CA1104010A - Methods of producing at least partially metallophobic surfaces on objects - Google Patents
Methods of producing at least partially metallophobic surfaces on objectsInfo
- Publication number
- CA1104010A CA1104010A CA281,246A CA281246A CA1104010A CA 1104010 A CA1104010 A CA 1104010A CA 281246 A CA281246 A CA 281246A CA 1104010 A CA1104010 A CA 1104010A
- Authority
- CA
- Canada
- Prior art keywords
- set forth
- weight
- antimony
- metallophobic
- soluble
- 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.)
- Expired
Links
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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A B S T R A C T
A method of treating surfaces of objects to render them at least partially metallophobic by the use of compounds containing an element with amphoteric characteristics. Stabilized and/or stable antimony compounds or complexes which are soluble in water and/or organic solvents are applied in and/or under the surfaces which are to be rendered metallophobic. The objects can then be partially metallized in conventional chemical or electrolytic baths. The method is particularly applicable to the manufacture of printed circuits.
A method of treating surfaces of objects to render them at least partially metallophobic by the use of compounds containing an element with amphoteric characteristics. Stabilized and/or stable antimony compounds or complexes which are soluble in water and/or organic solvents are applied in and/or under the surfaces which are to be rendered metallophobic. The objects can then be partially metallized in conventional chemical or electrolytic baths. The method is particularly applicable to the manufacture of printed circuits.
Description
4 0 i ~
~he invention relates to methods of producing at - least par-tially me-tallophobic surfaces on objects. ,Such methods may be used in the production o~ printed circuit boards.
~he constantly increàsing use of numerous known processes for electrolytic as well as non-electroly-tic chemical metallizing of objec-ts of all kinds has led to '' ~ many improvements and rationalizations, including those~ ' concerned with constantly rlsing en~ironmental pollution.
,~ 10 ~or eæample, in -the produc-tion of prin-ted circuits f'or , electronic apparatus there has been some departure from the originally conventional su'btracti~e process in which ~', , the base material is completely coated on one or both sides ' wîth copper and in which the copper not required for ~', ;'~4 15 , ' conductor tracks is again removed from the base material.,., -.~,, ~ .. . .
This method has been largely replaced by the additive process ' in which only those places of the base material which are intended for the conductor tracks are coated ~ith copper or ' ~l other metals. If'this additive method is to be employed .,~ .
`~r 20 for printed circuit boards in which only one side of the - base material is to be provided with metallic conductor runs, J
" it is necessary to protect the base material agains-t metallization on the side which does not contain conductor runs. A very efficient me-thod to this end is to render -the ; 25 affected base material side metallophobic, i.e. to render .
~; it metal-repellent.
:; ~ ' - . .
-: ' ' . . : ' ~he prior ar~ discloses a me-thod for producing pa-tterns on suitable bases by means o~ radiation action7 more particularly for the production of printed circuit boards in accordance with the so-called facing process. In -this method, -the surface of -the base, suitably pre-treated where necessary, is -treated wl-th a solution with a p~I value . be-tween ~.5 and 4~0 and contai.ning a small quantity of at ; least one halogen ion of -the chlorine, bromine and/or iodine gxoup, and at least one reducible salt of a non-precious ~ 10 metal in an ion concentration greater than that corresponding .~ to the halogen conten-t and a component adapted to respond to -the radiation energy employed. q1he zones corresponding : . to the desired pattern on -tne surface -thus treated are exposed ... .
~ to the radiation source so as to produce in the zones affected "1 ~
by radiation a real image of the desired pa-ttern consisting of reduced me-tal seeds9 whereafter the surface is rinsed so that the~metal salt is removed from zones not exposed to :radiation and the surface, having the real image, is exposed to a suitable autocatalytic precipita-tion bath in which the radiation-reduced me-tal seeds catalytically cause -the non-electrolytic depositing of metal in -the surface zones covered by the me-tal seeds. ~here is thus produced an image.
of the desired pattern consisting of non-electrolytically :, ' , . deposited metal, the metal thickness depending on the aoti.vity time o~ the autocatalytic bath~ ~he surface of . the base,~at least in the zones thereof in which no non-electrolytical metal deposition is desired, is treated wi-th
~he invention relates to methods of producing at - least par-tially me-tallophobic surfaces on objects. ,Such methods may be used in the production o~ printed circuit boards.
~he constantly increàsing use of numerous known processes for electrolytic as well as non-electroly-tic chemical metallizing of objec-ts of all kinds has led to '' ~ many improvements and rationalizations, including those~ ' concerned with constantly rlsing en~ironmental pollution.
,~ 10 ~or eæample, in -the produc-tion of prin-ted circuits f'or , electronic apparatus there has been some departure from the originally conventional su'btracti~e process in which ~', , the base material is completely coated on one or both sides ' wîth copper and in which the copper not required for ~', ;'~4 15 , ' conductor tracks is again removed from the base material.,., -.~,, ~ .. . .
This method has been largely replaced by the additive process ' in which only those places of the base material which are intended for the conductor tracks are coated ~ith copper or ' ~l other metals. If'this additive method is to be employed .,~ .
`~r 20 for printed circuit boards in which only one side of the - base material is to be provided with metallic conductor runs, J
" it is necessary to protect the base material agains-t metallization on the side which does not contain conductor runs. A very efficient me-thod to this end is to render -the ; 25 affected base material side metallophobic, i.e. to render .
~; it metal-repellent.
:; ~ ' - . .
-: ' ' . . : ' ~he prior ar~ discloses a me-thod for producing pa-tterns on suitable bases by means o~ radiation action7 more particularly for the production of printed circuit boards in accordance with the so-called facing process. In -this method, -the surface of -the base, suitably pre-treated where necessary, is -treated wl-th a solution with a p~I value . be-tween ~.5 and 4~0 and contai.ning a small quantity of at ; least one halogen ion of -the chlorine, bromine and/or iodine gxoup, and at least one reducible salt of a non-precious ~ 10 metal in an ion concentration greater than that corresponding .~ to the halogen conten-t and a component adapted to respond to -the radiation energy employed. q1he zones corresponding : . to the desired pattern on -tne surface -thus treated are exposed ... .
~ to the radiation source so as to produce in the zones affected "1 ~
by radiation a real image of the desired pa-ttern consisting of reduced me-tal seeds9 whereafter the surface is rinsed so that the~metal salt is removed from zones not exposed to :radiation and the surface, having the real image, is exposed to a suitable autocatalytic precipita-tion bath in which the radiation-reduced me-tal seeds catalytically cause -the non-electrolytic depositing of metal in -the surface zones covered by the me-tal seeds. ~here is thus produced an image.
of the desired pattern consisting of non-electrolytically :, ' , . deposited metal, the metal thickness depending on the aoti.vity time o~ the autocatalytic bath~ ~he surface of . the base,~at least in the zones thereof in which no non-electrolytical metal deposition is desired, is treated wi-th
2 -& .. ., _ . . ~ . - ' : '' ~ '~ ' :, .
~4~
~: a medium which reduces the ca-talytic activity of open surface places and advantageously represents a compound containing one more element of the series sulphur, tellurium, selenium, polonium? and arsenic. lt has been proposed to use 2-mercaptobenzothiazole or nickel dibut~ldithiocarbamate . as the compound (German Offenlegungsschrlft 25 ~0 L~15, ;` more particularly claims 12 and 13).~
1 ~his me-thod suffers from a number of disadvantages.
,,. ~ .
~" In the first place~ the above~ment;.oned elements and their compounds are difficult to handle and are -t~o some extent toxic or radloactive and therefore pollute the environment.
- ~urthermore, treatment with -the proposed ele~ents and their .~ ` compounds of the zones requiring non-electrolytic metal - ~ deposition is complex and with some elements and compounds is posslble~only by the very expensive vacuum depositing process. Another important disadvantage o~ -the known process ~ ; ` is~that~the~zones in which no non-e~lec~rolytic metal deposits u ~ are required cannot be readily protected agai~st the deposition of me-tals when using more rapldly-acting, relativel~ corrosive further developments of metalli~ing baths. ; .
According to the invention, there is provided a method of producing an at least partially metallophobic ~metal-repellent) surface on an object, ~hich is to be metallized ` ~ 25 in conventiona~ chemical or electroLytic baths, by the use of compounds containing an element with ampho-teric -~ characteristlos, in which stabilized and/or stable antimo~y F
~ ~ .
O
compounds (complexes) which are soluble in water and/or in organic solven-ts are applied in and/or under the surfaces ~hich are to be rendered me-tallophobic.
~he present method may be used ~or producing metallo-~¦ 5 phobic (metal repellent) surfaces on objects of all kinds ~; and gives reliable protection against metal deposition on y the surfaces thus produced, even in the pre~iously men-tioned - rapid-acting metal deposi-ting baths. A compound from the ~.
~ ~ abo~e mentioned group is used which can be readily handled ~ .
and is versatile and can be rendered suitable for large batch production.
In one embodiment of the invention, -the soluble antimony - compounds are used as solutions in water and/or organic `~ solven-ts.
Reliable protection can be provided aga1ns-t any form ` of metal deposition from all known baths for non-electroly-tic and~electrolytlc~metallizing. ~urprising~y, it was fourld : {~
~ that this protection against metallizing remains ~ully ~
~i~ effective if the layers of paper, tex-tile fabric or glass ~; 20 fibre fabrlc, intended for the outer layers of a laminated material, are lmpregnated with the solu-tion of an-timony compounds and are subsequently processed in a conven-tional t : ~:
- manner to form laminated materials. Ano-ther advantage consists in the equally surprising ac-tion of the treatment of prepregs on the corrosion values of the finished laminated ;~ ~ ~ material. Electrolytic edge corrosion conditions are more ~ ; ~
'R~ ~ particularly substantially improved, a feature which can /~l lead to further fields of appiication for the present method.
:,1, : :
, ~ ~ ., . i The invention will be Eurther described, by way of example only, with reference to the following examples. ~
Example 1. A paper web, for example consisting of ~ ~ ;
cotton-S-impregnating paper with a surface weight of 50 to 120 g/cm2, intended for the production of laminates, is impregnated ;
in a vertical or horizontal coating machine by the immersion method with a solution of 4.1 to 12.9% by weight, preferably 10.6% by weight, of antimony glycerate in 1. a to 5.6% by weight, preferably 4.6% by weight, of dimethylformamide (DMF) and water. After drying at temperatures be-tween 100 and 120C, preferably at 11~C
a solids deposit of 7.7 to I5.4% by weight, preferably adjusted to 12.3% by weight, is obtained, depending on the processing speed. The paper web thus pre-treated is pre-impregnated with a . ~
first coat varnish containing low-molecular phenolic prepreg resins and is then dried. The finishing coat is applied in the same manner by the use of phenolic resin varnishes which are known for the production of laminated phenollc resin papers.
Sheets of the paper web thus treated are used as cover sheets `~
when press moulding the laminate. The side of compressed laminates having such a pre-treated covering sheet does not take up any .
-copper in conventional electrolytic and/or chemical baths.
Example 2. A manufacturing process for moulded laminates according to Example 1 in which a solution of 7.1 to 22.1% by weight, preferably 18.2% by weight, of antimony mucate is used for impregnating the web intended for the covering sheet and the solids deposit is adjusted to 13.2 to 26.4% by weight, perferably to 21.1% by weight.
Fxample 3. A manufacturing process for moulded ~ laminates according to Example 1 in which a solution of 3.3 to 10.2% by weight, preferably 8.4% by weight, of antimony glycolate is used for impregnating the web intended for the covering sheet and the solids deposit is adjusted to 6.1 to 12.2% by weight, - ,. . : . .: .,, ,: .: .::.: ~ :.
~ 4~3 preferably to 9.8% by weight.
Example 4. A manufacturing process for moulded laminates !`' according to Example 1 in which a solution of 3.7 to 11.5%
~` by weight, preferably 9.4% by weight, of antimony lactate is used :
~` for impregnating the web intended for the covering sheet and the solids deposit is adjusted to between 6.8 and 13.6% by weight, ' ' preferably to 10.9% by weight.
Example 5. A manufacturing process for moulded " ~ laminates according to Example 1 in which a solution of 5.4 to ' ~' 10 16.8% by weight, preferably 13.8% by weight, or antimony tartrate is used :Eor impregnating the web intended for the covering sheet ' ~ .~ .. .
$ and the solids deposit is adjusted to between 10 and 20% by weight, preferably to 16% by weight.
Examp'le 6. A manufacturing process for moulded l~''` laminates, according to Example 1, in which a solution of 6.6 ';
'~/ to 20.6% by weight, preferably 17.0% by weight, of antimony citrate is used for impregnating the web intended for the covering ' sheet and the solids deposit is adjusted to between 12.3 and 24.6%
: .
: ~ :
by~weight, preferably 19.7% by weight.
Exampl'e 7. A manufacturing process for moulded laminates according to Example 1, in which a solution of 4.9 to 15.4% by weight, preferably 12.6~ by weight, of antimony malate is used for the web intended for the covering sheet and the solids deposit is `~
adjusted to between 9.2 and 18.4% by weight, preferably to 14.7%
by weight.
'Ex'ample 8. A manufacturing process for molded ' laminates as described in any one of Examples 1 to 7, in which a ~; non-iogenous wetting medium, preferably free of silicones, for example the Fluorad FC 340 produced by the 3M Company, is added ;~ 30 to the above mentioned impregnating solutions at the rate of 0.01 ~- to 0.20~ by weight, preferably 0.10% by weight.
` Example 9. A manufacturing process for moulded ' laminates as described in any one of Examples 1 to 8, in which :~ ;
the impregna-ting solution is applied to the web intended for the covering sheet on one side hy means of an applicating roller by . .
the so-called Kiss-Coat process.
. Example 10. A manufacturin~ process for moulded laminates according to Example 1, in which a solution o F 7.5 to :: :,:
:~: 23.4% by weight, preferabl 19.3~ by weight, of phenylamidoantimonyl- ~
, . ~
tartrate in an organic solvent such as formamide (FA), acetamide - (AA), tetrameth~l urea (TMH), dimethylsulphoxide (DMS~, mono-: ::
methylformamide ~MMF), dimethylformamide (DMF), monomethylacetamide ~-. (MMAA), dimethyl.acetamide (DMAA), or N-methylpyrolidone, prefer~
` abl~ DMAA and DMF is used for impregnating the web intended for :~
, ~ : ' : ,' 20 ~
;:!
. .
, ;
' :~ i ' ~' ~ 7 -. i t~
the covering sheet and the solids deposit is adaustecl to 1~.9 to 27.8% by weight, preferably to 22.2% by weight.
~ e 11. A manu~acturing process for moulded i laminates according -to hxample 1, in which a so]ution of ;~
4.6 to 14.4% by weight, preferably 11.8% by weight, of methylc~idoantlmonyltartra-te is used for impregnating the web in-tended for -the covering shee-t and the solids '''t deposit is adjusted to be-tween 8.6 and 17.~o b~ weight, preferably to 13.7% by weight.
x mple 12. ~ manufacturi~g process for moulded `J ~ ` laminates according ta ~xampie 1, in which a solution of ~ 1Q.6 to 3~.1% by weight, preferably 27.2% by weigh-t, of ~, , dichlorphenylamidoantimonyltartrate is used for impregnating . the web intended for -the covering shee-t and the solids deposit is adjus-ted to between 19.7 and 39.4% b~J weigh-t, ` preferably 31.5% by weight.
~ , y~ A manufacturing process for moulded laminates according to Example 1, in which a solution of 7.0 to 21.7% by weigh-t, preferably 17.8% by weight, of n-butylamindoantimonyltartrate is used for impregna-ting the web intended .for the coveri~g sheet c~nd -the solids`
deposit is adjusted -to between 12.9 and 25.8% ~y weight, preferably to 20.6% by weight.
_x~le 14. A manufacturing process according to the processes described in ang one of Examples 10 to 13 in which the above mentioned solution of a tar-trate is replaced by a solution of a corresponding glycerate, mucate~
~ .
.
i'`"'"'' ' ` ' ~ ~ - 8 -, . .
j .
: , _, , , ., ~, .
.
:
glycola-te, lac-tate, citrate or mala-te in a corresponding molar ratio as impregna-ting solution for -the web used as ' covering sheetO
~ p ~ A sligh-tly adhering plastics film~ for ,, ; 5 example ~edlar (R), regis-tered, as a trade mar~ by Messrs.
; Dupont~ with a surf'ace weigh-tof approximately 70 g/m2, is ` coated on o.ne side, for example by means o~ -the previously ~`.; mentioned Kiss-Coa~t process, with a phenolic resin varni.sh : i known for the produc-tio~ of lamina-ted phenolic resin papers and con-taining 12.8 to 25.6% by welgh-t~ preferably 20.5%
' by weight, of phenylamidoantimonyltar-trate and,one or more ~'' ' of the solvents men-tioned in Example 10 in the quantities , stated therein. ~he film is -then dried at temperatures between 110 and 1~0C, preferably at 130C, and a solids deposit of 9.9 to 19.9 g/m2, corresponding to approximately : :
.5 mol% of anti~ony is:se-t. Sheets of the film coated on one side in this manner are placed with the,coated side on :; .
~ a stack of prepregs and are moulded lnto a laminate. ~he :'',: film can be drawn off immediately after the pree~moulding ; ' : 20 operation. ~he side o~ -the laminate previously in contact with said film will then be me-tal-repellen-t (me-tal.lophobic)..
- In some cases it may be advantageous to draw off the film only immedia-tely prior -to further processing.
. Exa ~ ~6. A manufacturing process according to ! 25 Example 15, in which a phenolic resin varnish, containing 7.9 to 15.8% by weight~ preferably 12.6% by weight, of ~,: . methylamidoantimonyltartrate is used for coating the film .. ''' and in which a solids deposit of 6.1 to 12.2 g/m2, preferably 9.8 g/m2~ is set, corresponding approximately to 3.5 mole%
of an-timony (~b).
; _ 9 _ ,...
~ , .
, o Examp]e ~Z~ A manu~acturing process according to Example 15, in which a phenolic resin containing 18~1% to 36.2/o by weigh-t, preferabl~ 29.0%, of dichlorophenylamido-antimon~ltartrate is used for coating the film and in ;~ 5 which a solids deposit of between 14.1 to 28.2 g/m2, preferabl~ 22.6 g/m , is set, corresponding approximately to ~.5 mole% of antimol1y (Sb).
Example lB. A produc-tion process according to xample 15 in which a phenolic resin, con-taining 11.9 to 23.8% by weight, preferabl-g 19.0% by weight, of n-butyl-.~ - amidoantimonyltartrate is used for coatlng the ~ilm and in which a solids deposit of between 9.2 to 18.4 g/m2, ,. ...
~ preferably 14.8 g/m', is set, corresponding approximately !~ ' to 3.5 mole% (~b).
~ manufacturin~ process according to any one of Examples 15 to 18~ in which a corresponding glycerate, mucate, glycolate, lactate, citrate or malate in the oorrespondlng~mole ratio is used in pIace of the relevant tartrate.
Example 20. A carrier material web, more particu]arl~
a paper web, in-tended as oovering layer in the produc-tion ¦ i of laminates, is impregnated by one of the known methods .
wlth a resIn varnich (more particularly phenolic resin varnish) used for the produc-tion o~ lamina-tes ~more par-ticularly hard paper) and co~alns a qua~tity of antimony compounds mentioned in the preceding ~xamples so as to produce a solids deposit of 2~2 to 4.4 mole% Sb, preferably : ' ?
~ - 10 -~, , - -. .. .
' ' , ''''''~ . -,: :
\~ :
~4~
~: a medium which reduces the ca-talytic activity of open surface places and advantageously represents a compound containing one more element of the series sulphur, tellurium, selenium, polonium? and arsenic. lt has been proposed to use 2-mercaptobenzothiazole or nickel dibut~ldithiocarbamate . as the compound (German Offenlegungsschrlft 25 ~0 L~15, ;` more particularly claims 12 and 13).~
1 ~his me-thod suffers from a number of disadvantages.
,,. ~ .
~" In the first place~ the above~ment;.oned elements and their compounds are difficult to handle and are -t~o some extent toxic or radloactive and therefore pollute the environment.
- ~urthermore, treatment with -the proposed ele~ents and their .~ ` compounds of the zones requiring non-electrolytic metal - ~ deposition is complex and with some elements and compounds is posslble~only by the very expensive vacuum depositing process. Another important disadvantage o~ -the known process ~ ; ` is~that~the~zones in which no non-e~lec~rolytic metal deposits u ~ are required cannot be readily protected agai~st the deposition of me-tals when using more rapldly-acting, relativel~ corrosive further developments of metalli~ing baths. ; .
According to the invention, there is provided a method of producing an at least partially metallophobic ~metal-repellent) surface on an object, ~hich is to be metallized ` ~ 25 in conventiona~ chemical or electroLytic baths, by the use of compounds containing an element with ampho-teric -~ characteristlos, in which stabilized and/or stable antimo~y F
~ ~ .
O
compounds (complexes) which are soluble in water and/or in organic solven-ts are applied in and/or under the surfaces ~hich are to be rendered me-tallophobic.
~he present method may be used ~or producing metallo-~¦ 5 phobic (metal repellent) surfaces on objects of all kinds ~; and gives reliable protection against metal deposition on y the surfaces thus produced, even in the pre~iously men-tioned - rapid-acting metal deposi-ting baths. A compound from the ~.
~ ~ abo~e mentioned group is used which can be readily handled ~ .
and is versatile and can be rendered suitable for large batch production.
In one embodiment of the invention, -the soluble antimony - compounds are used as solutions in water and/or organic `~ solven-ts.
Reliable protection can be provided aga1ns-t any form ` of metal deposition from all known baths for non-electroly-tic and~electrolytlc~metallizing. ~urprising~y, it was fourld : {~
~ that this protection against metallizing remains ~ully ~
~i~ effective if the layers of paper, tex-tile fabric or glass ~; 20 fibre fabrlc, intended for the outer layers of a laminated material, are lmpregnated with the solu-tion of an-timony compounds and are subsequently processed in a conven-tional t : ~:
- manner to form laminated materials. Ano-ther advantage consists in the equally surprising ac-tion of the treatment of prepregs on the corrosion values of the finished laminated ;~ ~ ~ material. Electrolytic edge corrosion conditions are more ~ ; ~
'R~ ~ particularly substantially improved, a feature which can /~l lead to further fields of appiication for the present method.
:,1, : :
, ~ ~ ., . i The invention will be Eurther described, by way of example only, with reference to the following examples. ~
Example 1. A paper web, for example consisting of ~ ~ ;
cotton-S-impregnating paper with a surface weight of 50 to 120 g/cm2, intended for the production of laminates, is impregnated ;
in a vertical or horizontal coating machine by the immersion method with a solution of 4.1 to 12.9% by weight, preferably 10.6% by weight, of antimony glycerate in 1. a to 5.6% by weight, preferably 4.6% by weight, of dimethylformamide (DMF) and water. After drying at temperatures be-tween 100 and 120C, preferably at 11~C
a solids deposit of 7.7 to I5.4% by weight, preferably adjusted to 12.3% by weight, is obtained, depending on the processing speed. The paper web thus pre-treated is pre-impregnated with a . ~
first coat varnish containing low-molecular phenolic prepreg resins and is then dried. The finishing coat is applied in the same manner by the use of phenolic resin varnishes which are known for the production of laminated phenollc resin papers.
Sheets of the paper web thus treated are used as cover sheets `~
when press moulding the laminate. The side of compressed laminates having such a pre-treated covering sheet does not take up any .
-copper in conventional electrolytic and/or chemical baths.
Example 2. A manufacturing process for moulded laminates according to Example 1 in which a solution of 7.1 to 22.1% by weight, preferably 18.2% by weight, of antimony mucate is used for impregnating the web intended for the covering sheet and the solids deposit is adjusted to 13.2 to 26.4% by weight, perferably to 21.1% by weight.
Fxample 3. A manufacturing process for moulded ~ laminates according to Example 1 in which a solution of 3.3 to 10.2% by weight, preferably 8.4% by weight, of antimony glycolate is used for impregnating the web intended for the covering sheet and the solids deposit is adjusted to 6.1 to 12.2% by weight, - ,. . : . .: .,, ,: .: .::.: ~ :.
~ 4~3 preferably to 9.8% by weight.
Example 4. A manufacturing process for moulded laminates !`' according to Example 1 in which a solution of 3.7 to 11.5%
~` by weight, preferably 9.4% by weight, of antimony lactate is used :
~` for impregnating the web intended for the covering sheet and the solids deposit is adjusted to between 6.8 and 13.6% by weight, ' ' preferably to 10.9% by weight.
Example 5. A manufacturing process for moulded " ~ laminates according to Example 1 in which a solution of 5.4 to ' ~' 10 16.8% by weight, preferably 13.8% by weight, or antimony tartrate is used :Eor impregnating the web intended for the covering sheet ' ~ .~ .. .
$ and the solids deposit is adjusted to between 10 and 20% by weight, preferably to 16% by weight.
Examp'le 6. A manufacturing process for moulded l~''` laminates, according to Example 1, in which a solution of 6.6 ';
'~/ to 20.6% by weight, preferably 17.0% by weight, of antimony citrate is used for impregnating the web intended for the covering ' sheet and the solids deposit is adjusted to between 12.3 and 24.6%
: .
: ~ :
by~weight, preferably 19.7% by weight.
Exampl'e 7. A manufacturing process for moulded laminates according to Example 1, in which a solution of 4.9 to 15.4% by weight, preferably 12.6~ by weight, of antimony malate is used for the web intended for the covering sheet and the solids deposit is `~
adjusted to between 9.2 and 18.4% by weight, preferably to 14.7%
by weight.
'Ex'ample 8. A manufacturing process for molded ' laminates as described in any one of Examples 1 to 7, in which a ~; non-iogenous wetting medium, preferably free of silicones, for example the Fluorad FC 340 produced by the 3M Company, is added ;~ 30 to the above mentioned impregnating solutions at the rate of 0.01 ~- to 0.20~ by weight, preferably 0.10% by weight.
` Example 9. A manufacturing process for moulded ' laminates as described in any one of Examples 1 to 8, in which :~ ;
the impregna-ting solution is applied to the web intended for the covering sheet on one side hy means of an applicating roller by . .
the so-called Kiss-Coat process.
. Example 10. A manufacturin~ process for moulded laminates according to Example 1, in which a solution o F 7.5 to :: :,:
:~: 23.4% by weight, preferabl 19.3~ by weight, of phenylamidoantimonyl- ~
, . ~
tartrate in an organic solvent such as formamide (FA), acetamide - (AA), tetrameth~l urea (TMH), dimethylsulphoxide (DMS~, mono-: ::
methylformamide ~MMF), dimethylformamide (DMF), monomethylacetamide ~-. (MMAA), dimethyl.acetamide (DMAA), or N-methylpyrolidone, prefer~
` abl~ DMAA and DMF is used for impregnating the web intended for :~
, ~ : ' : ,' 20 ~
;:!
. .
, ;
' :~ i ' ~' ~ 7 -. i t~
the covering sheet and the solids deposit is adaustecl to 1~.9 to 27.8% by weight, preferably to 22.2% by weight.
~ e 11. A manu~acturing process for moulded i laminates according -to hxample 1, in which a so]ution of ;~
4.6 to 14.4% by weight, preferably 11.8% by weight, of methylc~idoantlmonyltartra-te is used for impregnating the web in-tended for -the covering shee-t and the solids '''t deposit is adjusted to be-tween 8.6 and 17.~o b~ weight, preferably to 13.7% by weight.
x mple 12. ~ manufacturi~g process for moulded `J ~ ` laminates according ta ~xampie 1, in which a solution of ~ 1Q.6 to 3~.1% by weight, preferably 27.2% by weigh-t, of ~, , dichlorphenylamidoantimonyltartrate is used for impregnating . the web intended for -the covering shee-t and the solids deposit is adjus-ted to between 19.7 and 39.4% b~J weigh-t, ` preferably 31.5% by weight.
~ , y~ A manufacturing process for moulded laminates according to Example 1, in which a solution of 7.0 to 21.7% by weigh-t, preferably 17.8% by weight, of n-butylamindoantimonyltartrate is used for impregna-ting the web intended .for the coveri~g sheet c~nd -the solids`
deposit is adjusted -to between 12.9 and 25.8% ~y weight, preferably to 20.6% by weight.
_x~le 14. A manufacturing process according to the processes described in ang one of Examples 10 to 13 in which the above mentioned solution of a tar-trate is replaced by a solution of a corresponding glycerate, mucate~
~ .
.
i'`"'"'' ' ` ' ~ ~ - 8 -, . .
j .
: , _, , , ., ~, .
.
:
glycola-te, lac-tate, citrate or mala-te in a corresponding molar ratio as impregna-ting solution for -the web used as ' covering sheetO
~ p ~ A sligh-tly adhering plastics film~ for ,, ; 5 example ~edlar (R), regis-tered, as a trade mar~ by Messrs.
; Dupont~ with a surf'ace weigh-tof approximately 70 g/m2, is ` coated on o.ne side, for example by means o~ -the previously ~`.; mentioned Kiss-Coa~t process, with a phenolic resin varni.sh : i known for the produc-tio~ of lamina-ted phenolic resin papers and con-taining 12.8 to 25.6% by welgh-t~ preferably 20.5%
' by weight, of phenylamidoantimonyltar-trate and,one or more ~'' ' of the solvents men-tioned in Example 10 in the quantities , stated therein. ~he film is -then dried at temperatures between 110 and 1~0C, preferably at 130C, and a solids deposit of 9.9 to 19.9 g/m2, corresponding to approximately : :
.5 mol% of anti~ony is:se-t. Sheets of the film coated on one side in this manner are placed with the,coated side on :; .
~ a stack of prepregs and are moulded lnto a laminate. ~he :'',: film can be drawn off immediately after the pree~moulding ; ' : 20 operation. ~he side o~ -the laminate previously in contact with said film will then be me-tal-repellen-t (me-tal.lophobic)..
- In some cases it may be advantageous to draw off the film only immedia-tely prior -to further processing.
. Exa ~ ~6. A manufacturing process according to ! 25 Example 15, in which a phenolic resin varnish, containing 7.9 to 15.8% by weight~ preferably 12.6% by weight, of ~,: . methylamidoantimonyltartrate is used for coating the film .. ''' and in which a solids deposit of 6.1 to 12.2 g/m2, preferably 9.8 g/m2~ is set, corresponding approximately to 3.5 mole%
of an-timony (~b).
; _ 9 _ ,...
~ , .
, o Examp]e ~Z~ A manu~acturing process according to Example 15, in which a phenolic resin containing 18~1% to 36.2/o by weigh-t, preferabl~ 29.0%, of dichlorophenylamido-antimon~ltartrate is used for coating the film and in ;~ 5 which a solids deposit of between 14.1 to 28.2 g/m2, preferabl~ 22.6 g/m , is set, corresponding approximately to ~.5 mole% of antimol1y (Sb).
Example lB. A produc-tion process according to xample 15 in which a phenolic resin, con-taining 11.9 to 23.8% by weight, preferabl-g 19.0% by weight, of n-butyl-.~ - amidoantimonyltartrate is used for coatlng the ~ilm and in which a solids deposit of between 9.2 to 18.4 g/m2, ,. ...
~ preferably 14.8 g/m', is set, corresponding approximately !~ ' to 3.5 mole% (~b).
~ manufacturin~ process according to any one of Examples 15 to 18~ in which a corresponding glycerate, mucate, glycolate, lactate, citrate or malate in the oorrespondlng~mole ratio is used in pIace of the relevant tartrate.
Example 20. A carrier material web, more particu]arl~
a paper web, in-tended as oovering layer in the produc-tion ¦ i of laminates, is impregnated by one of the known methods .
wlth a resIn varnich (more particularly phenolic resin varnish) used for the produc-tion o~ lamina-tes ~more par-ticularly hard paper) and co~alns a qua~tity of antimony compounds mentioned in the preceding ~xamples so as to produce a solids deposit of 2~2 to 4.4 mole% Sb, preferably : ' ?
~ - 10 -~, , - -. .. .
' ' , ''''''~ . -,: :
\~ :
3.~ ~ole% Sb. Th1s op-timvm rati.o is unaffec-ted irrespecti.~e o~ whe-ther it is applied to the pre1-.;minary impreg.na-tion, th~ covering impregnation or a onc.e only impregna-tion o.
th~ web.
~- 5 ~Lx~m~le ~1. A finished hard pape~ panel was coa-ted on one side o~ a ~iss Coating m~chine wi-th a varnish described m ~amples 15 to 19 ~hil@ maintalning the stated re~e~ant solids deposits and wa.s dried. '.rhe coa-ted sIde . .
ha~ a metal-.repellent (metallophobic) charac-teristlc in 10 co~entional elec-troly-tic and~or che~nical metallizing baths~
- ~xam~le 22. ~ ~i.nished laminated paper panel was .,, _...... _ p ætially printed on a screen printing machine with a co~ercial screen prin-ting pas-te~ mixed with one of the . ~ anti.~oI~ co~pounds men-tioned i.n ~x~mples 15 -to 19 in -the - 15 co~resporlding concentration. ~he printed places of -the panel did not absorb any me-tal in the conventional . .
. ~ ele¢trolytic and/or chemical metallizlng baths.
o~summarize, it may be stated that the metallophobic actio~ of;the antimony compounds ~ccording to the invention 20~ was surprislngly fully ~aintained in all cases under , ~ ~ investigation.
. ' . .
~ : :
' ' -' , . -. : :
- :
~: .
~i :
:~.~ - :
th~ web.
~- 5 ~Lx~m~le ~1. A finished hard pape~ panel was coa-ted on one side o~ a ~iss Coating m~chine wi-th a varnish described m ~amples 15 to 19 ~hil@ maintalning the stated re~e~ant solids deposits and wa.s dried. '.rhe coa-ted sIde . .
ha~ a metal-.repellent (metallophobic) charac-teristlc in 10 co~entional elec-troly-tic and~or che~nical metallizing baths~
- ~xam~le 22. ~ ~i.nished laminated paper panel was .,, _...... _ p ætially printed on a screen printing machine with a co~ercial screen prin-ting pas-te~ mixed with one of the . ~ anti.~oI~ co~pounds men-tioned i.n ~x~mples 15 -to 19 in -the - 15 co~resporlding concentration. ~he printed places of -the panel did not absorb any me-tal in the conventional . .
. ~ ele¢trolytic and/or chemical metallizlng baths.
o~summarize, it may be stated that the metallophobic actio~ of;the antimony compounds ~ccording to the invention 20~ was surprislngly fully ~aintained in all cases under , ~ ~ investigation.
. ' . .
~ : :
' ' -' , . -. : :
- :
~: .
~i :
:~.~ - :
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of producing an at least partially metallo-phobic (metal-repellent) surface on an object, which is to be metallized in conventional chemical or electrolytic baths, by the use of compounds containing an element with amphoteric characteristics, the method comprising applying at least one antimony compound selected from stabilized antimony compounds (complexes) and stable antimony compounds (complexes) which are soluble in water or organic solvents, in or under the surfaces which are to be rendered metallophobic.
2. A method as set forth in claim 1, wherein said soluble antimony compounds are used as solutions in at least one of water and organic solvents.
3. A method as set forth in claim 1, wherein the objects to be rendered metallophobic are at least partially coated with one of a soluble antimony compound and a substance mixture containing such antimony compound.
4. A method as set forth in claim 3, wherein a film at least partially covered by an antimony compound which is insoluble in water but is soluble in organic solvents is pressed on the covering sheet of a laminate material, after which said film is drawn off.
5. A method as set forth in claim 4, wherein said film is used in the form of a negative print to produce a partially metallophobic surface.
6. A method as set forth in claim 1, wherein the soluble antimony compounds are introduced into the object at regions near its surface, in one or more covering layers of a laminate material, on partial surfaces.
7. A method as set forth in claim 6, wherein the antimony compounds are applied during manufacture of at least one of the carrier material and its initial products.
8. A method as set forth in claim 6, wherein carrier materials intended for prepregs of the laminates are impregnated on a varnish coating machine with the solution of the antimony compounds and are then dried, followed by conventional further processing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2628350A DE2628350C3 (en) | 1976-06-24 | 1976-06-24 | Process for the production of non-metallizable surfaces on laminates using a dissolved antimony complex and application of the process |
| DEP2628350.1-45 | 1976-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104010A true CA1104010A (en) | 1981-06-30 |
Family
ID=5981334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA281,246A Expired CA1104010A (en) | 1976-06-24 | 1977-06-23 | Methods of producing at least partially metallophobic surfaces on objects |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS537538A (en) |
| AT (1) | AT351885B (en) |
| CA (1) | CA1104010A (en) |
| CH (1) | CH632299A5 (en) |
| DE (1) | DE2628350C3 (en) |
| FR (1) | FR2355923A1 (en) |
| GB (1) | GB1547079A (en) |
| IT (1) | IT1077233B (en) |
| SE (1) | SE424005B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151313A (en) * | 1977-03-11 | 1979-04-24 | Hitachi, Ltd. | Method for production of printed circuits by electroless metal plating employing a solid solution of metal oxides of titanium, nickel, and antimony as a masking material |
| JPS60185818A (en) * | 1984-03-01 | 1985-09-21 | Nikkiso Co Ltd | Preparation of carbon fiber by gaseous phase method |
| JPS6054998A (en) * | 1983-09-06 | 1985-03-29 | Nikkiso Co Ltd | Production of carbon fiber grown in vapor phase |
| JPS6074599A (en) * | 1983-09-30 | 1985-04-26 | 株式会社日立製作所 | Printed circuit board and method of producing same |
| JPS60224816A (en) * | 1984-04-20 | 1985-11-09 | Nikkiso Co Ltd | Gas-phase production of carbon fiber |
| FR2564110B1 (en) * | 1984-05-10 | 1986-09-05 | Lorraine Carbone | PROCESS FOR PRODUCING VAPO-DEPOSITED CARBON FIBERS FROM METHANE |
| US4861539A (en) * | 1986-11-20 | 1989-08-29 | Allied Colloids Ltd. | Process of making water-absorbent, water-insoluble, cross linked fiber or film |
| JP4794248B2 (en) * | 2005-09-14 | 2011-10-19 | 卓 新井 | Surface treatment agent for zinc or zinc alloy products |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775121A (en) * | 1972-08-09 | 1973-11-27 | Western Electric Co | Method of selectively depositing a metal on a surface of a substrate |
-
1976
- 1976-06-24 DE DE2628350A patent/DE2628350C3/en not_active Expired
-
1977
- 1977-05-27 AT AT380177A patent/AT351885B/en not_active IP Right Cessation
- 1977-06-08 IT IT24504/77A patent/IT1077233B/en active
- 1977-06-10 GB GB24333/77A patent/GB1547079A/en not_active Expired
- 1977-06-17 SE SE7707077A patent/SE424005B/en unknown
- 1977-06-23 CA CA281,246A patent/CA1104010A/en not_active Expired
- 1977-06-23 CH CH773777A patent/CH632299A5/en not_active IP Right Cessation
- 1977-06-24 JP JP7536177A patent/JPS537538A/en active Pending
- 1977-06-24 FR FR7719444A patent/FR2355923A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS537538A (en) | 1978-01-24 |
| AT351885B (en) | 1979-08-27 |
| IT1077233B (en) | 1985-05-04 |
| GB1547079A (en) | 1979-06-06 |
| ATA380177A (en) | 1979-01-15 |
| DE2628350C3 (en) | 1978-12-07 |
| DE2628350A1 (en) | 1977-12-29 |
| CH632299A5 (en) | 1982-09-30 |
| SE424005B (en) | 1982-06-21 |
| FR2355923B1 (en) | 1981-10-16 |
| SE7707077L (en) | 1977-12-25 |
| FR2355923A1 (en) | 1978-01-20 |
| DE2628350B2 (en) | 1978-04-20 |
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