CA1234254A - Solution for preliminary treatment of polyimide - Google Patents
Solution for preliminary treatment of polyimideInfo
- Publication number
- CA1234254A CA1234254A CA000460364A CA460364A CA1234254A CA 1234254 A CA1234254 A CA 1234254A CA 000460364 A CA000460364 A CA 000460364A CA 460364 A CA460364 A CA 460364A CA 1234254 A CA1234254 A CA 1234254A
- Authority
- CA
- Canada
- Prior art keywords
- accordance
- solution
- polyimide
- litre
- metallizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Chemically Coating (AREA)
- Paints Or Removers (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A B S T R A C T
The invention relates to an aqueous solution for pretreatment of polyimide containing an alkali hydroxide possibly mixed with an organic nitrogen com-pound to increase the adhesion of metal layers deposited chemically or possibly by electro-plating processes after subsequent activation, characterised by the fact that the solution additionally contains a bivalent metal in the form of its compounds.
The invention relates to an aqueous solution for pretreatment of polyimide containing an alkali hydroxide possibly mixed with an organic nitrogen com-pound to increase the adhesion of metal layers deposited chemically or possibly by electro-plating processes after subsequent activation, characterised by the fact that the solution additionally contains a bivalent metal in the form of its compounds.
Description
The invention relates -to an aqueous solution contain-in an alkali metal hydroxide for pretreatment of a polyamide to increase the adhesion of metal layers deposited chemically or by electroplating processes and a process for strongly ad-hornet metallizing of the polyamide.
Polyamide sheet material is being used increasingly to advantage in the field of electronics instead of fibre-glass mats impregnated with epoxide resin. Polyamide sheets coated on both sides with copper are suitable for multi-layer circuits, because they have must greater insulation properties and for this reason, at the same total -thickness of the multi-layer circuit, lend themselves to pressing in much more layers than material impregnated with epoxide resin. In this connect lion the copper must, however, be applied by means of a suitable adhesive since polyamide, in contrast to plastics based on epoxide resin, is not able to bind rolled-on copper with firm adhesion, a factor which results in unfavorable processing properties.
A process for adherent metallizing of polyamide by pretreatment of -the polyamide with an aqueous solution on an alkali metal hydroxide and an organic nitrogen compound without the disadvantages encountered in the use of an adhesive has already been published (DEMOS 31 I 919).
The present invention provides a solution for pro-treatment of polyamide with superior proper-ties.
In accordance with the invention, there is provided an aqueous solution containing alkali metal hydroxide which may be mixed with an organic nitrogen compound and also containing a bivalent metal in the form of its compounds.
I", The solution in accordance with the invention in comparison to the present state of the art brings about an increase in the bonding of the polyimidewith the deposited metal coat which may possibly be traced back to chemical interactive processes between the polyamide surface and the treatment solutions.
A particularly advantageous factor can be seen in the fact that this increased adhesion can be achieved with polyamide of any origin, i.e. it is independent of the quality of the raw material.
The solution in accordance with the invention may contain pro-fireball as the bivalent metal, magnesium, calcium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium or men-cur in the form of their compounds, e.g. oxides or inorganic or organic salts, or in the form of complexes.
An extremely pronounced effect is achieved by zinc which pro-dupes a particular increase in the adhesion.
The metal compounds are employed in concentrations of 1 to 20 gloater, and preferably 10 gloater referred to the metal.
As the alkali hydroxide, the solution may contain lithium ho-dioxide, sodium hydroxide and/or potassium hydroxide at con-cent rations of 5 to 600 gloater and preferably 50 gloater.
As the organic nitrogen compound, the solution may contain a primary, secondary or tertiary amine such as, e.g. an aliphatic or cycloaliphatic moo, do or polyamide or their hydroxy, car boxy, sulfa and/or phosphoryl derivatives, an aromatic
Polyamide sheet material is being used increasingly to advantage in the field of electronics instead of fibre-glass mats impregnated with epoxide resin. Polyamide sheets coated on both sides with copper are suitable for multi-layer circuits, because they have must greater insulation properties and for this reason, at the same total -thickness of the multi-layer circuit, lend themselves to pressing in much more layers than material impregnated with epoxide resin. In this connect lion the copper must, however, be applied by means of a suitable adhesive since polyamide, in contrast to plastics based on epoxide resin, is not able to bind rolled-on copper with firm adhesion, a factor which results in unfavorable processing properties.
A process for adherent metallizing of polyamide by pretreatment of -the polyamide with an aqueous solution on an alkali metal hydroxide and an organic nitrogen compound without the disadvantages encountered in the use of an adhesive has already been published (DEMOS 31 I 919).
The present invention provides a solution for pro-treatment of polyamide with superior proper-ties.
In accordance with the invention, there is provided an aqueous solution containing alkali metal hydroxide which may be mixed with an organic nitrogen compound and also containing a bivalent metal in the form of its compounds.
I", The solution in accordance with the invention in comparison to the present state of the art brings about an increase in the bonding of the polyimidewith the deposited metal coat which may possibly be traced back to chemical interactive processes between the polyamide surface and the treatment solutions.
A particularly advantageous factor can be seen in the fact that this increased adhesion can be achieved with polyamide of any origin, i.e. it is independent of the quality of the raw material.
The solution in accordance with the invention may contain pro-fireball as the bivalent metal, magnesium, calcium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium or men-cur in the form of their compounds, e.g. oxides or inorganic or organic salts, or in the form of complexes.
An extremely pronounced effect is achieved by zinc which pro-dupes a particular increase in the adhesion.
The metal compounds are employed in concentrations of 1 to 20 gloater, and preferably 10 gloater referred to the metal.
As the alkali hydroxide, the solution may contain lithium ho-dioxide, sodium hydroxide and/or potassium hydroxide at con-cent rations of 5 to 600 gloater and preferably 50 gloater.
As the organic nitrogen compound, the solution may contain a primary, secondary or tertiary amine such as, e.g. an aliphatic or cycloaliphatic moo, do or polyamide or their hydroxy, car boxy, sulfa and/or phosphoryl derivatives, an aromatic
2 -moo, do or polyamide or their hydroxy, car boxy, sulfa and/or phosphoryl derivatives, a heterocyclic moo, do or polyamide or their hydroxy, car boxy and/or sulfa derivatives N-con-twining, moo or polynuclear heterocyclic compound or their hydroxy, car boxy and/or sulfa derivatives which may possibly be substituted preferably with alkyd or neutral groups.
The following are quoted as such nitrogen compounds:
Methyl amine, ethyl amine, propylamine, butylamine, ethylene-Damon, propylenediamine, isopropylenediamine, tetramethylene-Damon, octamethylenediamine, piperidine, piperazine, purl-iodine, benzylamine, diethylenediamine, ethylenediaminetetraacetic acid, butylenediaminetetraacetic acid, hexamethylene-diamine-tetraacetic acid, octamethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediamine-N,N'-dipropionic acid, hexamethylenediamine-N,N'-dipropionic acid,ethylenediamine-tetrakis-isopropanol, ethylenediamine-tetrakis-ethanol, N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylene-Damon, triethanolamine, ethanol amine, O-phenyldiamine, aniline, Teledyne, triethylamine, tributylamine, N,N,N',N'-tetra-methylethylenediamine, N,N'-dimethylethylenediamine, NUN-dimethylethylenediamine, N-methylethylenediamine, deathly-amine, dibutylamine.
Imldazole, 1-methylimidazole, 1-propylimidazole, Dow-methylimidazole, 4-methylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 1-benzylimidazole, B-imidazolopropionic acid, 1,2-dimethylimidazole, 1-methyl-2-hydroxymethyl-imidazole,4-sulpho-imidazole, 2-methyl-4-sulpho-imidazole, 2-(sulphophenyl)-imidazole,2-isopropyl-4-sulpho-immidazole, 1-n-propyl-5-sulpho-imidazole, 1-n-propyl-4-sulpho-imidazole, 1,2-bis-(1'-imidazolyl)-ethane, 1-(p-sulphophenyl)-imidazole, histidine, 2-(imidazoloethyl)-pyridine, 1-(2'-aminoethyl)-imidazole-hydrochloride, 1-(3'-aminopropyl)-imidazole-hydro-chloride, 1-methyl-2-carboxymethyl-imidazole, 2-(p-sulpho-~23~S~
phenol sulpho-imidazole, l-methyl-2-sulpho-imidazole, 2-sulphoimidazole, 1,2-bis-(1'-methyl-5'-imidazolyl) ethanes 5-sulpho-benzimidazole, 5,7-disulphobenzimidazole, Boyce-(5'sulphobenzimidazolyl-(2'))-ethane, 1,~-bis-(5'-sulpho-benzimidazolyl-(2'))-butane, polyvinylimidazole degree of polymerization = 2 to 500), polyallylimidazole (degree of polyp merisation = 2 to 500), 3,5-dimethylpyrazole, 4-sulphopyrazole, 1-methylpyrazole, 3-methylpyrazole, 1,3-dimethylpyrazole, 1-phenylpyrazole, 1-carboxymethylpyrazole, 1-carboxyethyl-porously, 1-aminoethyl-pyrazole-hydrochloride, 1-aminopropyl-pyrazole-hydrochlcride, 3,3-dipyrazolyl, 1,3-dimethyl-5-hydroxy-pyrazole, 1-phenyl-3-methyl-5-hydroxy-pyrazole, 1-(p-sulphophenyl)-3-methyl-5-hydroxy-pyrazole,1-((m-sulpho-phenyl)-3-methyl-5-~hydroxy-pyrazole, 1-(p-aminuphenyl)-
The following are quoted as such nitrogen compounds:
Methyl amine, ethyl amine, propylamine, butylamine, ethylene-Damon, propylenediamine, isopropylenediamine, tetramethylene-Damon, octamethylenediamine, piperidine, piperazine, purl-iodine, benzylamine, diethylenediamine, ethylenediaminetetraacetic acid, butylenediaminetetraacetic acid, hexamethylene-diamine-tetraacetic acid, octamethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediamine-N,N'-dipropionic acid, hexamethylenediamine-N,N'-dipropionic acid,ethylenediamine-tetrakis-isopropanol, ethylenediamine-tetrakis-ethanol, N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylene-Damon, triethanolamine, ethanol amine, O-phenyldiamine, aniline, Teledyne, triethylamine, tributylamine, N,N,N',N'-tetra-methylethylenediamine, N,N'-dimethylethylenediamine, NUN-dimethylethylenediamine, N-methylethylenediamine, deathly-amine, dibutylamine.
Imldazole, 1-methylimidazole, 1-propylimidazole, Dow-methylimidazole, 4-methylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 1-benzylimidazole, B-imidazolopropionic acid, 1,2-dimethylimidazole, 1-methyl-2-hydroxymethyl-imidazole,4-sulpho-imidazole, 2-methyl-4-sulpho-imidazole, 2-(sulphophenyl)-imidazole,2-isopropyl-4-sulpho-immidazole, 1-n-propyl-5-sulpho-imidazole, 1-n-propyl-4-sulpho-imidazole, 1,2-bis-(1'-imidazolyl)-ethane, 1-(p-sulphophenyl)-imidazole, histidine, 2-(imidazoloethyl)-pyridine, 1-(2'-aminoethyl)-imidazole-hydrochloride, 1-(3'-aminopropyl)-imidazole-hydro-chloride, 1-methyl-2-carboxymethyl-imidazole, 2-(p-sulpho-~23~S~
phenol sulpho-imidazole, l-methyl-2-sulpho-imidazole, 2-sulphoimidazole, 1,2-bis-(1'-methyl-5'-imidazolyl) ethanes 5-sulpho-benzimidazole, 5,7-disulphobenzimidazole, Boyce-(5'sulphobenzimidazolyl-(2'))-ethane, 1,~-bis-(5'-sulpho-benzimidazolyl-(2'))-butane, polyvinylimidazole degree of polymerization = 2 to 500), polyallylimidazole (degree of polyp merisation = 2 to 500), 3,5-dimethylpyrazole, 4-sulphopyrazole, 1-methylpyrazole, 3-methylpyrazole, 1,3-dimethylpyrazole, 1-phenylpyrazole, 1-carboxymethylpyrazole, 1-carboxyethyl-porously, 1-aminoethyl-pyrazole-hydrochloride, 1-aminopropyl-pyrazole-hydrochlcride, 3,3-dipyrazolyl, 1,3-dimethyl-5-hydroxy-pyrazole, 1-phenyl-3-methyl-5-hydroxy-pyrazole, 1-(p-sulphophenyl)-3-methyl-5-hydroxy-pyrazole,1-((m-sulpho-phenyl)-3-methyl-5-~hydroxy-pyrazole, 1-(p-aminuphenyl)-
3-methyl-5-hydroxy-pyrazole, 1-(p-chlorophenyl)-3-methyl-5-hydroxy-pyrazole, 1-tp-sulphophenyl)-3-carboxy-5-hydroxy-porously, 1,2-bis-(1'-pyrazolyl)-ethane, 7-sulpho-benzopyrazole, 1-carboxyethyl-benzopyrazol, 1,2-bis-(3'pyrazolyl)-ethane, di-(3-pyrazolyl)-methane.
Pardon, 2-aminGpyridine, 3-aminopyridine, 4-aminopyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 2-aminomethylpyridine, 3-aminomethylpyridine, Mooney-methylpyridine, 4-picoline, 3-picoline, 2-picoline, 2,6-letdown, letdown, 3-pyridinesulphonic acid,2,2'-dipyridyl, 1,2-di-(2'-pyridyl), 2,2'~dipyridylmethane, 2,2'-dipyridyl-amine, 1,2-dihydroxy-1,2-di-(2'-pyridyl)-ethane, Dow-pyridylethylene, 4,4'-dipyridylethylene, sulfa'-dipyridyl, 1,2-di-(4'-pyridyl~-ethane.
2-Aminopyrimidine, 2,4,6-triaminopyrimidine, 1,4-dimethyl-pyrirnidine, 1,5-dimethylpyrimidine, 4,5-dimethylpyrimidine,
Pardon, 2-aminGpyridine, 3-aminopyridine, 4-aminopyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 2-aminomethylpyridine, 3-aminomethylpyridine, Mooney-methylpyridine, 4-picoline, 3-picoline, 2-picoline, 2,6-letdown, letdown, 3-pyridinesulphonic acid,2,2'-dipyridyl, 1,2-di-(2'-pyridyl), 2,2'~dipyridylmethane, 2,2'-dipyridyl-amine, 1,2-dihydroxy-1,2-di-(2'-pyridyl)-ethane, Dow-pyridylethylene, 4,4'-dipyridylethylene, sulfa'-dipyridyl, 1,2-di-(4'-pyridyl~-ethane.
2-Aminopyrimidine, 2,4,6-triaminopyrimidine, 1,4-dimethyl-pyrirnidine, 1,5-dimethylpyrimidine, 4,5-dimethylpyrimidine,
4,6-dimethylpyrimidine, 2,4-bis-(diethylamino)-pyrimidine, 3,6-bis-(dimethylamino)-pyrimidine, 3,6-bis-tethylamino~-pyrimidine,2-hydroxypyrimidine, 4-hydroxypyrimidine, 4,6-dihydroxypyrimidine, barbituric acid, citizen, pyrimidine, Lo bis-(2-methyl-4-pyrimidyl), 2,2'-dipyrimidyl, dopier-muddle, Ursula, 5-methylcytosine, 2-methylpyrimidine, 2-ethylpyrimidine, 2-phenylpyrimidine, 2-amino-6-ethylpyri-midline, 2-amino-6-methylpyrimidine, 2-amino-5-methoxypyri-midline, 2-amino-4-hydroxypyrimidine, 2-carboxypyrimidine,
5-carboxymethylpyrimidine, 2-carboxymethyl-5,6-dimethyl-pyrimidine, 2-methyl-5-carboxymethylpyrimidine, pyridazine, 3-methylpyridazine, porcine, 2,3,5-6-tetramethylpyrazine, 2,5-dimethyl-6-hydroxypyrazine, 2-hydroxypyrazine, 2-aminopyrazine.
Urotropine, 2,6-diamino-4-methyltriazine-(1,3,5), Dow-amino-4-ethyltriazine-(1,3,5), 2,6-diamino-4-propyltri-assign), 2,6-diamino-4-carboxymethyltriazine-(1,3,5), Damon carboxyethyltriazine-(1,3,5), Damon-4-sulphopropyltriazine-(1 t 3,5), mailmen, cyan uric acid, 2,4,6-tris-methylaminotriazine-(1,3,5), 2,4,6-tris-ethvlamino-treason), 2,4,6-tris-diethylaminotriazine-(1,3,5), bis-~4,6-diamino-2-triazinyl-(1,3,5~)-methane, Boyce-(4',6'-diamino-triazinyl-(1',3',5'))-ethane, Boyce'-diamino-2'-triazinyl-(1',3',5'))-propane, Boyce'-diaminotriazinyl-2'-amino)-ethane, 2,4-diaminotriazine-(1,3,5), 2,4-diamino-6-(p-sulphophenyl)-triazine-(1,3-5), 2,4-diamino-6-ethyltriazine-(1,3,5), 2,4-dihydroxy-6-methyltriazine-(1,3,5), cyan uric acid hydroxyethyl ester, 2,4-dihydroxy-6-carboxymethyltriazine-(1,3,5), 2-amino-4-carboxymethyl-6-n-butylaminotriazine-(1,3,5), 2-amino-4-carboxy-6-n-butylaminotriazine-(1,3,5), 2-amino-4-carb-oxyethyl-6-n-butylaminotriazine-(1,3,5), 2-amino-4-hydroxy-treason), 3~amino-triazine-(1,2,4), amend-methyltriazine-(1,2,4), 4-hydroxy-5,6-dimethyltriazine-(1,2,4~, 4-hydroxy-5-phenyltriazine-(1,2,4), treason), 3,3'-bis-~5,6-dimethyltriazine-~1,2,4), 3,5-dihydroxy-treason), 3,5-dihydroxy-6-methyltriazine-(1,2,4), 3,5-dihydroxy-6-butyltriazine-(1,2,4), 3,5-dihydroxy-6-phenyltriazine-(1,2,4), 3,5-dihydroxy-6-carboxypropyl-treason).
I
Triazole-(1,2,~l), 4~ethyltriazole-(1,2,~), 4-methyl--triazole-(1,2,4J, 4-phenyltriazole-(1,2,4), 3,4,5-trimethyltriazole-(1,2,4), 4-(p-sulphophenyl)-triazole-(1,2,4), 3-methyltria-Zulu), 3-ethyltriazole-~1,2,4),3,5-dimethyltriazole-(1,2,4), 3-phenyltriazole-(1,2,4), 1-methyltriazole~(1,2,4), 1-ethyltriazole-(1,2,4), 1-phenyltriazole-(1,2,4), sulfa-triazole-(1,2,4), 3-amino-triazole-(1,2,4), Damon-triazole-(1,2,4), 1,2-bis-t5'-sulpho-3'-triazolyl)-ethane, 1,2-bis-(5'-amino-3'-triazolyl)-ethane, boisterously-yl)-ethane, 1,2-bis-(4'-methyl-3'-triazolyl)-ethane, Boyce-triazolyl)-methane, bis-(5-sulpho-3-triazolyl)-methane, bus-(S-amino-3-triazolyl)-methane, bis-(3-triazolyl)-methane, bis-(5-sulpho-3-triazolyl), bis-(5-amino-3-triazolyl~, 3,3'-bis-triazolyl, 1,2-(1'-triazolyl)-ethane, 3-(2'-aminoethyl)-triazole-(1,2,4), B-(1-triazolyl)-propionic acid, Boyce-(5'-sulpho-3'-triazolyl)-butane, 1,4-bis-(5'-amino-3'-tri-azolyl)-butane, 1-(3-sulphopropyl)-triazole-(1,2,4), Boyce-(4'-triazolyl)-ethane, 1-methyl-triazole-(1,2,3), 1-ethyl-triazole-(1,2,3), 2-ethyl-triazole-(1,2,3), 2-propyltriazole-(1,2,3), 1-~2'-carboxyethyl)-triazole-(1,2,3), 5-sulphobenzo-triazole, 5,7-disulphobenzotriazole, benzotriazole, 4-methyl-triazole-(1,2,3), 4,5-dimethyltriazole-(1,2,3), bottle-triazole-(1,2,3), 4-phenyltriazole-(1,2,3), Amman-propyl)-triazole-(1,2,3), 1-(2'-aminoethyl)-triazole-(1,2,3), 1,2-bis-(1'-triazolyl)-ethane.
Purl, 1-methylpyrrole, 1-ethylpyrrole, 1-(2'-carboxy-ethyl)-pyrrole, 2-methylpyrrole, 2,5-dimethylpyrrole, dip (2-pyrrolyl)-methane, di-(1-methyl-2-pyrrolyl)-methane, 2-ethylpyrrole, tryptophan.
Polyethyleneimine, N,N-dimethylpolyvinylamine, polyvinylimid-azalea, polyallylimidazole, polyvinylpyridine, polyvinylpyrrol-done, polyvinylmorpholine, polyvinylmorpholinone, polyvinyl-5-alkyl-oxazolidone, N-polyvinyl-N,N'-ethylene urea, soya proteins, albumins, ethylenediaminotetra-(methylphosphonic acid), hexamethylphosphoric trimmed.
US
It will be clear that these compounds can in each case be used alone or mixed with each other.
Particular importance is attached to N,N,N',N'-tetrakis-(2-hydroxypropyl~-ethylenediamine, ethylenediaminetetra-acetic acid and nitrilotriacetic assiduous of which produces stronger inner bonding between the polyamide and the metal coating.
The organic nitrogen compounds are used at concentrations of 5 to 30 gloater and preferably 20 gloater.
ho The term polyamide implies all plastics which are described for example in Ullmanns Encyclopedia don technician Chemise, 1970, Supplement, pp. 266 to 26B and pp. 318 and 319, published by Urban & Schwarzenberg, Munich, Berlin and Vienna.
It can be produced by what in fact is a well-known method for example by reaction of carboxylic acid androids with aromatic dominoes.
The substances involved are largely linear plastics highly stable to heat, with the general formula:
{ CO N - - O - } n The polyamide is used to advantage in sheet form for the pro-cuss in accordance with the invention.
. .
It will be clear that not only plastics of pure polyamide can be treated in accordance with the invention, but also those which, for instance, are coated on one side with other plastics.
The polyamide is treated with the solution in accordance with the invention at temperatures of 15 to 30 C and preferably at 20 C.
After pretreatment, the polyamide is activated in the usual manner, conveniently by means of a palladium-containing anti-valor, whereupon a metal coating, preferably of copper or nickel, is applied chemically in the usual manner.
Especially strong adhesion can be achieved when the polyamide after pretreatment and metallisation is heated to 70 to 140 C
and preferably to 130 C.
A further increase in the adhesion of the deposited metal coating Jan finally be achieved when the polyamide after pro-treatment is first dipped in an aqueous solution containing am-minim ions for which purpose organic and inorganic ammonium salts, such as ar~monium acetate are suitable.
In addition it has proved advantageous to use a palladium no-diction bath which contains a N-containing, cation-active wet-tying agent. Suitable wetting agents are for example quoter-nosed fatty aminopolyglycol ethers with the general formula OR - N / ~CH2CH2O~ OH-L --( SCHICK ) Shea where R is an alkyd radical preferably with 12 to 18 C-atoms and aback = 10. These welting agents are conveniently used at concentrations of 0.005 to 2 gloater and preferably 0.05 gloater.
I
Subsequent use of a chemical metallizing bath likewise contain-in ammonium ions finally leads to a lasting increase in ad-lesion.
The solution in accordance with the invention permits, in a surprisingly advantageous manner, production of a composite polyimide-metal material and preferably a composite polyamide-copper material which can be used for mounded parts, preferably in the field of electronics and electrical engineering.
The further merits associated with the possibility of producing such a composite material lie in the fact that all the sources of error arising with the use of an adhesive are avoided. More-over the possibility is created of using polyamide as the last layer for the production of base material in semi-additive technology to permit resort in this field to chronic acid as a conversion agent to be overcome. To this must be added the much better electrical characteristics which permit design of much denser circuits than was possible with conventional ad-lesion agents hitherto.
Surprisingly, the composite materials in accordance with the invention are of superior stability.
I The following examples will serve to explain the invention.
g I
The polyamide sheet commonly used in the electrical industry was treated in a solution of 100 g of potassium hydroxide and 20 g ofN,N,N',N'-tetrakis-~2-hydroxypropyl)-ethylenediamiire in 1 lithe of water for 5 minutes and then rinsed. In a further step the sheet was activated with palladium ions in a manner known in the art. After rinsing with water the remaining ad-sorbed palladium ions were reduced to palladium metal using a 1% aqueous solution of dimethylaminoborane. Flawless metallic station of the sheet prepared in this manner was achieved in a chemical copper bath of the kind known in the art with formal-Dodd as a reduction agent. A tempering process at 100 C
followed to fix the deposited chemical copper. Following the tempering process the extremely thin (0.5 my coat of copper was briefly deoxidized with sulfuric acid at a concentration of 10% by volume and then raised to 40 em by the usual electron lyric copper-plating process in a sulfuric acid bath. Ad-lesion was determined by the peeling test in conformity with DIN standards. It amounted to 1 to 2 N/cm.
1~3~
10 g of zinc in the form of zinc oxide was added to the so-lotion of 100 g of potassium hydroxide and 20 g of N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylenediamine in 1 lithe of water described in Example 1. Subsequently a sheet of polyamide was pretreated with this solution in a way similar to the process described in Example 1, then activated and copper-plated both by electroplating and chemical methods. The adhesion (peeling test as stipulated by DIN standards) amounted to 4 to 5 N/cm.
of ~23~
-The test described in Example 3 was repeated using a solution of dimethylaminoborane as a reducing agent which contained 0.05 g of a quaternised fatty aminopolyglycol ether.
The adhesion was determined to amount to 5 to 7 Ntcm twin peeling test).
~23~Z5~
The test described in Example 3 was repeated. However, the sheet of polyamide was dipped after pretreatment into a solution containing 20 g of ammonium acetate per lithe of water.
The adhesion (DIN peeling test) amounted to 11 to 16 N/cm.
Urotropine, 2,6-diamino-4-methyltriazine-(1,3,5), Dow-amino-4-ethyltriazine-(1,3,5), 2,6-diamino-4-propyltri-assign), 2,6-diamino-4-carboxymethyltriazine-(1,3,5), Damon carboxyethyltriazine-(1,3,5), Damon-4-sulphopropyltriazine-(1 t 3,5), mailmen, cyan uric acid, 2,4,6-tris-methylaminotriazine-(1,3,5), 2,4,6-tris-ethvlamino-treason), 2,4,6-tris-diethylaminotriazine-(1,3,5), bis-~4,6-diamino-2-triazinyl-(1,3,5~)-methane, Boyce-(4',6'-diamino-triazinyl-(1',3',5'))-ethane, Boyce'-diamino-2'-triazinyl-(1',3',5'))-propane, Boyce'-diaminotriazinyl-2'-amino)-ethane, 2,4-diaminotriazine-(1,3,5), 2,4-diamino-6-(p-sulphophenyl)-triazine-(1,3-5), 2,4-diamino-6-ethyltriazine-(1,3,5), 2,4-dihydroxy-6-methyltriazine-(1,3,5), cyan uric acid hydroxyethyl ester, 2,4-dihydroxy-6-carboxymethyltriazine-(1,3,5), 2-amino-4-carboxymethyl-6-n-butylaminotriazine-(1,3,5), 2-amino-4-carboxy-6-n-butylaminotriazine-(1,3,5), 2-amino-4-carb-oxyethyl-6-n-butylaminotriazine-(1,3,5), 2-amino-4-hydroxy-treason), 3~amino-triazine-(1,2,4), amend-methyltriazine-(1,2,4), 4-hydroxy-5,6-dimethyltriazine-(1,2,4~, 4-hydroxy-5-phenyltriazine-(1,2,4), treason), 3,3'-bis-~5,6-dimethyltriazine-~1,2,4), 3,5-dihydroxy-treason), 3,5-dihydroxy-6-methyltriazine-(1,2,4), 3,5-dihydroxy-6-butyltriazine-(1,2,4), 3,5-dihydroxy-6-phenyltriazine-(1,2,4), 3,5-dihydroxy-6-carboxypropyl-treason).
I
Triazole-(1,2,~l), 4~ethyltriazole-(1,2,~), 4-methyl--triazole-(1,2,4J, 4-phenyltriazole-(1,2,4), 3,4,5-trimethyltriazole-(1,2,4), 4-(p-sulphophenyl)-triazole-(1,2,4), 3-methyltria-Zulu), 3-ethyltriazole-~1,2,4),3,5-dimethyltriazole-(1,2,4), 3-phenyltriazole-(1,2,4), 1-methyltriazole~(1,2,4), 1-ethyltriazole-(1,2,4), 1-phenyltriazole-(1,2,4), sulfa-triazole-(1,2,4), 3-amino-triazole-(1,2,4), Damon-triazole-(1,2,4), 1,2-bis-t5'-sulpho-3'-triazolyl)-ethane, 1,2-bis-(5'-amino-3'-triazolyl)-ethane, boisterously-yl)-ethane, 1,2-bis-(4'-methyl-3'-triazolyl)-ethane, Boyce-triazolyl)-methane, bis-(5-sulpho-3-triazolyl)-methane, bus-(S-amino-3-triazolyl)-methane, bis-(3-triazolyl)-methane, bis-(5-sulpho-3-triazolyl), bis-(5-amino-3-triazolyl~, 3,3'-bis-triazolyl, 1,2-(1'-triazolyl)-ethane, 3-(2'-aminoethyl)-triazole-(1,2,4), B-(1-triazolyl)-propionic acid, Boyce-(5'-sulpho-3'-triazolyl)-butane, 1,4-bis-(5'-amino-3'-tri-azolyl)-butane, 1-(3-sulphopropyl)-triazole-(1,2,4), Boyce-(4'-triazolyl)-ethane, 1-methyl-triazole-(1,2,3), 1-ethyl-triazole-(1,2,3), 2-ethyl-triazole-(1,2,3), 2-propyltriazole-(1,2,3), 1-~2'-carboxyethyl)-triazole-(1,2,3), 5-sulphobenzo-triazole, 5,7-disulphobenzotriazole, benzotriazole, 4-methyl-triazole-(1,2,3), 4,5-dimethyltriazole-(1,2,3), bottle-triazole-(1,2,3), 4-phenyltriazole-(1,2,3), Amman-propyl)-triazole-(1,2,3), 1-(2'-aminoethyl)-triazole-(1,2,3), 1,2-bis-(1'-triazolyl)-ethane.
Purl, 1-methylpyrrole, 1-ethylpyrrole, 1-(2'-carboxy-ethyl)-pyrrole, 2-methylpyrrole, 2,5-dimethylpyrrole, dip (2-pyrrolyl)-methane, di-(1-methyl-2-pyrrolyl)-methane, 2-ethylpyrrole, tryptophan.
Polyethyleneimine, N,N-dimethylpolyvinylamine, polyvinylimid-azalea, polyallylimidazole, polyvinylpyridine, polyvinylpyrrol-done, polyvinylmorpholine, polyvinylmorpholinone, polyvinyl-5-alkyl-oxazolidone, N-polyvinyl-N,N'-ethylene urea, soya proteins, albumins, ethylenediaminotetra-(methylphosphonic acid), hexamethylphosphoric trimmed.
US
It will be clear that these compounds can in each case be used alone or mixed with each other.
Particular importance is attached to N,N,N',N'-tetrakis-(2-hydroxypropyl~-ethylenediamine, ethylenediaminetetra-acetic acid and nitrilotriacetic assiduous of which produces stronger inner bonding between the polyamide and the metal coating.
The organic nitrogen compounds are used at concentrations of 5 to 30 gloater and preferably 20 gloater.
ho The term polyamide implies all plastics which are described for example in Ullmanns Encyclopedia don technician Chemise, 1970, Supplement, pp. 266 to 26B and pp. 318 and 319, published by Urban & Schwarzenberg, Munich, Berlin and Vienna.
It can be produced by what in fact is a well-known method for example by reaction of carboxylic acid androids with aromatic dominoes.
The substances involved are largely linear plastics highly stable to heat, with the general formula:
{ CO N - - O - } n The polyamide is used to advantage in sheet form for the pro-cuss in accordance with the invention.
. .
It will be clear that not only plastics of pure polyamide can be treated in accordance with the invention, but also those which, for instance, are coated on one side with other plastics.
The polyamide is treated with the solution in accordance with the invention at temperatures of 15 to 30 C and preferably at 20 C.
After pretreatment, the polyamide is activated in the usual manner, conveniently by means of a palladium-containing anti-valor, whereupon a metal coating, preferably of copper or nickel, is applied chemically in the usual manner.
Especially strong adhesion can be achieved when the polyamide after pretreatment and metallisation is heated to 70 to 140 C
and preferably to 130 C.
A further increase in the adhesion of the deposited metal coating Jan finally be achieved when the polyamide after pro-treatment is first dipped in an aqueous solution containing am-minim ions for which purpose organic and inorganic ammonium salts, such as ar~monium acetate are suitable.
In addition it has proved advantageous to use a palladium no-diction bath which contains a N-containing, cation-active wet-tying agent. Suitable wetting agents are for example quoter-nosed fatty aminopolyglycol ethers with the general formula OR - N / ~CH2CH2O~ OH-L --( SCHICK ) Shea where R is an alkyd radical preferably with 12 to 18 C-atoms and aback = 10. These welting agents are conveniently used at concentrations of 0.005 to 2 gloater and preferably 0.05 gloater.
I
Subsequent use of a chemical metallizing bath likewise contain-in ammonium ions finally leads to a lasting increase in ad-lesion.
The solution in accordance with the invention permits, in a surprisingly advantageous manner, production of a composite polyimide-metal material and preferably a composite polyamide-copper material which can be used for mounded parts, preferably in the field of electronics and electrical engineering.
The further merits associated with the possibility of producing such a composite material lie in the fact that all the sources of error arising with the use of an adhesive are avoided. More-over the possibility is created of using polyamide as the last layer for the production of base material in semi-additive technology to permit resort in this field to chronic acid as a conversion agent to be overcome. To this must be added the much better electrical characteristics which permit design of much denser circuits than was possible with conventional ad-lesion agents hitherto.
Surprisingly, the composite materials in accordance with the invention are of superior stability.
I The following examples will serve to explain the invention.
g I
The polyamide sheet commonly used in the electrical industry was treated in a solution of 100 g of potassium hydroxide and 20 g ofN,N,N',N'-tetrakis-~2-hydroxypropyl)-ethylenediamiire in 1 lithe of water for 5 minutes and then rinsed. In a further step the sheet was activated with palladium ions in a manner known in the art. After rinsing with water the remaining ad-sorbed palladium ions were reduced to palladium metal using a 1% aqueous solution of dimethylaminoborane. Flawless metallic station of the sheet prepared in this manner was achieved in a chemical copper bath of the kind known in the art with formal-Dodd as a reduction agent. A tempering process at 100 C
followed to fix the deposited chemical copper. Following the tempering process the extremely thin (0.5 my coat of copper was briefly deoxidized with sulfuric acid at a concentration of 10% by volume and then raised to 40 em by the usual electron lyric copper-plating process in a sulfuric acid bath. Ad-lesion was determined by the peeling test in conformity with DIN standards. It amounted to 1 to 2 N/cm.
1~3~
10 g of zinc in the form of zinc oxide was added to the so-lotion of 100 g of potassium hydroxide and 20 g of N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylenediamine in 1 lithe of water described in Example 1. Subsequently a sheet of polyamide was pretreated with this solution in a way similar to the process described in Example 1, then activated and copper-plated both by electroplating and chemical methods. The adhesion (peeling test as stipulated by DIN standards) amounted to 4 to 5 N/cm.
of ~23~
-The test described in Example 3 was repeated using a solution of dimethylaminoborane as a reducing agent which contained 0.05 g of a quaternised fatty aminopolyglycol ether.
The adhesion was determined to amount to 5 to 7 Ntcm twin peeling test).
~23~Z5~
The test described in Example 3 was repeated. However, the sheet of polyamide was dipped after pretreatment into a solution containing 20 g of ammonium acetate per lithe of water.
The adhesion (DIN peeling test) amounted to 11 to 16 N/cm.
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In an aqueous solution for the pre-treatment of a polyimide substrate containing an alkali metal hydroxide at a concentration of 5 to 600 g/litre to increase adhesion of metal layers deposited thereon, after activation, chemically and with or without electrolytical deposition, the improvement in which said solution also containing a divalent metal selected from the group consisting of magnesium, calcium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium and mercury at concen-trations of 1 to 20 g/litre.
2. A solution in accordance with claim 1, which also contains an organic nitrogen compound in a concentration of 5 to 30 g/litre.
3. A solution in accordance with claim 2, which con-tains a primary, secondary or tertiary amine as the organic ni-trogen compound.
4. A solution in accordance with claim 3, which con-tains, as the organic nitrogen compound, an aliphatic or cy-cloaliphatic mono, di or polyamine or a hydroxy, carboxy, sulpho and/or phosphoryl derivative thereof, an aromatic mono, di or polyamine or a hydroxy, carboxy, sulpho and/or phosphoryl deriva-tive thereof, a heterocyclic mono, di or polyamine or a hydroxy, carboxy and/or sulpho derivative thereof.
5. A solution in accordance with claim 4, in which the organic nitrogen compound is substituted with alkyl or nitrilo groups.
6. A solution in accordance with claim 5, which con-tains N,N,N',N -tetrakis-(2-hydroxypropyl)-ethylenediamine, ethylenediaminetetraacetic acid or nitrilo-triacetic acid.
7. A solution in accordance with claim 2, 3 or 4, which contains 5 to 30 g/litre of an organic nitrogen compound.
8. A solution in accordance with claim 2, 3 or 4, which contains 20 g/litre of an organic nitrogen compound.
9. A solution in accordance with claim 1, 2 or 3, in which the bivalent metal is contained at concentrations of 10 g/litre.
10. A solution in accordance with claim 1, 2 or 3, which contains at least one of lithium hydroxide, sodium hydrox-ide and potassium hydroxide as the alkali metal hydroxide.
11. A solution in accordance with claim 1, 2 or 3, which contains 50 g/litre of alkali metal hydroxide.
12. A process for strongly adherent metallizing of a polyimide which comprises subjecting the polyimide to a pretreat-ment with a solution in accordance with claim 1 at a temperature from 15 to 30°C.
13. A process for strongly adherent metallizing of a polyimide which comprises subjecting the polyimide to a pretreat-ment with a solution in accordance with claim 1 at a temperature of 20°C.
14. A process in accordance with claim 13, in which the polyimide after pretreatment is dipped first into an aqueous so-lution containing ammonium ions.
15. process in accordance with claim 13, in which the polyamide is subsequently activated in a palladium reduction bath which contains an N-containing cation-active wetting agent at concentrations of 0.005 to 2 g/litre.
16. A process in accordance with claim 13, in which the polyamide is subsequently activated in a palladium reduction bath which contains an N-containing cation-active wetting agent at a concentration of 0.05 g/litre.
17. A process in accordance with claim 15, in which the wetting agent is a quaternized fatty amide polyglycol ether of the general formula where R is an alkyl radical of 12 to 18 carbon atoms and a + b +
c = 10.
c = 10.
18. A process in accordance with claim 13, in which the chemical metallizing process takes place by means of a chemical bath containing ammonium ions.
19. A process in accordance with claim 13, in which the polyimide after pretreatment and metallizing is heated to a tem-perature from 70 to 140°C.
20. A process in accordance with claim 13, in which the polyimide after pretreatment and metallizing is heated to a tem-perature of 130°C.
21. A process in accordance with claim 13, in which a composite polyimide-metal material is produced.
22. A process in accordance with claim 13, in which a composite polyimide-copper material is produced.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833328765 DE3328765A1 (en) | 1983-08-05 | 1983-08-05 | SOLUTION FOR PRE-TREATING POLYIMIDE |
| DEP3328765.1 | 1983-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1234254A true CA1234254A (en) | 1988-03-22 |
Family
ID=6206159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000460364A Expired CA1234254A (en) | 1983-08-05 | 1984-08-03 | Solution for preliminary treatment of polyimide |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0139090B1 (en) |
| JP (1) | JPS6075581A (en) |
| AT (1) | AT383146B (en) |
| CA (1) | CA1234254A (en) |
| DE (2) | DE3328765A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147518A (en) * | 1991-03-07 | 1992-09-15 | E. I. Du Pont De Nemours And Company | Process for adhering metal to polyimide film |
| US9918389B2 (en) | 2013-09-04 | 2018-03-13 | Rohm And Haas Electronic Materials Llc | Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3530617A1 (en) * | 1985-08-23 | 1987-02-26 | Schering Ag | CONDITIONERS FOR TREATING BASE MATERIALS |
| DE3612822A1 (en) * | 1986-04-14 | 1987-10-15 | Schering Ag | METHOD FOR ADHESIVE METALIZATION OF POLYETHERIMIDE |
| US4725504A (en) * | 1987-02-24 | 1988-02-16 | Polyonics Corporation | Metal coated laminate products made from textured polyimide film |
| US5242713A (en) * | 1988-12-23 | 1993-09-07 | International Business Machines Corporation | Method for conditioning an organic polymeric material |
| DE4008482A1 (en) * | 1990-03-16 | 1991-09-19 | Asea Brown Boveri | GALVANIZATION PROCEDURE |
| US5441770A (en) * | 1990-05-18 | 1995-08-15 | Shipley Company Inc. | Conditioning process for electroless plating of polyetherimides |
| DE10143520A1 (en) * | 2001-09-05 | 2003-04-03 | Siemens Dematic Ag | Solution and method for processing the surface of plastics, in particular LCP substrates, to improve the adhesion of metallizations and use of such a solution |
| JP5930525B2 (en) * | 2011-12-20 | 2016-06-08 | 株式会社Adeka | Electroless plating pretreatment agent and electroless plating pretreatment method using the pretreatment agent |
| EP2845923B1 (en) * | 2013-09-04 | 2018-11-28 | Rohm and Haas Electronic Materials LLC | Electroless metallization of dielectrics with stable alkaline catalysts containing pyrazine derivatives |
| EP2845922A1 (en) * | 2013-09-04 | 2015-03-11 | Rohm and Haas Electronic Materials LLC | Electroless metallization of dielectrics with alkaline stable pyrimidine derivative containing catalysts |
| JP7017436B2 (en) * | 2017-10-31 | 2022-02-08 | 東京応化工業株式会社 | Surface treatment methods, surface treatment liquids, and surface-treated articles |
| CN113957421B (en) * | 2021-10-21 | 2023-09-05 | 广州三孚新材料科技股份有限公司 | PET surface roughening liquid and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652351A (en) * | 1970-05-13 | 1972-03-28 | Carus Corp | Processes for etching synthetic polymer resins with alkaline alkali metal manganate solutions |
| CA954391A (en) * | 1971-06-14 | 1974-09-10 | Western Electric Company, Incorporated | Method of improving adhesive properties of a polymeric material to a species deposited thereon |
| BE792310A (en) * | 1971-12-08 | 1973-06-05 | Kalle Ag | PROCESS FOR DEPOSITING COPPER COATS ON MOLDED PARTS OF POLYIMIDES |
| US3791848A (en) * | 1972-05-19 | 1974-02-12 | Western Electric Co | A method of improving the adherence of a metal deposit to a polyimide surface |
| DE2239908C3 (en) * | 1972-08-14 | 1979-12-13 | Aeg Isolier- Und Kunststoff Gmbh, 3500 Kassel | Base material for the production of printed circuits |
| JPS5126979A (en) * | 1974-08-30 | 1976-03-05 | Matsushita Electric Works Ltd | PURASUCHITSUKUSUMETSUKIKITAI NO MAESHORIHO |
| US4327157A (en) * | 1981-02-20 | 1982-04-27 | The United States Of America As Represented By The Secretary Of The Navy | Stabilized nickel-zinc battery |
| DE3149919A1 (en) * | 1981-12-11 | 1983-06-23 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | METHOD FOR ADHESIVELY METALLIZING POLYIMIDE |
-
1983
- 1983-08-05 DE DE19833328765 patent/DE3328765A1/en not_active Withdrawn
-
1984
- 1984-06-30 DE DE8484107617T patent/DE3472975D1/en not_active Expired
- 1984-06-30 EP EP84107617A patent/EP0139090B1/en not_active Expired
- 1984-08-02 AT AT0249584A patent/AT383146B/en not_active IP Right Cessation
- 1984-08-03 CA CA000460364A patent/CA1234254A/en not_active Expired
- 1984-08-06 JP JP59163916A patent/JPS6075581A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147518A (en) * | 1991-03-07 | 1992-09-15 | E. I. Du Pont De Nemours And Company | Process for adhering metal to polyimide film |
| US9918389B2 (en) | 2013-09-04 | 2018-03-13 | Rohm And Haas Electronic Materials Llc | Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3328765A1 (en) | 1985-02-14 |
| EP0139090A1 (en) | 1985-05-02 |
| EP0139090B1 (en) | 1988-07-27 |
| ATA249584A (en) | 1986-10-15 |
| DE3472975D1 (en) | 1988-09-01 |
| AT383146B (en) | 1987-05-25 |
| JPS6075581A (en) | 1985-04-27 |
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