating.The EPDM adhesive film of using in the embodiment 8 is sticked on the end face of using Pd-P surface-treated silicon steel plate and aluminum matrix.Then, on its top, be stained with the thick Copper Foil of the surface treated 18 μ m of its shiny surface, with the shiny surface of Copper Foil to this sheet.At 160 ℃ of temperature, 30kg/cm ²Pressure laminated 30 minutes makes to stick into one whole, thereby obtains the metal-based layer pressing plate.Survey its 90 degree peel strength value by JIS-C6481, under the room temperature be 〉=2kg/cm, immersing 6N hydrochloric acid is 〉=2.3kg/cm to be 〉=1.5kg/cm after 1 hour after 48 hours 180 ℃ of heating.After immersing 260 ℃ of welding agent and bathing for 5 seconds, the result is 〉=2kg/cm.Under 150 ℃ of high temperature, its 90 degree peel strength is 1.0kg/cm.260 ℃ welding hear resistance is 〉=15 seconds.All these data are parity with or superiority over those results with conventional adhesive bonds hair side.

Should be pointed out that after using the salt acid soak peel strengths improved.

Embodiment 10

Electricity consumption be plated in the thick electrodeposited copper foil of 35 μ m shiny surface (surface irregularity: Ra:0.2 μ m), dull surface (surface irregularity Ra1.2 μ m) and the band coarse particles dull surface (surface irregularity Ra1.5 μ m) on, form three thick metalloid layers of 0.6 μ m: Cu-Zn(30wt%Zn), Ni-P(weight ratio 94: 6) and Pd-P(weight ratio P4: 6).The thick rubber based adhesives sheet of following two class 0.2mm is sandwiched between these surface-treated layers and 6 the FR-4 level glass cloth basic ring epoxy resins coated cloths.At 160 ℃, 50kg/cm ²Made it stick into one whole in 30 minutes their laminations down.

The composition of rubber based adhesives sheet

1) 100 weight portion hydrogenated nitrile butadiene rubbers (Japanese Zeon Co., Ltd, Zetpol 1020)

2.0 the anti-maturing agent of weight portion (diphenylamine derivatives)

5.0 weight portion ZnO

1.0 weight portion stearic acid

The white carbon of 40 weight portions (PPG Industries, Inc., HiSil 233T)

1.5 weight portion tetramethylthiuram disulfide (TT)

0.5 weight portion 2-mercaptobenzothiazole (M)

1.0 weight portion cobalt naphthenate

1.5 weight portion sulphur,

2) 100 weight portion chloroprene rubbers (Du Pont-Showa Denko Co., Ltd, GW)

18 weight portion ZnO

The white carbon of 40 weight portions (the HiSil 233T of PPG Industries, Inc.)

4 weight portion 2-sulfydryls-2-imidazolone (22R)

1 weight portion dibenzothiazyl disulfide (DM)

1 weight portion tetramethylthiuram disulfide (TT)

1.0 weight portion cobalt naphthenate

0.5 weight portion sulphur.

Press 90 degree peel strengths of JIS-C 6481 these laminates of test.The result is under the room temperature 〉=2.0kg/cm, in 6N hydrochloric acid, soak after 1 hour to be 〉=2.5kg/cm, 180 ℃ down heating be 〉=1.5kg/cm in 260 ℃ of welding agent are bathed, to soak and 5 seconds be 〉=2kg/cm after 48 hours after the kind.90 degree peel strengths are 〉=1.0kg/cm under 150 ℃ of high temperature.260 ℃ welding hear resistance is 〉=15 seconds.The light face has and the identical level of handling through hacking of face in actual use with dull surface.What especially Pd handled is not only stable but also good.Should be pointed out that and form that the performance of making sheet also is good behind the open-work.Can guarantee also that on the light face fact that high-quality bonds reliably shows, in adopting sandwich construction, need not to carry out the blackout processing or the control surface raised structures of trouble in the paper tinsel of manufacturing copper foil, this expression hacking is handled no longer necessity.This is great for the contribution that reduces cost.

Embodiment 11

Comprise that triazine sulphur piperazine is the rubber based adhesives in the listed ratio mixing of table 1 of vulcanizing agent, with the light hand-deliver connection of the former Copper Foil of the thick electrolytic deposition of 35 μ m of electroplating the surface metal-layer (94wt%Ni, 0.5 μ m is thick) that forms by Ni-P.

The rubber of mixing ratio shown in the table 1 becomes the thick sheet material of 0.2mm by the calender kneading.

With all kinds of sheet rubbers shown in the table 1, adhere to 7 layers of paper that covers that is used for FR-1 level paper substrate phenol resin copper clad laminate (MCL 437F) that Hitachi chemical Co., Ltd produces, contact with the treated side of above-mentioned Copper Foil is bonding again.At 160 ℃, 150kg/cm ², 30 minutes condition laminated and be bonded to whole.

Press 90 degree peel strengths of JIS-C 6481 these laminates of test.Under its value room temperature be 〉=the 2.0kg/cm(standard value is 2.00 ± 0.30), be dipped in hydrochloric acid (6N) and be the 2.5kg/cm(standard value after 1 hour, degradation ratio :≤10%), 180 ℃ of following heating after 48 hours are 〉=1.5kg/cm.Immerse and be 2kg/cm(standard value 2.00 ± 0.30 after 260 ℃ of welding agent bathed for 5 seconds).90 degree peel strengths under 150 ℃ of high temperature are 1.0kg/cm(standard value 〉=0.45).260 ℃ welding hear resistance is 〉=20 seconds (standard value is 〉=15 seconds).Therefore, product is enough to satisfy required standard.No.2 has added triazine with No.4 but the sample that do not add sulphur demonstrates similar premium properties.After soaking in hydrochloric acid, they all demonstrate improved performance.

1) triazine thiol A1:2,4-dimercapto-6-phenylamino-1,3,5-triazines

2) triazine thiol B1:2,4,6-tri-thiol-1,3,5-triazines

3) TS: single sulfuration tetra methylthiuram

4) MBTS: dibenzothiazyl disulfide

5) TT: tetramethylthiuram disulfide

6) NBR: Japanese synthetic rubber Co., Ltd, merchant's name: 2025

7) SBR: Japanese synthetic rubber Co., Ltd, merchant's name: 1500

8) BR: Japanese Zeon Co., Ltd, merchant's name: BR1220

9) EPDM:Mitsui petrochemistry company, merchant's name: 4070

10) ACM: Japanese synthetic rubber Co., Ltd, merchant's name: AR420

11) CR:Denki Kagaku Kogyo Kabushiki Kiasha, merchant's name: A-120

12) mixing ratio: represent with weight portion

Embodiment 12

With mixing the rubber kneading of forming shown in the table 2, form the thick sheet of 0.2mm with calender.

1) NBR: Japanese synthetic rubber Co., Ltd, merchant's name: 2025

2) hydrogenated nitrile butadiene rubber: Japanese Zeon Co., Ltd, merchant's name: 2020

3) EPDM rubber: Mitsui petro chemical industry Co., Ltd, merchant's name: 4010

4) BR: Japanese Zeon Co., Ltd, merchant's name: BR1220L

5) triazine thiol C-1:2,4-dimercapto-6-acrylamido-1,3,5-triazines

6) DCP: dicumyl peroxide

7) Percadox 14: α, α '-two (t-butyl peroxy isopropyl) benzene

8) Perhexa 25B:2,5-dimethyl-2,5-two (t-butyl peroxy) hexane

9) mixing ratio: represent with weight portion

All kinds of sheet rubbers are adhered to 7 layers of paper that covers that is used for FR-1 level paper substrate phenol resin copper clad laminate (MCL437F) that Hitachi chemical Co., Ltd produces, in the above, be stained with charged plating Ni-P(94wt% Ni in the face of rubber) the light face of the former Copper Foil of the thick electrolytic deposition of 35 μ m of surface metal-layer (0.5 μ m is thick).

Press 90 degree peel strengths of JIS-C 6481 these laminates of test.Under its value room temperature be 〉=the 2.0kg/cm(standard value is 2.00 ± 0.30), be dipped in hydrochloric acid (6N) and be the 2.5kg/cm(standard value after 1 hour, degradation ratio :≤10%), 180 ℃ are heated after 48 hours down is 1.5kg/cm.Immerse and be 2kg/cm(standard value 2.00 ± 0.30 after 260 ℃ of welding agent bathed for 5 seconds).90 degree peel strengths under 150 ℃ of high temperature are 1.0kg/cm(standard value 〉=0.45).260 ℃ welding hear resistance is 〉=20 seconds (standard value is 〉=15 seconds).Therefore, product is enough to satisfy required standard.The sample that has added triazine but do not added sulphur demonstrates similar premium properties.After soaking in hydrochloric acid, they all demonstrate improved stability (from 2kg/cm-3kg/cm).

Embodiment 13

Go up plating at the thick roll-in copper-clad surface of 18 μ m (surface irregularity: Ra 0.15 μ m) and form the thick Ni-P layer of 0.5 μ m.Then with propylene diene trimer (EPDM4010 that Mitsui petro chemical industry Co., Ltd produces, ethene 63wt%, 10.6wt% diene (EBN), Mooney viscosity ML ₁₊₄(100 ℃) 8) with polybutadiene (the Nipol BR1220L of general purpose, Japan Zeon Co., Ltd) and liquid polybutadiene (Japanese Soda Co., Ltd, NiSSO-PB-PB 3000), mix in various ratios shown in the table 3, make 51 class adhesive compounds of two class peroxide cure derivative combinations shown in the sulfur vulcanization derivative that comprises shown in the table 4 and the table 5.Then they are dissolved in the mixture of toluene and dimethylbenzene (weight ratio 50: 50), produce the adhesive lacquer.They are applied on the treated side of the Copper Foil with Ni-P surface metal-layer, form the thick film of about 20 μ m.With covering on the paper of above-mentioned copper-clad laminate (MCL 437F), and in the face of covering paper, according to a conventional method at 170 ℃, 150kg/cm ², 40 minutes condition laminated, produce a copper clad laminate and two sides copper clad laminate.

Table 6 is listed above-mentioned laminate is carried out result by JIS-C 6481 test.Peel strength and welding all show aspect the hear resistance two than with conventional adhesive better.In addition, the adhesive of using among the present invention is applied on the smooth copper foil, can allow used coating content reduce to conventional adhesive be coated onto rough surface consumption 1/2 to 1/5, cost is reduced.

Mainly comprise the composition (Nos.1,2,3,5,6,8,9,10,11 and 12) of the EPDM with good anti-tracking performance, the measurement of pressing UL Subject 746A is its feature with fabulous anti-tracking performance.Conventional adhesive contains inorganic additive such as aluminium hydroxide and Malaysia amine, to improve anti-tracking character.Owing to be difficult to coating and not quite smooth, and productivity ratio descended.In contrast, there is not this class problem fully in adhesive of the present invention, thereby has high coating operating efficiency.

The manufacturing of peroxide cure derivative in the table 5 is described below:

Percumyl-D:NOF company, (u.k.)

Nocrac MB:Ouchi Shinko chemical industrial company

Triazine thiol A-1: Sanyo Kasei Co., Ltd

Acryloyl ester: Shin Nakamura chemistry Co., Ltd

Triazine thiol B-1: Sanyo Kasei Co., Ltd

Embodiment 14

The main adhesive components that present inventor's use table 7 provides, and with embodiment 13 in 15 class adhesive components identical materials and the production methods listed of table 4 and table 5, produce copper clad laminate.Press room temperature peel strength that JIS-C 6481 measures, 180 ℃ peel strength and welding hear resistance and salt tolerant acidity after 48 hours, good equally with the listed example character of the present invention of table 6.Mixing ratio with EPDM is the Nos3-5 sample of 〉=50wt%, shows the good anti-tracking performance of 〉=200 losses.

Table 7

Embodiment 15

On the one side of the thick roll-in Copper Foil of 18 μ m (surface irregularity: Ra0.15 μ m) form 0.5 μ m and electroplated the Pd-P(weight ratio 94: 6).Use following main adhesive components to prepare the adhesive lacquer:

(I) 100 weight portion polybutadiene, Nipol BR 1220L, Japanese Zeon Co., Ltd

(II) 20 weight portion liquid polybutadienes, LPB-300, Japan petroleum chemistry Co., Ltd

(III) 1.0 weight portion 2-mercaptobenzimidazoles (Noccler M, Ouchi Shinko chemical industrial company)

(IV) 1.5 weight portion tetramethylthiuram disulfides, Noccler M, Ouchi Shinko chemical industrial company)

(V) 1.5 weight portion lists sulfuration tetra methylthiuram, Noccler M, Ouchi Shinko chemical industrial company)

(VI) 4.0 weight portions are dissolved in the sulphur powder in toluene and the dimethylbenzene mixed liquor.

On the face that its palladium that is coated on Copper Foil is handled, form the thick film of about 15 μ m.This Copper Foil is placed on the prepreg (epoxide modified hydrocyanic ester resin, Mitsubishi aerochemistry company) of 4 layers of fiberglass-based BF resin 810, make adhesive surface with face-to-face, thus according to a conventional method, at 170 ℃, 100kg/cm ²With 40 minutes laminations, make a copper clad laminate and two sides copper clad laminate.

Press JIS-C 6481 and measure these laminates.The results are shown in table 6, show it is good.Press UL Subject 746A and measure the arc resistant performance, show 〉=200 such good results of loss, meet the demands fully.Show that at 〉=1GHz high frequency waveforms transmission test they do not produce wave distortion, are suitable for frequency applications.

Embodiment 16

On the thick paper tinsel S face of the thick electrodeposited copper foil of 35 μ m (surface irregularity: Ra 0.2 μ m), electroplate the thick Ni-P layer (weight ratio 94: 6) of last 0.5 μ m.Then, with following three compounds, every class is dissolved in and produces 20-25wt% solution in the dimethylbenzene:

I) 75 parts by weight of ethylene propylene diene trimers (EBDM K9720, Mitsui petro chemical industry company) and 25 weight portion liquid polybutadienes (LPB-3000, Japan petroleum chemical company)

II) 100 weight portion butyl rubbers (JSR Butyl 365, Japan SYnthetic Rubber Co. Ltd) and

III) 100 weight portion polybutadiene (Nipol BR 1220L, Japanese ZeOn company).Vulcanizing agent in embodiment 13 tables 4 and vulcanization accelerator are mixed with it, and careful the stirring fully disperseed it.

Above-mentioned three compounds are coated on the Ni-P treated side of Copper Foil, dry back forms the thick adhesive film of 10-25 μ m.7 layers of FR-1 level paper-based phenolic resin copper clad laminate (MCL437F) usefulness that Hitachi Chemical Company Ltd. is produced cover paper, be placed on these and be coated with on the adhesive surface with the Copper Foil of adhesive, thus at 170 ℃, 150kg/cm ²Lamination is made a copper clad laminate and two sides copper clad laminate after 40 minutes.

Measure above-mentioned laminate by JIS-C6481.The results are shown in table 6 shows good; Prove that they have good peel strength and anti-tracking performance.

Embodiment 17

With the 1-4 in the table 8 number with embodiment 13 in the table 4 and 5 all vulcanizing agents combine (mixing ratio is to provide with respect to 100 parts by weight resin components, similar in appearance to the situation of EPDM) be used to form the 50wt% methyl ethyl ketone solution.They with resin impregnated glass colth (WEA18W105F115, E glass, Nitto Boseki company), are made coated cloth (coating content: 40-45wt%).On the light face (surface irregularity: Ra 0.30 μ m) of the thick electrodeposited copper foil of 18 μ m, electroplate the thick Ni-Zn(60wt%Zn of 0.5 μ m) layer.On the coated cloth of making more than four layers, put paper tinsel, face down, at 170 ℃, 100kg/cm with Ni-Zn ²Add the hot pressing layer 1 hour, and formed laminate.

Press JIS-C 6481 these copper clad laminates of assessment.Under the room temperature and 180 ℃ of peel strength 〉=2.0kg/cm after 48 hours.This is better than the epoxy resin copper clad laminate peel strength 1.3kg/cm at room temperature that routine is used the Copper Foil system of handling through hacking.

Embodiment 18

1-4 composition epoxy resin in the table 9 is combined with all vulcanization accelerator shown in table 4 and 5 (mixing ratio is to provide with respect to 100 parts by weight resin components), be used to form the methyl ethyl ketone solution of 50wt%.They are used for impregnated glass colth (WEA18W105F115, E glass, Nitto Boseki company), to produce coated cloth (coating content: 40-45wt%).Simultaneously, on the bulging face (S face) (surface irregularity: Ra 0.30 μ m) of the thick Copper Foil of 18 μ m, electroplate the thick about 94wt%Ni of Ni-P(of 0.5 μ m) layer.On above-mentioned four layers of coated cloth making, put paper tinsel, face down with Ni-P, at 170 ℃, 100kg/cm ² Heated lamination 1 hour forms laminate.

Press JIS-C 6481 these copper clad laminates of assessment.Under the room temperature and 180 ℃ of peel strength 〉=2.0kg/cm after 48 hours.This numeral is much better than the analog value 1.3kg/cm of conventional example, clearlys show the extremely excellent sulfurization of this metal and adhesive.

Embodiment 19

The BT resin combination of table 10 1-4 number combines (48 classes, mixing ratio is by providing with respect to 100 parts by weight resin components) with all vulcanization accelerator shown in table 4 and 5 and vulcanizing agent, is used to form the 50wt% methyl ethyl ketone solution.

To immerse in this lacquer with used the sort of similar glass cloth E in the embodiment 17, drying forms coated cloth (coating content: 40-45wt%).Copper Foil and four layers of coated cloth lamination are made the such copper clad laminate of embodiment 18.

Press JIS-C 6481 these copper clad laminates of assessment.Under the room temperature and 180 ℃ of peel strength 〉=2.0kg/cm after 48 hours.This numeral is better than conventional copper clad laminate peel strength 1.6kg/cm and 180 ℃ of peel strength 1.3kg/cm after 48 hours at room temperature, clearlys show the extremely excellent sulfurization of this metal and adhesive.

Can know from above-mentioned embodiment and to find out that the present invention has following effect: the grappling effect, be used to improve the adhesion strength between Copper Foil and insulating barrier, this effect can prevent that circuit from narrowing.First effect of the present invention is, might use and not do the Copper Foil that hacking is handled, because directly sulfurization has guaranteed not have the powerful adhesion strength of the light face of grappling effect Copper Foil.Cancelled and need hacking to handle to have reduced process, to have improved productivity ratio, this has reduced the production cost of Copper Foil conversely again, thereby has also reduced the production cost of copper clad laminate.In addition, for the roll-in Copper Foil that is difficult to form big hacking particle, its powerful viscosity intensity also is guaranteed by direct sulfuration.This just makes and might adopt the production of roll-in Copper Foil in copper clad laminate.

Second effect of the present invention is to have reduced the adhesive material cost and reduced the coating consumption.It is because can use inexpensive general purpose rubber that the coating consumption greatly reduces, and can be on the light face of Copper Foil adhesive coating.Coating thickness is 20-30 μ m in prior art, and the situation of the used adhesive of the present invention makes coating thickness only for this reason 1/2 of value to 1/5.

First effect of the present invention is that to the improvement of performance it is to making the contribution of forming fine wiring pattern.If the light face Copper Foil of handling without hacking is used as the Copper Foil of copper clad laminate of the present invention, then might form the circuit of 20 μ m wide (18 μ m are thick), far surpass the requirement of conductor separation 0.1mm, the latter has been the limit that forms circuit in the conventional etching; Thereby contribute to making the forming fine wiring pattern.Comprise in production in the multilayer circuit board process such as glass cloth epoxy resin that the present invention has saved to improving the blackout that cementing property will do the light face of Copper Foil and handled, the latter causes productive rate to reduce.The result who saves the blackout processing procedure has guaranteed improvement productivity ratio and has reduced cost.

Second effect is the invention provides good anti-tracking performance.When the material with good anti-tracking or propylene diene trimer with fabulous anti-tracking use, in conventional adhesive, to add inorganic additive or a lot of Malaysias polyimide resin improves anti-tracking; Therefore the slip between the Copper Foil is unsmooth, causes uneven coating.This has been the permanent problem that exists.In contrast, in non-aromatics and non-polar polymer, the propylene diene trimer with good anti-tracking performance can be used for the used adhesive of the present invention, thereby can save and need use inorganic additive, thereby has improved the coating operating efficiency.

The 3rd effect be the present invention to allow to use tow sides all be the Copper Foil of light face, thereby reduced the distortion of high-frequency signal waveform.This will solve a key issue in the developing mechanics of communication, and printed circuit board (PCB) expanded application in the frequency applications field has been made significant contribution.

As discussed above, because adhesion strength is improved between insulating barrier and the Copper Foil, the advantage of bringing comprises the expansion of the scope of properties of product and production technology.

Claims (18)

1, a kind of have by the mutually bonding Copper Foil of lamination and the copper clad laminate of the adhesive surface between the insulating barrier, wherein Copper Foil with the face of insulating barrier bonding on have a metal level, metal level and insulating barrier are cross-linked with each other by the chemical bond through sulphur atom.

2, the copper clad laminate of claim 1, wherein Copper Foil has a metal level, and this metal level comprises and is selected from the metal or alloy that contains following at least one dvielement: B, Al, P, Zn, Ti, V, Cr, Mn, Fe, Co, Ni, Ag, In, Zr, Sn, Nb, Mo, Ru, Rh, Pd, Ta, W, Ir and Pt.

3, the copper clad laminate of claim 2, wherein metal level comprises Cu-Zn alloy, Ni-Zn alloy, Ni-Sn alloy, Ni-Cu alloy, Pd-P alloy or Ni-P alloy.

4, claim 1,2 or 3 copper clad laminate, wherein Copper Foil is the Copper Foil that roll-in or electrolytic deposition are made, thick 3-500 μ m, metal level are thick non-magnetic metal layer or alloy-layers of 0.01-5 μ m.

5, the copper clad laminate of claim 1, wherein insulating barrier is by containing the cross-linked rubber adhesive layer that adhesive with the compound that can vulcanize unsaturated bond and at least one class vulcanizing agent that is selected from sulphur, sulfur donor and mercaptan are cross-linked to form.

6, the copper clad laminate of claim 1, wherein insulating barrier is by containing the adhesive with the compound that can vulcanize unsaturated bond, the mercaptan of at least a do sulfuration usefulness and the cross-linked rubber adhesive layer that at least a peroxide crosslinking forms.

7, the copper clad laminate of claim 5, adhesive wherein contains a kind of vulcanization accelerator.

8, the copper clad laminate of claim 5, wherein having the compound that can vulcanize unsaturated bond is the ethene-alpha-olefin copolymer that is obtained by ethene, alhpa olefin and the copolymerization of dienes compound.

9, the copper clad laminate of claim 7, ethene-alpha-olefin copolymer wherein are propylene diene trimer (EPDM), or ethylene butene diene trimer (EBDM).

10, the copper clad laminate of claim 5, adhesive wherein contain at least one class material that is selected from natural rubber, isoprene rubber, styrene-butadiene-copolymer, polybutadiene, butyl rubber, acrylonitrile butadiene copolymer, halogenated butyl rubber, chloroprene rubber and acrylic rubber.

11, the copper clad laminate of claim 5, layer structure wherein be this dielectric substrate be by laminate adhesive to the cross-linked rubber adhesive layer.

12, the copper clad laminate of claim 5, layer structure wherein be this metal matrix be by laminate adhesive to the cross-linked rubber adhesive layer.

13, the copper clad laminate of claim 1, wherein insulating barrier is the dielectric substrate that is cross-linked to form by the matrix of having flooded adhesive and at least one class vulcanizing agent, wherein Jin Zi adhesive contains and has the compound that can vulcanize unsaturated bond, and vulcanizing agent then is selected from sulphur, sulfur donor and thio-alcohol.

14, a kind of multilayer board with multilayer circuit Copper Foil of the Copper Foil formation in dielectric substrate, its improvement is that described circuit Copper Foil has the metal level on the insulating barrier of the insulated substrate of adhering on its surface, and this metal level and insulating barrier are crosslinked by the chemical bond through sulphur atom.

15, the multilayer board of claim 13, wherein on dielectric substrate, form, every block of circuit Copper Foil all has a pair of circuit Copper Foil of a metal level on the surface, be cross-linked with each other by at least a vulcanizing agent that contains dielectric adhesive and be selected from sulphur, sulfur donor and thio-alcohol with the compound that can vulcanize unsaturated bond.

16, the multilayer board of claim 13, wherein on dielectric substrate, form, every block of circuit Copper Foil all has a pair of circuit Copper Foil of a metal level on the surface, by impregnated in being cross-linked with each other of matrix insulating binder with at least one class vulcanizing agent, wherein Jin Zi insulating binder contains the compound with vulcanizable insatiable hunger key, and vulcanizing agent then is selected from sulphur, sulfur donor and thio-alcohol.

17, a kind of method of handling copper clad laminate wherein makes the copper clad laminate of claim 1 be dipped in the aqueous solution of hydrochloric or its salt.

18, a kind of method of handling multilayer board wherein makes the multilayer board of claim 13 be dipped in the aqueous solution of hydrochloric or its salt.

Images