Improved method for pre-treating a polymer surface prior to its plating and an improved metal-plated plastic article formed by the method

[Detailed Description of the Invention]

Field of the Invention The present invention relates to the method of improving for plating metal on the polyimide surface, especially improvement of the quality of a polyimide group object by which metal plating was carried out. PRIOR ART The printing circuit board serves as main media for attaching electronic parts and connecting mutually, in order to manufacture a desired electronic circuit. A printing circuit board consists of a sheet of the dielectric base formed from the quality of a compound which does not usually blend or blend a bulking agent. The base has a pattern of a metal thin film which functions as an electric conduction way on the whole surface or both sides. These electric conduction ways, i.e., a "locus", are usually formed from steel, palladium, nickel, or a conductive substance like gold. These loci specify collectively all the electrical links between the components on a circuit board, and appoint the passage between suitable positions. Especially thermoplastics like polyimide is suitable as an object for the bases of the standpoint of those intensity, heat resistance, dimensional stability, and formability to a printing circuit board. However, a polyimide group object does not give a strong adhesive metal locus easily. That is, a printing circuit, i.e., the electric conduction way of the plated metal, has a possibility that damage may be separated from Acceptance or a base while using [ the manufacture process after following, or ] a circuit board. Various researches have been made in order to improve the adhesiveness to the polyimide group object of a conductive metal locus. Generally, Do measurement of the adhesiveness is carried out with the power of requiring a metal locus for exfoliating, from a base under "peel strength, i.e., a control condition." One of the methods by which the conventional proposal is made for an adhesive improvement gives the rough side to which you make it the metal tunic which carries out grid blasting of the base surface, and is given after following fixed. Other methods swell the surface using a chemical swelling agent or an osmosis agent. Since it was the adhesive reinforcement art mentioned above or a dissatisfied thing, some new knowledge was brought about in this technical field. For example, U.S. patent application SN of Dumas and others for whom it applied on December 29, 1986, The adhesiveness of the plating layer on the surface of polyimide is improvable by processing the surface with an adhesive reinforcement compound, wherein existence of a >No-molecule portion like hydroxylamine so that it may be written in No. 947,116 specification. Foust and others is teaching the adhesive reinforcing method which uses an organic double bond content compound like thiourea in U.S. patent application SN dated September 28, 1987, and a No. 103.618 specification. Each of these methods contacts the surface to a relief etching compound, and it contacts them in the basic solution which subsequently often contains short chain alcohol, It is often improved by first performing surface preliminary treatment which consists of making the solution of alcohol and another relief etching compound contact after that. Especially this preliminary treatment gives the pure water wettability surface suitable for the adhesive reinforcement processing after following. The concern about the plating method which does not need use of an inflammable solvent like methanol and ethanol in industrial plating equipment is increasing. In other chemical industry, similarly, it is nonflammability and, moreover, attentions have gathered for use of a water system for avirulence and the reason for dealing with it and being easy. However, there is a difficulty that generally water solution does not have solubilization ability like most organic solvents. For example, in the preliminary treatment method mentioned above, the surface residual substance of the plastic formed into the first etching process is removed very effectively from the surface in the process after following [ which uses methanol or other alcohol ]. In contrast, water is not effective in removal of this residual substance, therefore it gives the base as for which appropriate The is not in particular in the adhesive reinforcement process and plating process after following. The first object of the present invention is processed [ Did it carry out? ] by an adhesive reinforcement agent after following, and it is in providing the preliminary treatment method of an effective water substrate to the polyimide surface by which metal plating should be attached and carried out. The another object of the present invention eliminates use of a volatile solvent, or reduces it as much as possible, and is to provide the method of giving a very adhesive metal layer on a polyimide group object. The another object of the present invention is a form of for example, a printing circuit board, and circuit metal is to provide the polyimide group object which is what is characterized by the advanced adhesiveness over the smooth appearance and polyimide surface which are finished and are glossy and by which metal plating was carried out. The gist of an invention If the present invention is followed, the above-mentioned object will be achieved by adopting the method of having been improved which carries out preliminary treatment of the polyimide surface as a preparatory step of adhesive reinforcement processing and the plating processing to up to the surface after following, and the preliminary treatment is the following process; (A) It consists of contact with the cation system surface-active agent from which the remains tunic formed on the surface after contact; with the surface mild base solution of the etching (henceforth relief etching); (B) surface and the process on the surface of (C) (A) can be removed. Further, like the above-mentioned, preliminary treatment of the present invention is carried out, and it includes an article including the polyimide group object subsequently processed by the adhesive reinforcement agent, The article contains the metal layer which was given in electrolysis on the metal layer further given in no electrolyzing on the base, and this unelectrolyzed layer and which does not contain a chemical additive agent substantially. The article may contain another layer containing the chemical additive agent given on the first above-mentioned electrolysis metal layer given in electrolysis. The detailed indication of an invention Selection of the polyimide substance of individual specification for processing according to the present invention is not criticality-like. Polyimide is common knowledge in the art concerned, for example, is a volume on Kirk-Othmer, and Encyclopedia of ChemrcalTechnology. It is indicated to the 3rd edition and the 18th volume. Especially desirable polyimide is formed in the present invention by the reaction with what is generally called "polyether imide", for example, bisphenol A and a Di anhydride, (BPADA), and Off 22 range amine. U.S. Pat. No. 3,983,093 by which the examples and those manufacturing processes of polyether imide were given to WNIjams, III et al., Bolon and others, respectively -- and -- said -- since it writes in the 4.360th and No. 633 specification, please refer to it. Polyimide may contain the bulking agent or reinforcement agent which is common knowledge in a various quantity in the art concerned. The example of the bulking agent and the reinforcement agent is written in United States patent 4.525th and No. 508 specification which are quoted as a reference here. These substances are talc, mica, aluminum silicate (clay), and a zinc oxide, Those mixtures, such as meta-calcium phosphate, a titanium dioxide, carbon black, franklinite, sedimentation or natural calcium carbonate, glass fiber, a glass bulb, a silicone polyimide copolymer substance, and carbon fiber, are included. These polyimide may contain other natural various additive agents, for example, paints, an ultraviolet ray absorbent, a shock-proof improvement agent, a plasticizer, an antioxidant, stabilizer, processing aid, a spray for preventing static electricity, etc. The base of the present invention can take various shape and sizes. for example, -- the base can be a printing circuit board with the surface which is even or Curvature(ed) -- that the circuit board is [ that further various cavities, projection parts, and through holes (through hole) can be included ] double or more than it -- separate -- polyimide layers -- for example, it may be a multi stage story circuit board. Before the polyimide surface by which preliminary treatment should be carried out according to the present invention performs the process after following, it should be moderately pure. It can be used unless various sanctification agents have an equivalent bad influence on the polyimide surface. A suitable sanctification agent includes a registered trademark Freon (Freon) type solvent like a Halo carbon substance, for example, 1, 1.2-Tori Krol 1 and 2, and 2-truffe Ruol ethane. Relief etching processing of the pure polyimide surface is carried out, and a remains tunic is made to form in surface" 2 in a process (A). The example of a relief etching compound suitable for using it on the polyimide surface includes sulfuric acid, N, and N-Dimethylform amide, an N-methyl 2-pylori boss, pyridine, a tetrahydro franc, and a methylene chloride. Although the layer on the surface of polyimide is removed so that these compounds may be mentioned below, Since these compounds do not carry out raw [ of swelling or the crack ] to the bulk of a polyimide group object at the time which often occurs when using swelling and etching technique of conventional technology, in using it in accordance with the method stated to the present invention, Etching with these compounds is considered un-eroding-like by relief etching. The "bulk" of the term used here and a base is a field of the base beyond about 15 microns or it under the base surface plated by various embodiments of the present invention. Sulfuric acid is cheap, and since it is water and miscibility, it is a desirable relief etching compound, and it is preferably used with a high-concentration form, i.e., underwater, with at least about 85% of the weight of concentration. A relief etching compound performs the well-known method, for example, brush coating, spraying or immersion of a base, - according [ on an embodiment desirable / that it can give "be alike" / and ] to the alcohol of water, methanol, or others following this processing, or the rinse washing process beyond it. Since one of the objects of the present invention is making use of a flammable solvent into the minimum, or eliminating, it is preferred in using water as a rinse agent. The desirable method of contacting a base to the arbitrary things of the object for a rinse of the present invention, the object for preliminary treatment, and the constituent for adhesive reinforcement processing is a method of making a base immersed in bath containing the constituent of individual specification. Therefore, especially a description here is emphasizing the immersing method, or the person skilled in the art should understand that it is what can be applied to known touch technique besides the time which mentioned such art above without the necessity for an excessive experiment. Processing with a relief etching compound may be performed the time for about 15 second~about 5 minutes, and rinse washing by water is usually performed after that. But effective processing time is related to the application method of individual specification [ a part ]. When a base should be immersed in the solution of a relief etching compound, processing is performed in time not to usually exceed about 3 minutes, but this time is influenced by the concentration of a relief etching compound, and the temperature of solution. Generally, although Room temperature bath is enough, processing time can be shortened if the degree of bath temperature is raised. Similarly, processing time can be shortened even if it increases the concentration of an etching compound (for example, sulfuric acid). The person skilled in the art can determine easily the combination of time / temperature / concentration suitable about the processor of individual specification. The remains tunic of various thickness is formed on the surface of polyimide between processings with a relief etching compound. This tunic remains on the surface, even after washing by rinsing. In a process (B), it processes for about 30 second~about 10 minutes with basic (namely, alkalinity) solution by one of the art which mentioned this tunic above. It seems that this process denatures a remains tunic and reduces that adhesiveness on the surface of polyimide. Suitable basic solution includes the solution formed by dissolving sodium hydroxide, a potassium hydrate, water oxidization tetramethylammonium, and those mixtures at a rate of 0.1 mol (M)~abbreviation 10M into a solvent like water. In an embodiment with the present invention, other solvents like methanol, ethanol, ethylene glycol, and those mixtures may be used. However, water is preferred at the point which is nonflammability. Generally, the person skilled in the art can select the suitable solvent for a case, Solute, and Solute concentration of individual specification, without conducting an excessive experiment. In a process (A), the solution of room temperature is enough similarly. Usually, following a process (B), it is water, and rinses and washes the surface. In a process (C), the tunic residual substance on the surface is removed by contacting the surface to a cation system surface-active agent. The central atom of this type of compound is usually nitrogen or a phosphorus cation, and like quarternary ammonium salt, it is combined with - or the organic side chain beyond it, or it often constitutes a part of organic heterocyclic system like pyridine. Two conditions are required about the cation system surface-active agent used in this process of the present invention. In the first place, the surface-active agent can remove a tunic residual substance from the polyimide surface. When a surface-active agent is a solid, carrier solution and usual must be [ second ] meltable in water. The maximum carbon chain length of the Alkyl machine combined with the cation of the cation surface-active agent is influenced by the solubility to the inside of the carrier solution of a surface-active agent. For example, the Alkyl pyridinium halide with 20 pieces or the carbon chain length beyond it has the usually limited degree of aqueous solution of aqueous solution, i.e., the degree lower than about 1~2 % of the weight. This compound can be used when effective in removing a remains tunic from about 1 % of the weight by low concentration. One of the signs which do not show solubility sufficient probably in order that a certain specific surface-active agent may use it for a process (C) is the point that Oiled surface appearance is accepted on polyimide after contact with a surface-active agent constituent. The examples of suitable cation system surface Active cutting for the process (C) of the present invention are enumerated to the following compound classification. (1) Alkyl pyridinium halide The example of this type of Alkyl pyridinium halide includes cetyl pyridinium chloride and Dodecyl pyridinium chloride. (2) The example of the suitable compound of the model of Alkyl trimethylammonium halide This is an octyl trimethylammonium star's picture, A Decyl trimethylammonium star's picture, a Dodecyl trimethylammonium star's picture, and a hexadecyl trimethylammonium star's picture are included. (3) Alkyl triphenyl phosphonium halide The example of this type of suitable compound includes a Decyl triphenyl phosphonium star's picture and a Dodecyl triphenyl phosphonium star's picture. This type with the alkyl chain containing carbon atoms fewer than about eight pieces of compound is not considered to be effective in surface sanctification as shown in the after-mentioned example. This type that contains about 15 or the carbon atom beyond it in the main alkyl chain of compound has the marginal degree of aqueous solution, therefore these are not usually suitable for it, either. (4) An example of this suitable type for the tetra-alkylammonium halide present invention of compound is tetrabuthyl ammoniumchloride. This type containing few carbon atoms in [ of about four pieces ] an alkyl chain of compound is not effective in removal of a remains tunic, these compounds that, on the other hand, contain about six pieces or the carbon atom beyond it in a main alkyl chain have the limited degree of aqueous solution, therefore these are not usually suitable for the object of the present invention, either. These compounds should be underwater used with at least about 1% of concentration, and the treatment temperature of at least about 50 degreeC. Another cation system surface-active agent which can be used by the method of the present invention is a stearyldimethylbenzylammonium star's picture. the hydrate of many above-mentioned compounds, for example, cetyl pyridinium chloride -, -- it may Also used 1 hydrate. Cation system surface-active agents desirable for a process (C) are cetyl pyridinium chloride and 1 hydrate, a cetyl pyridinium star's picture and 1 hydrate, a Dodecyl trimethylammonium star's picture, and a hexadecyl trimethylammonium star's picture. Cetyl pyridinium chloride and 1 hydrate is the most preferred in respect of a price, acquisition ease, and validity. The cation system surface-active agent which is a solid is usually used in the form of solution. Although a liquefied cation system surface-active agent may be used directly, without diluting with a solvent, it is convenient to usually use it in the form of solution. the concentration of the long-chain cation system surface-active agent in solution -- about -- about [ 3x10-M~] -- about [ the range of 0.3M preferably about 0, and / OIM~] -- it is the range of 0.1M. each in within the limits of these -- specific concentration is a required thing which conducts an excessive experiment on a person skilled in the art and it can be determined that will carry out by taking into consideration various factors like the solubility of a surface-active agent, the quantity of the residual substance which exists on the polyimide surface, and the validity of a specific surface-active agent. As for the contact time on a cation system surface-active agent and the surface of polyimide, a part is determined by the concentration of the surface-active agent in solution, and contact time is usually a range for target 2 Of course~about 10 minutes, when a base is immersed into the solution of a surface-active agent. Desirable immersion time is a range for about 5 minute~about 10 minutes. Although surface-active agent solution is used at room temperature and is effective, the temperature of the range of about 40 degrees C~60 degreeC is often preferred, and it is desirable when the solubility of the surface-active agent of individual specification is limited especially a little. It is thought that a higher temperature in within the limits of this promotes removal of a remains tunic. Solution containing Deleting outside cation system Survival - is aerated often gently, in order to promote removal of a remains tunic. This can be attained by only carrying out foaming of the air into solution. Since foaming of a surface-active agent may take place during aeration, in solution, an antifoaming agent is also an effective amount and it can usually add it in the quantity of about 1100 pp(s)~about 2500 pp+11 based on the full weight of solution, for example. It can be used on the conditions that a wide range antifoaming agent does not have a bad influence on the polyimide surface, and does not react to a cation system surface-active agent. The examples of an antifoaming agent are AF9000 of General Electric Company, and a product of 544 series of Dow Corning. Usually, rinse washing by water is performed following a process (C). The polyimide group object in this stage has the pure water wettability surface which shows advanced receptiveness to adhesive reinforcement processing and subsequent plating processing. As shown in the after-mentioned example, the preliminary treatment mentioned above improves the adhesiveness of the metal layer to a base notably, and when especially a base contains a bulking agent, it shows a remarkable improvement. In an embodiment with the present invention, a process (B) and a process (C) are combinable, unless all ingredients cause the disadvantageous reaction for mutual. The disadvantageous reaction will occur, when mixing with basic solution the cation system surface-active agent containing for example, a pyridine ring. Therefore, when using a pyridine ring content cation system surface-active agent, a separate process is preferred as mentioned above. In everything but a large majority, these two processes are combinable by mixing each ingredient at same rate, if it is used when performing these processes separately. however, contact time does not need it twice the contact time of each separate process -- because -- instead, it is because other parameters can be adjusted. For example, means, such as raising the degree of aeration and the degree of churning of the tub holding a treating solution, or raising solution temperature again, can be adopted, a workpiece being immersed into a treating solution. It is clear from the place mentioned above that preliminary treatment's of the present invention in a desirable embodiment it is a thing in a water system, i.e., it is what uses water at the process of using a solvent. However, this does not except existence of the organic solvent of the few rate in various processes, unless this rate produces the damage on healthy of ignition or others. The present invention pretreats the polyimide surface by relief etching further, The surface is contacted in basic solution and the surface is contacted to a long-chain cation system surface-active agent, Subsequently, it processes by the adhesive reinforcement agent chosen from the group which consists of a compound including the compound and the organic double bond by which the surface is characterized by existence of a >No-molecule portion, and provides the method of giving a metal layer on the polyimide surface which turns into the surface from carrying out unelectrolyzed plating of the metal after that. The compound for adhesive reinforcement, wherein existence of a >No-molecule portion is written in U.S. patent application SN dated December 29, 1986 of Dumas and others quoted as reference data here, and No. 947,116 specification. This type of compound is usually Y\. N-0-R, Yl =N-0-R, and those 2/ Salt or a hydrate (inside of a formula) R -- hydrogen; -- about 1~ -- about ten carbon atoms The included Alkyl machine; the carbon atom of 20 abbreviation 6~abbreviation included aromatic series machine; -- it is the atom or basis chosen from the group which consists of sulfonic group Nia Schill machine; and an amide machine --;Y and Z -- respectively -- hydrogen; -- about 1~ -- Alkyl machine; containing about 20 carbon atoms -- about 6~ -- the aromatic series machine Nia Schill machine containing about 20 carbon atoms, And it is the atom or basis chosen from the group which consists of an amide machine, and; or Y, and 2 are nitrogen atoms together. At least one heterocycle type carbon content ring is formed, and :, or Z and R are the molecule portion together. forming at least one heterocycle type carbon content ring --; and Yl -- about 1~ -- the alkylidene group containing about 20 carbon atoms and about 1~ -- it characterizes according to the structure chosen from the group which consists of being the basis chosen from the group which consists of a cyclo alkylidene group containing about 20 carbon atoms. the desirable compound for adhesive reinforcement corresponding to the above-mentioned formula -- benzo[ O,N-Dimethyl hydroxylamine hydrochloride, acetone oxime, 2-pyridine Aldoxime, N-hydroxy Phthal imide, and / 1-hydroxy ] -- it is doria SoleandR20. This type of especially desirable compound for adhesive reinforcement is salt of hydroxylamine or hydroxylamine. In the U.S. patent application specification of Dumas and others mentioned above, the method of preparation and directions of the compound solution for adhesive reinforcement are also written further. for example, the time by which the compound for adhesive reinforcement is defined there -- the inside of the non-eroding-like fluid -- about -- about [ 0.5M~] -- it can blend at the concentration of the range of 4 *0M. Subsequently, in adhesive reinforcement agent solution, about 10 minute~about 60 part carries out time immersion, and it obtains the polyimide surface. Although these fluid ingredients may be organic ingredient, for example, pyridine, methylene chloride, N, and N-Dimethylform amide, methanol, or those mixtures, it is preferred that it is water. Another group of the above-mentioned compound for adhesive reinforcement is a compound which includes an organic double bond at the time written in U.S. patent application SN dated September 28, 1987 of Poust and others quoted as reference data here, and No. 103,618 specification. these compounds -- usually -- formula: -- % type % (X expresses oxygen or sulfur each independently among a formula,;R1 and R2 become independent, and it is hydrogen) about 1~ -- the Alkyl machine containing about 15 carbon atoms and about 6~ -- the aromatic series machine containing about 20 carbon atoms and about 1~ -- expressing the atom or basis chosen from the group which consists of an alkoxy group containing about ten carbon atoms R3 and R4 become independent, and it is basis R'. S, -, Nl2. NHRI, The basis chosen from the group which consists of NHNH2 and RICO is expressed, R5 expresses the basis chosen from RNHR+ and S-,;R6 and R7 express the Alkyl machine which contains independently hydrogen or about 1~10 carbon atoms, respectively, and;Y is NH. NHN1.-8-8. 1~ -- the Al Killen machine containing about ten carbon atoms and about 1~ -- expressing the basis chosen from the group which consists of an Ally Wren machine containing about 20 carbon atoms --; and n -- 1 or 2 -- it is -- they are the compounds which it has and those salt, or a hydrate. It is chosen out of the group which consists independently of hydrogen, a low-grade Alkyl machine, a lower alkoxy group, and a phenyl group preferably [ R1 and R2 ], respectively in formula 1~■. R3 and R4 are preferred, and it becomes independent, respectively, and is low-grade Alkyl machine +. N R2 and NHNR2+ It is chosen out of the group which consists of a lower alkylamino group and a CI3CO-basis, On the other hand, R5 is NHCH3 or NHCH2CH3 preferably, and R6 and R7 are preferred, and it is chosen independently from hydrogen or a low-grade Alkyl machine, respectively. As this type of desirable compounds [ some ] for adhesive reinforcement, it is the following compound, Namely, thiosemicarbazide hydrochloride, 2, 4-dithio biuret, semi Carbazide chloride salt, acetylthio urea, thiourea, the aceto amide, urea, N N-Dimethyl aceto amide, Thioacet amide, and Thiocyanian acid can be raised. The most desirable compound for adhesive reinforcement for the object of the present invention is thiourea. this type of compound for adhesive reinforcement -- desirable -- the inside of a non-erosive fluid -- about -- 0. 1mm%~ -- it is blended at the concentration of z% of about 50-fold range, more preferably about 1 % of the weight ~ about 20% of the weight of the range. A non-erosive fluid is water preferably. As for this solution, in a certain case, although neutral pH is usually substantially preferred about the solution of the compound for adhesive reinforcement, it is advantageous to acidify by addition of acid, such as citrate, phosphoric acid, sulfuric acid, and chloride. When copper exists on a base in advance of processing with the compound for adhesive reinforcement so that it may be written in the U.S. patent application specification of Foust and others mentioned above, use of an acidic solution is preferred. Acid is made to exist in a quantity effective in holding pH to about 4, less than [ preferably ] 4, and less than about 1.0 value. As for the temperature of the solution containing an adhesive reinforcement agent, it is preferred to hold to with a processing width [ on the surface of polyimide ] of about 65 degrees C~85-degreeC. The person skilled in the art can determine the optimal temperature easily based on the aqueous solution degree characteristic of the adhesive reinforcement agent of individual specification [ a part ]. After processing by exposing the polyimide surface to the compound for adhesive reinforcement, Rinse washing of this base can fully be carried out with water by a method at the time written in the U.S. patent application specification of for example, the common knowledge to a person skilled in the art, a U.S. Pat. No. 3,589,916 specification and Foust et al. that quoted [ above-mentioned ], Dumas and others, and, subsequently to [ for plating processing ], it can be activated. For example, this base can be contacted sufficient time to occur acid solution of the precious metals like the palladium chloride in chloride, and the contact activation on the surface of a base. It is often useful to start activation of a base by processing with the additive agent which promotes absorption of the catalyst for plating. This additive agent is common knowledge in the art concerned. Absorption of a catalyst Sibley whose example of the additive agent which promotes is Sibley's (Shjpley Company) product (Shipley) Metex (Metex) 9420 which is a product of 1175 A and a pine Cedar mid company (MacDer[l1id Corporation) is included. either of these additive agents -- about -- the inside of the solution 0. 1~capacity [ about 5 ] % included -- about -- if immersed for about 1~10 pieces at the temperature of 40 'C~about 80' C, it will usually come out enough. For the present invention although [ darn processing / criticality ], the use often promotes the uniform Analysis arrival of the metal by unelectrolyzed plating of a up to [ a base ]. An example of activation art includes the process that a base is immersed into the solution of registered trademark Shipley Caterprep (ShipleyCataprep) 404 which is Sibley's product. This solution provides the protecting agent for the catalyst for plating given after following, and this contains sodium hydrogensulfate and various surface-active agents. Subsequently, you may make it a base immersed into the solution of registered trademark Caterpid (Cataposit) 44 of Sibley who is an unelectrolyzed plating catalyst containing the ingredient, tin, and palladium of registered trademark Caterpupu 404. It can be immersed into the solution of registered trademark Cuisit (Cuposit) accelerator 19 of Sibley who is a fluoboric acid containing composition which is water, and is used in order to succeed to the base after rinsing and washing and to separate tin from a plating catalyst. W which quotes activation suitable for the present invention, and the plating method as reference data here, It writes also in T, U.S. patent application SN dated December 22, 1986 of Grubb and others, No. 944*728 specification, the U.S. Pat. No. 3011.920 specification of 5hipley, and United States patent m No. 3.841 or 881 specification of Pe1dstein and others. Rinse washing by indifferent water is performed after an active chemically-modified [ this ] degree. Unelectrolyzed plating can be performed after surface-activity-izing and rinse processing. The example of the metal used in order to form a plating layer includes copper, palladium, nickel, and gold. When forming a printing circuit, copper is usually selected as a metal. The volume on Kirk-Otbmer and Encyclopediaof'Chemical Technology which unelectrolyzed Plating bath is common knowledge at a person skilled in the art, for example, it quotes as a reference here, The 3rd edition is generally indicated to the 8th volume. Selection of specific Plating bath or the unelectrolyzed plating method is not criticality-like for the present invention. The content of bath and the parameter of the plating process of individual specification, for example, temperature, pH, and immersion time will be influenced with the metal of individual specification by which Analysis arrival is carried out to the natural individual specific plastic substance offered as a base, and its surface. Suitable Plating bath includes Sibley's registered trademark Cuisit 250 system and registered trademark Entry (Enthone) 406 system. The suitable unelectrolyzed plating bath composition thing for the U.S. patent application specification of Grubb et al., Dumas and others which quoted [ above-mentioned ] is listed. Immersion time, the degree of bath temperature, and other work parameters can be determined and controlled according to a manufacturer's proposal. The person skilled in the art about plating art can determine the plating method and conditions optimal about the situation of individual specification. The polyimide surface is offered by heat treatment after the Analysis arrival by unelectrolyzed plating of metal. Although oven heating of the base which has a metal tunic in the whole article, i.e., the surface, is enough because of this object, arbitrary heating methods can be used suitably. If this heat-treatment is typically performed for about 5 minute~about 120 minutes at the temperature of the range of about 60 degreeC~about 170-degreeC and a higher temperature within the limits of this is used, generally processing time can be shortened more and that contrary is also the same. It seems that the time required for it attaining the optimal adhesion can be shortened although the mechanism of heat-treatment has not been clarified yet. Heat treatment of the above-mentioned when another metal layer should be given, for example by electroplating on this surface can be omitted, when heat-treating after plating of this another metal so that it may mention below. However, a desirable embodiment includes the heat treatment process in front of the Analysis arrival of this another metal. But a desirable embodiment includes the heat treatment before the Analysis arrival of this another metal layer (that is, given after radio analysis arrival) with another heat-treatment after giving the last metal layer so that it may mention below. Electroplating is a desirable method for the application of this second metal layer. Before a base usually immerses into Electroplating bath, it is sanctified. Sanctification can be attained by being rare solution of strong acid like 10% of the weight of underwater sulfuric acid solution, and rinsing a base. Electroplating bath is written in the U.S. Pat. No. 4,555,315 specification which is common knowledge in the art concerned, and it quotes as a reference here. However, not each specific Electroplating bath used is criticality-like for the present invention. It is related to the metal of individual specification with this natural selection in which Analysis arrival of the part is carried out. A suitable metal includes the metal which indicated radio analysis arrival. What the content of Yoku of individual specification will be influenced for by the factor of shoes to probably be taken into consideration about the radio analysis arrival of the metal mentioned above is clear to a person skilled in the art. Electroplating bath for copper is typically operated using the cathode current density of the range of about I ASP~about 8 OASF(s) at the temperature of the range of 6 degrees of Strike C~about 38-degreeC. Plating bath of copper or other various metal is indicated volume [ 8th ] the literature of Kirk-Otbmer which quoted [ above-mentioned ], and after the 826th page. Yoku used in order to use a copper layer for a radio analysis arrival layer contains other well-known various ingredients typically in acid copper sulfate type or acid fluoboric acid copper type water acidity copper electrolysis solution; halite ion like a water electrolysis solution, for example, chloride, star's picture ion;, and a person skilled in the art. Probably, the thickness of this second metal layer is related to the end use of the request of a base by which metallic coating was carried out, of course. As it writes also in the above-mentioned U.S. patent application specification of Foust et al., Grubb and others, the metal given on the polyimide group object can be a form of a pattern. The example of the pattern drawing method is written also in the U.S. Pat. No. 3,562,005 specification of DeAngelo and others quoted as a reference here. In the desirable embodiment of the present invention, electrolysis Deposition layer given to the surface of a radio analysis arrival layer does not contain substantially the chemical additive agent which usually exists in electrolysis Deposition layer like a Uniformity exhibition agent and a brightening agent. Therefore, electrolysis Plating bath used as this For deposition is often called "additive agent additive-free" Yoku in this specification. These artificers found out that additive-free [ of these additive agents ] gave the exceptionally high level adhesiveness of the polyimide surface and a radio analysis arrival metal layer as shown in the after-mentioned example. The example of Electrolytic bath which does not contain a Leveling agent or a brightening agent contains strong acid like copper sulfate of about 100 g/rho~about 160 g/omega, and sulfuric acid of about 50 g/D~about 70g /, and rho, and the chloride ion of 75 ppm of about 35 ppffl(s)~abbreviation usually supplied in the form of chloride. Electroplating bath of other common knowledge can also be used in this embodiment on the conditions that a brightening agent, a Uniformity exhibition agent, and other chemical additive agents are excepted from Yoku. The rinse process by indifferent water is adopted following a plating process. Heat treatment can be used at the time mentioned above also in this stage. Typical heating conditions are about 1 hour~about 24 hours in about 75 degreeC~about 150-degreeC. The plating layer given from the solution which does not add a chemical additive agent at the time mentioned above usually has a little coarse wen-like appearance. To a certain end use, this surface is suitable, and is obtained, or, in other cases, the smooth and level surface is desired. The smooth surface can be attained by giving the second electrolysis Deposition layer containing a chemical additive agent to the surface of the first electrolysis Deposition layer. Yoku used in order to give this layer is often called "additive agent addition" Yoku in this specification. Before an etching agent often gives this second electrolysis Deposition layer, it is used. The example of an etching agent includes the mixture of ammonium persulfate or sodium and hydrogen peroxide, and sulfuric acid. The rinse process by indifferent water is performed following an etching process. Subsequently, the remains oxide of the metal which is dilution solution of strong acid again, rinsed the surface, processed, and was plated is removed. Probably, the example of the process stated to this last is the method of immersing a base for about 10 second~about 120 seconds into sulfuric acid solution of 10 % of the weight of abbreviation 1~abbreviation. The plating processing after following can be presented with a base in this way. Electrolytic bath for the application of the second electrolysis Deposition layer may be one of the Yoku of known common use in the art concerned. These Yoku contains an effective amount of brightening agents, a Uniformity exhibition agent, and other additive agents, and these all are common knowledge at a person skilled in the art, and it is a volume James M and on Margolis. Hanser Publishers 1986 issue and DecoratingPlastics ; J, D, Re1d, A, P, David work, 6~70 pages of Plating(s); The volume Frederick A and on Lowenhein, ModernElectroplating, the 3rd edition, and John Wiley & 5ons. It writes in the British patent application GB2123036A specification of Inc and issue:, Ri, Morrissey and others. The example of other chemical additive agents is an additive agent used for a stress relief agent, battery depolarizer, a plating depressant, a wetting agent, hardening, crystal microatomization, reduction of a dendrite crystal, and limitation of current density. Therefore, the term "chemical additive agent" used on these specifications shall be used in the meaning which includes the arbitrary things of the additive agent mentioned above. After the Analysis arrival of the second electrolysis Deposition layer, it is water again, a base is rinsed, and subsequently it heat-treats, and further reinforces the adhesiveness to the base of a metal layer. Typical heat treatment for this process is performed by the conditions of about 1 hour~about 24 hours at the temperature of the range of about 75 degreeC~about 150-degreeC. This heat treatment excludes the heat treatment used after the first electrolysis Analysis arrival. The metal layer which is characterized by the adhesiveness of the high level to a polyimide group object and which is smooth and glossy is given as a result of the second electrolysis Analysis arrival. The unelectrolyzed plating layer of usual 0.255 Mif Ron~2 micron thickness [ the product manufactured by the method of the present invention in the desirable embodiment ]; it has the second electrolysis plating layer with first electrolysis plating layer; of at least about 5 microns, and a thickness of at least about 5 microns. The product of various embodiments of the present invention is suitable as a printing circuit board which contains a metal layer at the time written in this specification in a printing circuit pattern or the form of a "locus." The specific example which makes an understanding of the present invention easier is shown below. These examples are only shown for the object of illustration, and should not be interpreted as adding limitation to the large concept of the present invention. Unless it is shown in particular, the ratio of all the fluids is a capacity ratio. In these examples, the adhesiveness to the metaled base was evaluated by measuring the power of requiring a metaled strip for exfoliating from the base surface. In this examination, the surface of metal of each plated sample is etched into a 1/8-inch strip. The end of each strip is stopped to the digital type power measuring instrument of All1etek connected to the computer processor. The power required for pulling up these metallic strips from a base is converted into the exfoliation value of a pound/inch by computer. Many exfoliation values are calculated about each strip, and, subsequently those average value is calculated. Example 1 The sample equivalent to each statement in the 1st table of a postscript was the base formed from the polyether imide material containing 30% of the weight of the glass fiber distributed by kneading. Unless it was shown in particular, each sample was processed according to the following method and conditions. A 1 and 1.2-1-Richlor 1.2.2-4 Refluol ethane C strong sulfuric acid which dries 2B base 0.5D It is underwater, rinse and wash. 2E Underwater pottasium hydroxide solution (5M) It is 5F underwater, rinses and washes. 2G It processes with a cation system surface-active agent (b). 50degreeC It is H underwater, rinses and washes. ■ Process by an adhesive reinforcement agent (0). It is 75-degreeCJ underwater, is K Sibley cleaner / conditioner 1175A (underwater 2.5 capacity % concentration) rinsed and washed, and 65-degreeCL underwater, rinses, and washes. M Sibley registered trademark Caterpupu 404N Sibley registered trademark Caterpid 44 (underwater 1.5 capacity % concentration), 44degreeC P Sibley registered trademark which is O underwater, and it rinses and washes Accelerator 19 It is Q underwater, rinses and washes. R Sibley registered trademark It is Cuisit 250 and 48-degreeC S underwater, rinses, washes, and sniffles. T Heat-treat in 75"C. Plating processing is carried out in 120U Copper Electroplating Bath (d). 60V It 95 degreeC Smells and heat-treats [ are and ]. A 16-hour (a) base was immersed into the fluid composition. (b) Use 0 or 05 % of the weight of underwater, 1 % of the weight of cetyl pyridinium chloride, and AF9000 antifoaming agent (C) underwater, and 12.5 % of the weight of thiourea with 1 % of the weight of citrate. (d) CuSO4phi5 120125 g/IH2SO460g/ (1; it plates with chloride ion 50ppm ; 36ASP in overall thickness of 2 mil.); It examined about adhesiveness after cooling to room temperature by the method which mentioned the sample above. A result is shown in the 1st table. 1st Table It carried out using the 5urface 5c1 enceX-ray Photoelectron 5 pectroscopic AnalyzerSSX-100 type which may be obtained from the apparatus part of the water system preliminary treatment of a first-as a result of [ three ] adhesive measurement invention, and owner ton. Nothing Glass 30% Glass 30%; Carbon black 1.5% (a) It is proved [ test result / which is indicated in the Example 1 of the U.S. patent application specification of Poust and others whom the organic-solvent system quoted / above-mentioned / thing above-mentioned ] that a result with water system preliminary treatment substantially comparable as the case of the preliminary treatment which uses an organic-solvent system about the adhesiveness to a metaled base is given. The 2nd table of a postscript shows the ultimate analysis result performed about the polyether imide (30% of glass bulking agent combination) base after performing each of the main processes of the preliminary treatment of a sample. Analysis is Kepex (Kevex Corporat The 2 table). Chick (a) 82.4 4.4 134 After +2 SO4 processing (Process C) 79.5 4.0 14J 1.4 KOH/H20 processing Later (process E) 78.6 3.8 15.0 0.8 Cation surface 85.4 after active agent processing 4.1 (process G) 9.6 (a) All over the surface of the base which oxidized with sulfuric acid, sulfur is combined so that it may be shown by theoretical composition sample 2 of polyether imide before processing. This process gives a remains white tunic on the surface. The ultimate analysis about sample 3 was the same as that of the result of sample 2, except that the oxygen content increased slightly and the sulfur content decreased slightly. When the surface in this stage was inspected, existence of many slots was shown between remains tunic fields. An operation of a cation system surface-active agent is proved [ sample / 4 ]. Sulfur was eliminated from the surface and the oxygen content also decreased. The microphotograph of this sample showed the surface of non-processing Control, and the pure surface which shows the same appearance. Example 2 This example explains the combination of the basic solution processing (process E of Example 1) at the time of using the base of the same model, and cation surface-active agent processing (process G of Example 1). The process shown below shows only the process of differing from the process of Example 1. Time Process Way Method (minute) E KOH (5M); Dodecyltrimethylan 5 Moonium star's picture (1%); room temperature Therefore, processes F and G were excepted. They were 9.6 bonds / inch about the average adhesion value. Example 3 This example explains the case where the organic solvent is included in process G of Example 1 at the time of using the base of the same model. Other processes of all the other than process G are the same as Example 1. Time Process Way Method (minute) GN-methyl pylori boss / water Cetyl pyridinium chloride in five (50150 capacity ratios) (0 or 5%); the room temperature average adhesion value was 11.3 pounds/inch. Example 4 Polyether imide (glass 30% content) was processed according to the process of Example 1 except having changed like cation system surface-active agent process (process G) Diamond. The average adhesion value was 14.5 pounds/inch. Example 5 Preliminary treatment was carried out, adhesive reinforcement processing was carried out and unelectrolyzed plating was carried out so that in Example 1 of the above-mentioned U.S. patent application specification of Pgust and others for the polyether imide base containing 30% of a glass bulking agent. It plated using one of the Plating bath which succeed to the selected base and are shown in the 3rd table of a postscript. An additive agent additive-free layer is CuSO45H20125 g/rho. ; H2S0a 60 g/rho ; And chloride ion 50ppm were included. Other Yoku contained the additive agent further shown there. In each case, the thickness of the electroplating layer was 2 mil. 3rd Table Additive agent additive-free It makes and makes and they are A addition addition 6 *3 additive-agent B addition addition 5.4 additive-agent C addition addition 5 and 2 10.0 additive agents. Roryal copper GREAM PCM plus containing the mixture of an additive-agent-D-addition-less 6.6 additive-agent A NisiSysfide type brightening agent and a poliomyelitis Leuganic oxide type Uniformity exhibition agent (Lea RonaI Copper Gleam PCM) Leona Corral pc GREAM (Lea Ronal PCGleam) additive agent C containing the mixture of a Plus additive-agent B Ndisulfide type brightening agent and a poliomyelitis Leuganic oxide type Uniformity exhibition agent: Erection Bio Chemicals (Electrochemicals) containing an organic dyestuff system P Registered trademark Pluronic (Pluronic)L 3 of BASF A.G. which contains poliomyelitis Lean gum as a C-667 additive-agent D= Uniformity exhibition agent The result of 1 above shows that adhesive reinforcement is attained by exclusion of an additive agent. The surface of metal about an additive agent additive-free layer was very coarse. Example 6 It pretreated similarly, and adhesive improvement processing was carried out, and unelectrolyzed plating processing was carried out [ in / for the polyether imide base containing 30% of a glass bulking agent / Example 1 of the above-mentioned U.S. patent application specification of Poust and others ]. The process shown below carries out Analysis arrival of the copper layer in electrolysis, without adding a chemical additive agent, and expresses the typical plating process of including the process to which Analysis arrival of the copper layer which subsequently contains a chemical additive agent is carried out in electrolysis. A Heat treatment in 75"C 120B 10%H2SOa O and a 5C chemical additive agent are not included. Electrolysis plating (b) 15 of copper D underwater rinse washing the micro of 2E copper -- dirty -- (0) 2 F underwater rinse washing 2G 10%H25O40 and a 5H chemical additive agent are included. Electrolysis Copper plating bath (d)4 * I underwater rinse washing 2J Heat treatment in 95 degreeC A 40-hour (a) base was immersed into the fluid ingredient. (b) Cu5Oa 5H20125 g/D ; H2SO460 g/omega; chloride ion 5oppm Containing bath: Plate with 36ASF to the overall thickness of 0 or 5 mil. (C) Erection Bio Chemicals CoBra Etch (d) which may be obtained from Ohio and the Youngstown In erection Bio Chemicals (Electrochemicals Inc) Lea Ronal Copper Gleam PCM Plus content electrolysis Copper plating bath Example 7 If it removed having given as an additive agent content copper layer and an additive agent additive-free copper layer were shown in the 4th table, various samples were processed as stated to Example 6. Gilt bronze layer thickness was held to the almost same value. 4th Table give -- things are made and giving the adhesiveness which can moreover be permitted to a lower layer base is shown. As mentioned above, although the present invention has been explained about a certain specific desirable embodiment, these statements are the things for illustration, and he should understand that various change can be added within the limits of the present invention shown in the claim, without deviating from the technical thought of the present invention. 2.0 0 0.5 1.5 0.33 1.5 0.17 1.5 0 2.0 (a) Measure by the Sloane Dictecta. 10.7 3,0 10.4 1.0 9.0 1.0 8.0 0.5 4.6 0.5