Note: Descriptions are shown in the official language in which they were submitted.
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
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 -
~, , - -. .. .
' ' , ''''''~ . -
,: :
\~ :
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
:
:~.~ - :
