Note: Descriptions are shown in the official language in which they were submitted.
~2~
K-18076/AICGM 371
Mixtures
The present invention relates to mixtures comprising an epoxy resin and a soluble
polyamide-polyimide (PA-PI) block copolymer, and to the laminates, coatings, foils or
bonded materials, especially bonded metal foils, prepared from those mixtures.
PA-PI block copolymers are materials having very good mechanical and thermal proper-
ties that are used inter alia for coating metnl foils. An important property of those
so-called flexible larninates is the fact that they can be folded a Inrge nurnber of times
before breaking. Such flexible laminates are described, for example, in EP Pntent 48 219.
The polymers processed in that patent are applied in the form of a polyaunide-polyamide
acid solution and after the coadng operadon are converted thermally into the insoluble
polyamide-polyirnide forrn by removing the elements of water. That reaction step can,
however, lead to undesired secondary phenomena such as bubble formation and degrada-
don of molecular weight. Furthermore, the polyamide-polyamide acid solution that is used
is not stable to storage.
For that reason it is advantageous to use for those coatings soluble PA-PI block co-
polymers, such as those known, for example, from EP-A 324 315 or DE-OS 37 38 4~8.
After being applied, however, those soluble polymers are sensitive to the solvents used.
Solvent-stable polymers can be obtained in the case of certain compositions by means of a
thermal after~eatment, but ~hat may require high temperatures andlor long reaction times.
It has now been found that a mixture comprising an epoxy resin having at least two epoxy
groups in the molçcule and a soluble PA-PI block copolyrner yields, after application, a
solvent-stable coating within a short time at relatively low reaction temperatures, while at
the same time the good mechanical properties of the polymer are very largely retained.
The present invention accordingly relates to mixtures comprising
(a) an epoxy resin having at least two epoxy groups in the molecule, and
(b) a polyamide-polyimide (PA-PI) block copolymer that is soluble in a polar aprotic
solvent, in a ratio by weight of a:b of from 1:1 to 1:200.
---` 2~2~
Here and hereinafter, PA-PI block copolymers shall be understood as being compounds
that are made up of polyamide and polyimide blocks, of polyamideimide and polyimide
blocks or of polyamide, polyamideimide and polyimide blocks.
In the mixture according to the invention, the ratio by weight of a:b is preferably from 1:4
to 1:100, especially from 1:5 to 1:50, more especially from 1:15 to 1:40.
Epoxy resins that can be used in the mixtures are preferably those having at least two
groups of formula I
--CH{~ - CH (1),
R~ Ru RU,
that are bonded directly to an oxygen, nitrogen or sulfur atom or atoms, wherein either R'
and R"' are each a hydrogen atom, in which case R" is a hydrogen atom or a methyl group,
or R' and R"' together are -OEI2CH2-, in which case R" is a hydrogen atom.
Examples of such resins are polyglycidyl and poly(~-methylglycidyl) esters which can be
obtained by reaction of a compound containing two or more carboxylic acid groups per
molecule with epichlorohydrin, glycerol dichlorohydrin or ~-methylepichlorohydrin in the
presence of aL~cali. Such polyglycidyl esters can be derived from aliphatic polycarboxylic
acids, for example oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, cyclo-
aliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydro-
phthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid, and aromatic
polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
Further examples are polyglycidyl and poly(~-methylglycidyl) ethers which can be ob-
tained by reaction of a compound containing at least two free alcoholic and/or phenolic
hydroxy groups per molecule with the corresponding epichlorohydrin under aL~caline con-
ditions, or alternatively in the presence of an acidic catalyst with subsequent aLlcali
treatment. These ethers can be prepared from acyclic alcohols, such as ethylene glycol,
diethylene glycol, and higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxy-
~L~2~
propylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols,
pentane-1,5-diol, hexane-l,~diol, hexane-2,4,6-triol, glycerol, l,l,1-trimethylolpropane,
pentaerythritol, sorbitol and polyepichlorohydrins, from cycloaliphatic alcohols, such as
resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)-
propane and l,l-bisthydroxymethyl)-3-cyclohexene, and from alcohols h~ving aromatic
nuclei, such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)di-
phenylmethane. They can also be prepared from mononuclear phenols, such as resorcinol
and hydroquinone, and polynuclear phenols, such as bis(4-hydroxyphenyl)methane,
4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)-
ethane, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-
propane, and novolaks formed from aldehydes, s~ch as formaldehyde, acetaldehyde,chloral and furfural, with phenols, such as phenol itself and phenol ring-s~lbstituted by
chlorine atoms or by alkyl groups each having up to nine carbon atoms, such as 4-chloro-
phenol, 2-methylphenol and 4-tert-butylphenol~
Poly(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination
of the reaction products of epichlorohydrin with amines containing a~ least two amine
hydrogen atoms, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylene-
diamine and bis(4-methylaminophenyl)methane, triglycidyl isocyanurate, and N,N'-digly-
cidyl derivatives of cyclic aLlcyleneureas, such as ethyleneurea and 1,3-propyleneurea, and
hydantoins, such as 5,5-dimethylhydantoin.
Poly(S-glycidyl) compounds are, for example, the di-S-glycidyl derivatives of dithiols,
such as ethanel,2-dithiol and bis(4-mercaptomethylphenyl) ether.
Examples of epoxy resins having groups of formula I wherein R' and R"' together form a
-~I2~H2- group, are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl
ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane, bis(3,4-epoxycyclohexylmethyl) adipate
or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
Also suitable are epoxy resins in which the 1 ~2-epoxy groups are bonded to hetero atoms
of various kinds, for example the N,N,O-triglycidyl derivative of 4-arninophenol or of
2,2-(4-aminophenyl-4'-hydroxyphenyl)-propane, the glycidyl ether/glycidyl ester of sali-
cylic acid, N-glycidyl-N'(2-glycidyloxypropyl)-5l5-dimethylhydantoin and 2-glycidyl-
oxy-1,3-bis(S,S-dimethyl-l-glycidylhydantoin-3-yl)propane. The epoxy resins used may
also be substituted by alkyl groups, alkenyl groups, aryl groups, halo~gen atoms, aryloxy or
2~2~9
by aLkoxy. A preferred example thereof is o,o'-diallylbisphenol A diglycidyl ether.
If desired, it is possible to use a mixture of epoxy resins.
Preferred epoxy resins are polyglycidyl ethers of phenols or novolaks, triglycidyl isocyan-
urate, N,N,O-triglycidyl-p-aminophenol, poly(N-glycidyl) derivatives of aromatic amines,
and cycloaliphatic epoxy resins. Especially preferred resins are the diglysidyl ethers of
bisphenols, such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bisphenol S and bis-
(4-hydroxyphenyl)methane (bisphenol F) or novolaks, o,o'-diallylbisphenol A diglycidyl
ether, triglycidyl isocyanurate, N,N,O-triglycidyl-p-aminophenol, bis[4-(diglycidyl-
amino)-phenyl]methane, tetra-(p-glycidyloxyphenyl)ethane and 3,4-epoxycyclohexyl-
methyl-3,4-epoxycyclohexanecarboxylate.
The expression "soluble PA-PI block copolymer" shall be understood gene~lly as mean-
ing a copolymer that is soluble in polar aprotic solvents and from which it is possible to
prepare soludons comprising at least 5 % by weight, especially at least 10 % by weight,
PA-PI block copolymer, based on the solution.
PA-PI block copolymers (b) that are soluble in a polar aprotic solvent are known, for
example from EP-A 324 315. Preferred are block copnlymers of type A having an average
molecular weight Ml, of from 1000 to 50 000 and recurring uni~s of forrnula II
~PA-PI~ (II),
wherein PA is a polyamide block having an average molecular weight MTI ~f from 300 to
20 000, comprising at least one (recurring) unit of formula III
O O
(DI),
~ C-Rl-C-NH-R2-NH ~
wherein Rl is a radical of forrnula -C"H2,l-, ~, ~ ~3,
2~2~
--~, ~ or ~ a ~3 and R2 is a radical
of formula ~CnH2n~~ --CH2 ~3 CH2--
~CH~ ~CH2~
~} o ~ ~3} a ~3} o ~3 or
~ Q ¢3 a ~ Q ~} , wherein Q is a direct bond,
-CH2-, -CH2CH2-. -CH(CH3)-, -C(CH3)2-, -C(CF3)-, -O-, -S-, -SO2- or -CO-, and n is
from 2 to 12, and Ya~ Yb, Yc and Yd each independently of the others are hydrogen,
halogen or Cl-C4alkyl, and PI is a polyimide block having an average molecuklr weight
Ml~ of from 300 to 20 000, comprising at least one (recurring) unit of formula IV
~ O O ~
--N R3~N--R2 (IV).
O O
whereinR3is ~, ~ or ~ ~, andQand
R2 are as defined above, with the pro~iso that from 25 to 100 mol% of all bridge members
` R2are ~S2~} and~or ~/SO~,andthe
proportion of (cyclo-)aliphatic bridge members R2 is not more than 10 mol%.
2~2~
Preferred block copolymers having the recurring unit of formula II have an average
molecular weight Ml, of from 4000 to 40 000.
In preferred block copolymers, the polyamide blocks and/or the polyimide blocks com-
prise more than one recurring structural unit of forrnula III or of formula IV as the case
may be. For prefeIred polyamide blocks and/or polyimide blocks this results in an average
molecular weight of from 500 to 20 000.
In the above formulae, Rl is, for example, phenylene-1,3; phenylene-1,4; naphthylene-1,5;
naphthylene-1l8; biphenylene-3,3', biphenylene-4,4'
~ o ~3 ~ so2~3 or butylene-1,4-
Phenylene-1,3 is preferred.
According to the invention, R2 in formulae m and/or IV is characterised in that from 25 to
100 mol% and especially from 50 to 100 mol% of the bridge members R2 occurring in the
copolymer represent groups of the formulae
~SO2~ andlor \~/SO~
It is not essential for both polyamide and polyimide blocks to comprise such bridge
members.
If Rl or R2 is a group -CnH2n-, then it is, for example, ethylene- 1,2; propylene- 1,3;
tetramethylene-1,4; pentamethylene-1,5; hexamethylene-1,6; heptamethylene-1,7; octa-
methylene-1,8; nonamethylene-1,9; decamethylene-1,10; dodecamethylene-1,12; deca-
methylene-2,9; or 2-methylpentamethylene- 1,5.
If Rl or R2 is a group ~, then it may be cyclohexylene- 1,2; cyclohexyl-
ene-1,3 or cyclohexylene-1,4.
2~24~
Further examples of specific cycloaliphatic grnups R2 are
A A --H2C ~, CH2-- --
CH2~ , ~J ~`CH2--
C,2Hs C2Hs
~} CH2~ ~ H2-- {} CH
C2Hs C2H5
Examples of specific aromadc groups R2 are phenylene-1~2; phenylene-1,3; phenyl-ene-1,4; methylpheaylene-2,4; 1,3,5-trimethylphenylene-2,5; xylylene-2,5; ~ chloro-
phenylene-1,3, 2,5-dichlorophenylene-1,4; or one of the following groupg
~/ ~, ~CH2~3 ,
~CH~ o o
--S O ~C~,
r~
.
0~
~-o-~o~3
--` 2~2~
~o~ ~' ~3{3
CH3 CH3 C2H5 C2H5
CH2~ ' ~ CH2~/~
C2H5 C2Hs
isoC3H7 isoC3H7
'~ CH2~, ~ C ~3
isoC3H7 IsoC3H7
~30~so2~o~,
~30~,
~3 o e~ ~ and ospecia~y ~ho groulls
~3
? o~3 ~s02
~SO~ for R2 in folmula III, and the groups
2 ~
g
~3 ' ~ S2~} and
SO2
~/ \~ for R2 in formula IV.
If a bridge member R2 comprises a divalent radical Q, then that radical is, for example,
-CH2(~I2- or -S-, or, preferably, -CHr, CH3-C-CH3, -O-, -SO2- or -CtO)-. If a bridge
member R2 comprises several radicals Q, those radicals may be identical or dif~erent.
The tetravalent radical R3 is derived from a tetracarboxylic acid that is capnble of ~orming
a dianhydride. That radical is, for exarnple, a group
='~ ='X~~'
~ ~ or
and especially ~ .
Examples of possible combinations of polyamide and polyimide blocks to form PA-PI
block copolymers of type A are indicated in Table I. Those PA-PI block copolymers can
be prepared in accordance with Example 1 of EP-A ~ 324 31~.
`
.
2~2~
- 10-
o
o t" o C,~ ~3
~ ~ ~ ~ o o o o o
,~ ~ ~
'~ F ~ ~ ~ ~; o o ~ o o ~
~ . ~ ~
.~ ~o ~ e ~ a ~ ~ ~ O
~3 0 ~ O ~ O a O ~ o ~ O t3 ;~5 ~ O
~ _ ~ ~ ~o ~ 8 ~ o ~ ~o ~ C- o
¢1 ~ ~ v~
_ ~ ~ o, ~ ~ o.~-- C~ . C~ C~ . ~:~ . ~ ~ ~ ~
C o ~ o P.O P.O P,O ~o ~o P.O ~o ~o
o ~ ~ ~
~ :~ Y ~ ~ ~ ~ ~ ~ O ~ ~ ~ O
,
.:
.
--- 2~l~2~9
s,'~ li v~ ~
~ a :~ ~ ~ O ~ ~
~ ~ a~
a~ a ~
2 0 ~
Further suitable PA-PI block copolymers of type B that are soluble in polar aprotic
solvents and have recurring units of formula II and an average molecular weight Mr, of
from 1000 to S0 000 are characterised in that they have a ratio of amide groups to imide
groups of approximately from 4:1 to 1:4 and that they have in the polyimide blocks a
content of at least 2 mol%, especially at least S mol%, based on the content of all the
carboxylic acid radicals in the copolymer, of radicals of the forrnula
CH3
~ (DMCD radicals~ which are derived from 5-(2,5-diketotetrahydrofur-
furyl)-3-methylcyclohexene-1,2-dicarboxylic acid.
The content of DMCD radicals in the PA-PI block copolymers that can be used accorcling
to the invention is generally from 2 to 80 mol%, based on the content of all the carboxylic
acid raclicals in the copolymer.
Preferred PA-PI block compolymers comprise combinations of blocks of formulae Vb and
IVa and/or IVc or of formulae lVb and Va and/or Vc
--NH--C--Rl--C ~NH--R2--NH--C--Rl--C ~ NH (IVa),
o o o
--N/ ~R3~ ~N--R4--N~ N aVb),
O - O
--NH--C--R5~ R6--Nll--C--R5~ ~N-- (IVc),
2 ~ 9
- o o
11 11
R2_--NH--C--Rl--C NH--R2--e (Va),
o o
C~ 3\C/ ~ ~Vb),
0 11
--R~ NH--C--R~ ~N--R6~ (Vc),
wherein the indices e, f and g, each independently of the others, are integers from 1 to 100,
Rl and R2 are as defined for formula III, R3 is a radical of the fonnula
CH3
~' ~Q{~ ~ or ~
wherein Q is a direct bond or is -CH2-, -CH2CH2-, -c~(cH3)-, -C(cH3)r, -C(CF3)2-~ -O-.
-S-, -SO2- or -CO-, R5 is a radical of the formula ~ , and R4 and R6 each inde-
pendently of the other have one of the definitions of R2, with the proviso that from 25 to
100 mol% of all the radicals R3 have the forrnula ~ .
In formulae IVa and Va, Rl and R2 have the same preferred meaning as for formula III.
The tetravalent radical R~ is derived from a tetracarboxylic acid that ;s capable of forming
a dianhydride~
Preference is given to radicals of the formula
2 ~
o
3 ~ or
c~3
G(CF3)~ ~ ~
~ ~J~ and especially ~ .
The proportion of DMCD radicals in the polyimide blocks of the block copolymers to be
used according to the invendon is preferably from 50 to 100 mol%, based on the propor-
don of tetracarboxylic acid radicals in those blocks.
Rs lS preferably a radical of the formula ~bJ--.
Possible combina~ons of polyamide and polyimide blocks to folm PA-PI block co-
polymers of type B are indicated in Table II. Those block copolymers can be obtained, for
example, in a manner known ~r se by reaction of preformed polyamide and poly~nide
acid blocks and subsequent cyclisation of the polyamide-polyamide acid.
2 ~
- 15-
,_ , ,
R E ~ O O O O ~ ~ O
.
-' .fi ~E E
_ ~ ~ O
.~
O
E$E e a 3 E ~ E e
. X
.o ~
Q ' ~ ~ ~ ~
~ 3 Cl~O ~ O CL O ~ O ~0 ~ ~ ,~ ~
Y 3 y .
o ~ R ,~ E.~ 3E
E 3 ~ ~ ~ ~ e ~ O a o E
.
~,, . : .
-` 2 ~ 2 ~
- 16-
Further suitable PA-PI block copolymers of type C that are soluble in polar aprotic
solvents and that have an average molecular weight Mn of from 1000 to 50 000 comprise
a combination of blocks of forrnula IVa and Vb and/or Vc or of formulae IVb and Va
and/or Vc or of formulae IVc and Va and/or Vb, with the different proviso that from 10 to
100 mol%, preferably from 25 to 100 mol%, especially from 50 to 100 mol%, of all the
radicals R2, R4 and R6, based on the total amount of those radicals, have the forrnula
~ CHz~ q , wherein p is 1 or 2 and q is zero, 1 or 2, and each of R7 and
R8 is Cl-C8alkyl, or wherein pairs of radicals R7 and R8 that are in ortho posidon relative
to one another together forrn an alkylene group.
An alkyl substituent R7 or R8 in the above forrnula may be branched or preferably
st~ight-chain. Straight-chain Cl-C6alkyl is preferred. Examples thereof are methyl, ethyl,
n-propyl, n-butyl, n-pentyl and n-hexyl. Methyl and ethyl are especially preferred.
If the radicals R7 or R8 together form an alkylene chain, then it is preferably trimethylene
and, especially, tetramethylene.
The preferred ratio of amide groups to imide groups in the PA-PI block copolymers to be
used is from 4:1 to 1:4.
The average molecular weights Ml, in the polyamide blocks IVa and Va or in the
polyirnide blocks IVb and Vb or in the polyamideimide blocks IVc and Vc of the PA-PI
block copolymers C are generally from 300 to 20 000, preferably from 500 to 10 000.
In addition to the above-mentioned combinations of two blocks, the PA-PI block copoly-
mers C to be used according to the invention may also comprise ~ee-block combinations
of formulae IVa, IVb and Vc or of formulae IVa, IVc and Vb or of formulae IVb, IVc and
Va.
Preference is given to the use of PA-PI block copolymers C that consist substantially of
polyamide blocks IVa and polyimide blocks IVb or of polyamide blocks Va and polyimide
blocks IVb.
The RA-PI block copolymers C that are to be used according to the invention can also be
-` 2~2~
prepared in a manner known ~ se by reaction of preforrned polyamide and polyamide
acid blocks and subsequent cyclisation of the polyamide-polyamide acid.
Examples of possible combinations of polyamide and polyimide blocks to fonn PA-PI
block copolymers C are given in the following Table m.
The following abbreviations are used in Table m:
~,: inherent viscosity measured using a 0.5% by weight solution of the polymer
at 25C (in NMP),
BTDA: 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride,
BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
IPC: isophthalic acid dichloride,
TMAC: trimellitic acid anhydride chloride,
BADM: bis(3,5-diethyl-4-aminophenyl)methane,
BEMA: bis(3-ethyl-5-methyl-4-aminophenyl)methane,
BIDM: bis(3,5-diisopropyl-4-aminophenyl)methane,
mDDS: 3,3'-diaminodiphenylsulfone,
pDDS: 4,4'-diaminodiphenylsulfone,
diarnine mixture: industrial product consisting of 4,4'-diaminodiphenylmethane,
3-ethyl-4,4'-diaminodiphenylmelhane and 3,3'-diethyl-4,4'-diaminodiphenyl-
methane,
PA-PAS: polyamide-polyamide acid.
- 2~2~
- 18-
~ ~ . ~
O A ~
~, o~ Vol o~ o ;50~ o ;~oS o o o o .'
1 o S ~
..... __ , , ~
s
y _ y ~ y y ~
~ .~ ~ ~ O m O m ~ ~ O ~ fi
,~ ~ , ~ g y~ 0 ~ o jj ~ n ~ o~
1 ~ ~ 8 ~ 8 ~ o ~ 8 ~ 8 ~ 8 ~ 8
~24~ 9
,9
Further suitable PA-PI block copolymers of type D that are soluble in polar aprotic
solvents and that have an average molecular weight Mn f from 1000 to 50 000,
preferably from 5000 to 40 000, comprise a combination of blocks of formulae IVa and
Vb and/or Vc or of formulae IVb and Va and/or Vc or of formulae IVc and Va and/or Vb,
with the different proviso that from 25 lo 100 mol% of all the radicals R2, R4 and R6,
based on the total amount of those radicals, have the forrnulae _ c
(y) m
and/or ~ CH2--, wherein Y is Cl-C8alkyl or halogen and m is a number from
Oto4.
The alkyl substituent Y in the above formulne may be branched or prefernbly straight-
chain. Straight-chain Cl-C6alkyl is preferred. Examples thereof are methyl, cthyl,
n-propyl, n-butyl, n-pentyl and n-hexyl. Methyl is especially preferred.
Y as halogen is preferably chlorine or bromine, and m is preferably zero or the number 1.
The ratio of polyamide blocks to polyimide blocks or to polyamideimide blocks in the
block copolymers D to be used according to the invention is generally deterrnined by the
desired solubility of those copolymers in polar aprotic solvents. The individual proportions
of those blocks and the content of xylylenediarnine units andlor aminobenzylamine units
are so selected that the block copolymer is soluble in polar aprotic solvents.
The preferred ratio of amide groups to imide groups in the PA-PI block copolymers D to
be used is from 4:1 to 1:4.
The average molecular weights Mn of the polyarnide blocks IVa or Va or of the poly-
imide blocks IVb or Vb or of the polyamideimide blocks IVc or Vc in the PA-PI block
copolymers D are generally from 300 to ~0 000, preferably from 500 to 10 000.
In addition to the above-mentioned combinations of two blocks, the PA-PI block copoly-
mers D tO be used according to the invention may also comprise three-block combinations
of formulae IVa, IVb and Vc or IVa, IVc and Vb or IVb, IVc and Va.
Especially preferred are PA-PI bl~xk copolymers D that consist substantially of the
~2 ~ ~ ~
- 20-
recurring structural units of foImulae I~la and IVb or IVb and Va.
Very especially prefelTed PA-PI block copolymers of that type are those in which the
xylylenediamine units or the aminobenzylamine units or a combination of xylylenedi-
amine units and aminobenzylamine units are present only in polyirnide blocks lXb or Xb.
The PA-PI block copolymers D to be used according to the invention can also be prepared
in a manner known Per se by reaction of preformed polyamide and polyamide acid bloclcs
and subsequent cyclisation of the polyamide-polyamide acid.
Examples of possible combinations of polyamide and polyimide blocks to form PA-PI
block copolymers D are given in the following Table IV, in which the following abbxevia-
tions nre used:
BTDA: 3,3',4,4'-benzophenonetetrncarboxylic acid dianhydride,
BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
IPC: isophthalic acid dichloride,
TMAC: trimellitic acid anhydride chloride,
mXDA: m-xylylenediar~une,
pXDA: p-xylylenediamine,
ABA: aminoben~ylamine (mixture of m- and p-isomers),
mPDA: m-phenylenediamine
mDDS: 3,3'-diaminodiphenylsulfone,
pDl)S: 4,4'-diaminodiphenylsulfone,
PA-PAS: polyamide-polyamide acid.
~ 2~24.~
~5
.,~ Y~
5~ .5 ~ ~ ~ A
~ ~ S ~o o ~ o ~
o ~o o ~o o ~ ~ ~ o~ ~ ~o ~o
~o ~ o P~ y~o ~
æ ~ 8 ~3 8 ~ O a ~ ~3 ~
,~ ~ u~ 0 ~0 .,
g ~y ~ ~0- s O ~0 ~ O s 0~ ~ æ ~D
8 ~ ~ ~ ~ æ ~ æ ~ æ ~ æ ~
D ,a ~ ~ v~ ¢ ~ ¢ ~n ~ ~ ¢ ~ ¢ ~ ~ ~
~ ~o ~oO ~0 ~00 ~0 ~0 ~0 ¢0 ~ol~o
~;1 ~ ~ 8 ~ 8 ~0~ ~0 ~o~ o~ ~0
a~ o m o m c; ~ O ~ o ~q o ~ o ~ o ~ o ~ o a~ o a: o
- . ~
2 ~ L~ 2
- 22-
The block copolymers to be used according to the invention are prepared in a manner
known ~ se, for exarnple in accordance with a procedure described in DE-A 2 342 464
by reaction of preformed polyamide and polyamide acid and/or polyamideamide acidblocks and subsequent cyclisation of the polyamide-polyamide acids.
In accordance with another method of preparation, polyamide acid blocks having suitable
end groups, preferably anhydride groups, can be reacted with diamines or dicarboxylic
acid derivatives, for example dicarboxylic acid chlorides and/or tricarboxylic acid
anhydride chlorides, and the resulting polyamide acids cyclised.
The block copolymers to be used according to the invention can also be prepared in a
manner known per se by first of all forming a polyamide and/or polyamidearnide ncid
block and then reacting the latter with a suitable tetracarboxylic acid derivative an~l a di-
amine or with a suitable dicarboxylic ncid dichloride nnd a diamine to form n polyamide-
polyamideamide acid block copolymer which is then cyclised. Such a process is
described, for example, in DE-A 2 342 454.
For example, a PA-PI block copolymer of type A can be prepared by reacting polyamides
of formula VII
O O
Il 11
. H~NH-R2-NH-C-Rl-C ] a NH-R2-NH2 (VII)
with polyamide acid dianhydrides of formula VIII
o o o o
~C~ ~C ~ R2~ NH~ C~ ~COOH 1 \R/ \o
C COOH HOOC C ~ NH--R2--NH---C C
Il _ 11 11 11
O O O O
~1
or reacting polyamides of formula IX
2~2~
-23 -
O O O O
Il 11 11 11
Cl-C-RI-C ~ NH-R2-NH-C-Rl-~Cl ax~
with polyarnide acids of formula X
II --NH-R2-NH-C~ / OOH
HOOC \C----NH-R2-N~I2
or by reacdng polyamide acids of formula VIII or X with dicarboxylic acid dichlorides of
forrnula XI
O O
Il 11
Cl-C-Rl-C-CI (XI)
and diamines of forrnula XII
H2N-R2-NH~2
and subsequently cyclising the resuldng polyarnide-polyamide acid copolymers, wherein
in formulae VII to XII Rl, R2 and R3 are as defined for formulae III and IV and a and b
each independently of the other are an integer of at least 2.
The compounds of formulae VII to XII are known. The preparation of the polyamide acids
of formulae vm and X is also described in DE-A 2 342 464 and is car~ied out, forexample, by reacdng tetracarboxylic acid dianhydrides of formula XIII
o o
oJ~R3~0 (XIII),
o o
wherein R3 is as defined hereinbefore, with a less than stoichiometric amount or with an
excess of a diamine of formula XII. It is a simple matter familiar to a person sl~lled in the
art to set the average molecular weights defined above ~and hence a and b) of the individ-
ual blocks by means of suitable reaction condidons, for example by a suitable choice of
the molar rados of the reactants. The polycondensation of the di- or tetra-carboxylic acid
derivadves of formulae VIII, IX or XI, as the case may be, with the diamines of for-
mulae VII or XII, as the case may be, can be carried out in a manner known per se, prefer-
- 2~2~
- 24 -
ably in an anhydrous organic solvent and with the exclusion of moisture, for example
under nitrogen, at temperatures of approximately from -20C to ~50C~ especially ap-
proximately from -15C to ~10C. Suitable organic solvents are polar aprotic solvents,
such as N,N-dimethylacetamide, N,N-diethylacetamide, N,Ndimethylforrnamide, N,N-di-
methylmethoxyacetamide, 2-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-methyl-~-
caprolactam, N,N,N',N'-tetramethylurea, tetrahydrothiophene dioxide (sulfolane) and
dimethyl sulfoxide.
The reaction can also be carried out in mixtures of those solvents. Alternatively, it is also
possible to dilute those preferred solvent systems with other organic aprotic solvents, such
as aromatic, cycloaliphatic or aliphatic hydrocarbons, for example toluene, xylenes, cyclo-
hexane, pentane, hexnne, methylene chloride, tetrahydrofurnn and cyclohexanone.
The polyamide blocks can also be prepared by means of interfacinl polycondensation.
The block copolymers of types B, C and D can be prepared using the correspondingstarting compounds by the same processes as those described above.
A further method for the preparation of block copolymers of types B, C and D comprises
reacting polyamide acids of formula VIIa and/or XIV
o o - o o ~ o o
~C~ ~C--NH-R4--NH- C~ ~C-OH HO--C~ ~C~
O\ ~R3~ HO--C `C ~ R4--NH- C/ ~C/
ll 11 _ 1' 11 1111
O o O O b-l
O O
~C\ ll r 11 ~C-OH 1
~ RS--C--NH- R6- N~--C--R5 C
C/ C NH--R6--NH-- -- -- C--R5 O
ll ll _ b'l 11 ~C/
O O 011
with diamines of formula XII
H2N-R2-NH2 (XII)
2~2~
and with dicarboxylic acid chlorides of forrnula XI
Cl-OC-Rl-CO-Cl ~XI)
and subsequently cyclising the resulting polyamide-polyamide acid block copolymers. In
formulae VIII, XIV, XII and XI, the symbols Rl, R2, R3, R4, Rs and R6 are as defined
above and b is an integer of at least 2.
The preparation of the polyamide acid of formula XIV is also known per se, and is carried
out, for example, by reacting a tricarboxylic acid anhydride of formula XV or a corres-
ponding tricarboxylic acid anhydride chloride
o
HO--C--R5 ~0 (XV),
o
wherein Rs is as defined above, with a less than stoichiometric amount o~ a diamine of
formula XII.
The starting materials of formula XV are known ~ se and some of them are comrner-
cially available.
The prepar300n of DMCD dianhydride ~ is known from
EP-A 9 645 and can be carried out by reacting 3-methyl-4-cyclohexene-1,2-dicarboxylic
acid anhydride with maleic acid anhydride. It is also commercially available.
By selecting suitable reaction conditions, for example by suitable selection of the molar
ratios of the reactants, it is possible to set the desired average molecular weights of the
individual blocks. This selection process is known per se to a person skilled in the art.
The polycondensation of the di-, tri- or tetra-carboxylic acid derivatives of formulae Vl:II,
XIV, XI and XV with the diamines of formula XII can be ca~ied out in a manner known
se, preferably in an anhydrous organic solvent and with the exclusion of moisture, for
example under nitrogen at temperatures of from -20C to +50C, especially approximately
from -15C to +10C.
2 ~
If desired, a mixture of different PA-PI block copolymers can also be used.
The rnixtures according to the invention are distinguished by good processability, and can
be used, for example, as matrix resins, surface coatings, adhesives, coating compositions,
compression moulding powders and sintering powders for the manufacture of industrial
products of all types, for example fibre-reinforced composites, laminates, bonded
materials, foarns, coverings, coatings, films, foils or compression-moulded articles.
Before processing the mixtures, which are, for example, in the forrn of powders or, espe-
cially, in the forrn of solutions, it is possible to add customary additives, for example
fillers, pigments, stabilisers or reinforcing agents, such as carbon fîbres, boron fibres,
melal fibres or glass fibres. The ad~lieion of so-called flow control agents, for example the
product BYK ~S 706, manufactured by BYK-Chemie, Wesel, can be especially advanta-
geous~ The addition of flow control agents is preferred according to the invention.
Owing to the good solubility of the mixtures according to the invention in polar aprotic
solvents, which solvents may be diluted with other customary solvents, such as halogen-
ated hydrocarbons, the mixtures can advantageously be processed from a solution to form
films or used for the preparation of coatings on substrates of all tvpes. Preferred solvents
are N-methylpyrrolidone, dimethyl sulfoxide and ~-butyrolactone~
Suitable substrates are: metals or alloys, such as copper, brass, aluminium, iron or steel;
asbestos or glass fibre materials; polymers, such as cellulose materials (cellulose esters or
ethers, paper), polyesters, polyamides, polyimides or polyurethanes~
After the coating has been applied and dried, for example for 30 minutes at 1 80C, brief
heating, for example at a temperature of from 220 to 280C, renders it resistant to sol-
vents~ The solvent-stable coatings are distinguished by good adhesion, especially to
metals, and by very good surface quality~ The mixtures according to the invention can
therefore be used to prepare coatings in which the good mechanical properties of the
PA-PI block copolymers, such as a high degree of flexibility, are retained, no brittleness
caused by the addition of epoxy resins is observed, and very good adhesive strength and a
high degree of resistance to solvents are achieved~
It has also been found that metal foils coated with the mixtures according to the invention
, . ..
2~2~
- 27 -
can be bonded directly to multi-layer larninates without the use of additional auxiliary
bonding materials, such as acrylate adhesives.
The present invention therefore relates also to larninates, pr~ferably metal l~uninates and
especially copper laminates, in which the bonding material consists of the mixture accord-
ing to the invention comprising an epoxy resin (a) and a soluble PA-PI block copoly-
mer (b). The bonded material is prepared under pressur~e and at a temperature that allows
the PA-PI block copolymer/epoxy resin mixture to flow at least to a slight extent, for
example at a temperature in the range of from 180 to 320C, preferably from 200 to
300C.
The temperature depends on the glass-transition temperature of the PA-PI bloclc copoly-
mer, the epoxy resin content and the desired compression nnd pressure time. For example,
in the case of a PA-PI block copolymer having a low glnss-trl~nsidon temperature ~nd a
high proportion of epoxy resin, it is preferable to select a low processing temperature. In
the case of a PA-YI block copolymer having a high glass-transitdon temperature and a low
proportion of epoxy resin, the compression temperature will preferably be in a relatively
high range.
A preferred field of application for such laminates, which are very flexible and can be
folded several times without breaking, is in the electronics industry for the manufacture of
circuits.
In the Exarnples that follow, the following epoxy resins are used.
Epoxy resin I: bisphenol A diglycidyl ether having an epoxy content of from 5.6 to
5.7 equivalents~cg and a viscosity of from 4500 to S900 rnPa-s at 25C.
Epoxy resin II: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane having an epoxy
content of from 7.5 to 8.5 equivalents/kg and a viscosi~ of from lO 000 to 17 000 rnPa-s
at 50C.
Epoxv resin III: N,N,Q-triglycidyl-p-aminophenol having an epoxy content of from 9.35
to 10.53 equivalents/lcg and a viscosity of from 550 to 850 mPa-s at 25C.
Epoxy resin IV: bisphenol F diglycidyl ether having an epoxy content of from S.S~ to
5.95 equivalents~cg and a viscosity of from 3000 to 10 000 mPa-s at 25C.
2~24~
-28 -
Epoxy resin V: triglycidyl isocyanurate having an epoxy content of from 9.3 to 10.0
equivalcnts/kg and a melting range of from 86 to 96C.
Epoxy resin VI: polyphenol A tetraglycidyl ether (tetra(p-glycidyloxyphenyl)ethane)
having an epoxy content of &om S.1 to 5~4 equivalents/kg and a softening point according
to Kofler of from 65 to 85C.
Epoxy resin VII: solid bisphenol A diglycidyl ether resin having an epoxy content of from
2.15 to 2.22 equivalents/kg and a softening point according to Kofler of 50C.
Epoxy resin VIII: o,o'-diallylbisphenol A diglycidyl ether having an epoxy content of
4.6 equivalents~cg.
Epoxv resin IX: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane having an epoxy
content of from 8.7 to 9.1 equivalents/kg ~md a viscosity of from 4000 to 6000 mPa-s at
50C.
Epoxv resin X: bisphenol S diglycidyl ether having an epoxy content of 5.3 equiva-
lents~g.
Epoxv resin XI: phenol novolak epoxy resin having an epoxy content of from 5.6 to
5.8 equivalents/kg and a viscosity of from 1100 to 1700 rnPa-s at 50C.
Epoxy resin XII: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate having an
epoxy content of from 7.0 to 7.5 equivalents~cg and a viscosity of from 450 to 520 n~a s
at 25C.
~or the following Examples, PA-PI block copolyrners are prepared in accordance with
processes known ~ se in the following compositions:
PA-PI block copolymer A: In accordance with Exarnple 1 of EP-A 0 324 315 a polyimide
block is synthesised from 120.84 g (0.375 mol) of 3,3`,4,4'-benzophenonetetracarboxylic
acid dianhydride, 38.88 g ~0.156 mol) of 4,4'-diarninodiphenylsulfone and 38.88 g
(0.156 mol) of 3,3'-diaminodiphenylsulfone and a polyamide block is synthesised from
44.48 g (0.2235 mol) of isophthalic acid dichloride, 31.1 g (0.125 mol) of 4,4'-diaminodi-
2~2~
- 29 -
phenylsulfone and 31.1 g (0.125 mol) of 3,3'-diaminodiphenylsulfone. The inherent vis-
cosity (0.5 % by weight polymer in N-methylpyrrolidone (NMP) at 25~C) is 0.40 dl/g.
PA-PI block copolvmer B: In accordance with Example 1 of EP-A 0 324 315, a polyimide
block is synthesised from 100.7 g (0.3125 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride, 32.4 g (0.1303 mol) of 4,4'-diaminodiphenylsulfone and 32.4 g
(0.1303 mol) of 3,3'-diaminodiphenylsulfone and a polyamide block is synthesised from
96.12 g (0.4693 mol) of isophthalic acid dichloride, 64.80 g (0.2606 mol) of 4,4'-diarnino-
diphenylsulfone and 64.80 g (0.2606 mol) of 3,3'-diaminodiphenylsulfone. The inherent
viscosity (0.5 % by weight polymer in NMP at 25C) is 0.57 dVg.
PA-PI block copolymer C:
Polvamide acid bloclc: 90.13 g (0.3125 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride and 500 g of NMP are weighed, under nitrogen, into a double-walled
reaction vessel equipped with protecdve gas connection, internal thermometer, dropping
funnel and sdrrer. The reacdon vessel is evacuated three dmes and gassed with nitrogen.
After cooling to -7C, a suspension is formed. Over a period of 80 minutes, at atemperature of from-7 to -4C, a solutdon of 30.57 g (0.1303 mol) of 4,4'-diamino-
diphenylsulfone and 16.52 g (0.1303 mol) of m-xylylenediamine in 156 g of NMP isadded by way of the dropping funnel. The reactdon mixture is then allowed to come to
room temperature and is stirred for 2 hours.
Polvamide-polvamide acid block copolvmer: The clear reaction mixture is cooled again
(-7C). 125.21 g (0.5210 mol) of 4,4'-diaminodipnenylsulfone in 300 g of NMP are then
added dropwise over a period of lS0 minutes by way of the dropping funnel. 90.6~ g
(0.4693 mol) of isophthalic acid dichloride are then added in portions so that the internal
temperature does not exceed 0C. Approximately lS0 minutes are required, the solution
becoming increasingly viscous. The polymer solution is then stiTred at room temperature
for S0 minutes. A further O.S l g (0.0025 mol) of isophthalic acid dichloride is added and
the reaction mixture is stirred for 3 hours to complete the polycondensation reaction. 34.00
g (0.4725 mol) of butylene oxide are then added by way of a dropping funnel over a period
of 20 minutes (internal temperature 20-25C), yielding a solution of a polyamide-poly-
amide acid block copolymer having an inherent viscosity of 0.64 dl/g (0.5 % by weight
solids in NMP/25C).
Cvclisation: The resulting polyamide-polyarnide acid block copolymer solu~on is then
subjected to chemical cyclisation to form the polyamide-polyimide block copolymer~ For
this purpose, at from 20 to 25C, using a dropping funnel, first 79.69 g (0.7875 mol) of
2~2~
- 30-
~iethylamine are added over a period of 45 minutes and then 80.40 g (0.7875 mol) of
acetic anhydride are added over a period of 40 minutes. The reaction mixture is then
stirred for a further 6 hours at room temperature. A portion of the above-described solution
is diluted with an equal amount of NMP, precipitated in 10 times the amount of
isopropanol and dried in a vacuum drying cabinet, the temperature being increased to
240C over a period of 72 hours. The inherent viscosity (0.5 % by weight solids, NMP,
25C) of a polyamide-polyimide block copolymer prepared in this manner is 0.69 dVg.
PA-PI block copolvmer D: In accordance with Example 1 of EP-A 0 381 620, a polyimide
block is synthesised from 120.84 g (0.375 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride and 66.12 g of a diamine mixture Z and a polyamide block is synthesised
from 57.76 g (0.238 mol) of isophthalic acid dichloride and 87.0 g of a diamine mixture Z.
The inherent viscosity (O.S % by weight polymer in NMP at 25C) is 0.52 dl/g.
The diamine mixture Z is an industrial mixture consisting of 4,4'-diaminodiphenyl-
methane, 3-ethyl-4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenyl-
methane, the proportion of substituted diaminodiphenylmethane being greater than 80 %
by weight.
PA-PI block copolvmer E: In accord~nce with Example 1 of EP-A 0 381 620, a polyimide
block is synthesised from 120.84 g ~0.375 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride and 66.12 g of diamine mixture Z and a polyarnide block is synthesised
from 56.46 g (0.278 mol) of isophthalic acid dichloride and 87.00 g of diamine mixture Z.
The inherent viscosity (O.S % by weight polymer in MMP at 25C) is 0.48 dVg.
PA-PI block copolvmer F: ~ accordance with Example 1 of EP-A 0 381 620, a polyimide
block is synthesised from 120.84 g (0.375 mol3 of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride and 71.48 g (0.281 mol) of 3,3'-diethyl-4,4'-diaminodiphenylmethane
and a polyamide block is synthesised from 57.65 g (0.284 mol) of isophthalic acid
dichloride and 95.65 g (0.375 mol) of 3,3'-diethyl-4,4'-diaminodiphenylmethane. The
inherent viscosity (O.S % by weight polymer in NMP at 25C) is 0.61 dVg.
PA-PI block copolvmer G: In accordance with Example 1 of EP-A 0 381 621, a polyimide
block is synthesised from 100.70 g (0.3125 mol) of 3,3',4,4'-benzophenonete~acarboxylic
acid dianhydride, 7.10 g (0.0521 mol) of m-xylylenediamine, 25.92 g (0.1042 mol) of
3,3'-diaminodiphenylsulfone and 25.92 g (0.1042 mol) of 4,4'-diaminodiphenylsulfone
2~ 2~
- 31 -
and a polyamide block is synthesised from 32.02 g (0.1579 rnol) of isophthalic acid
dichloride, 25.92 g (O.lW2 mol) of 3,3'-diaminodiphenylsulfone and 25.92 g (0.1042 mol)
of 4,4'-diaminodiphenylsulfone. The inherent viscosity (0.5 % by weight polymer in
NMP at 25C) is 0.66 clVg.
PA-PI block coPolYmer H: In accordance with Example 1 of EP-A 0 381 620, a polyimide
block is synthesised from 120.84 g (0.375 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride and 71.48 g (0.281 mol) of 3,3'-diethyl-4,4'-diaminodiphenylmethane
and a polyamide block is synthesised from 57.65 g (0.284 mol) of isophthalic acid di-
chloride and 95.61 g (0.375 mol) of 3,3'-diethyl-4,4'-diaminodiphenylmethane. The
inherent viscosity (0.5 % by weight polymer in NMP at 25C) is 0.60 dVg.
PA-PI block copolYmer I: In accord.mce with Example 1 of EP-A 0 381 620, a polyirnide
block is synthesised from 73.52 g (0.25 mol) of 3,3',4,4'-biphenyltetracarboxylic acid di-
anhydride and 43.50 g of diamine mixture Z and a polyamide block is synthesised from
39.89 g (0.1895 mol) of trimellitic acid anhydride chloride and 58.00 g of diamine
mixture Z. The inherent viscosity (0.5 % by weight polymer in NMP at 25C) is 0.80 dl/g.
PA-PI block copolYmer J: In accordance with Example 1 of EP-A 0 381 620, a polyimide
block is synthesised from 73.64 g (0.3375 mol) of pyromellitic acid dianhydride, 33.11 g
(0.1125 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 97.19 g of diarnine
mixture Z and a polyamide block is synthesised from 15.2 g (0.0946 mol) of isophthalic
acid dichloride and 28.32 g of diamine muxture Z. The inherent viscosity (0.5 % by weight
polymer in NMP at 25~C) is 0.63 dVg.
PA-PI block copolymer K: In accordance with Example 1 of EP-A 0 381 620, a polyimide
block is syn~hesised from 80.56 g (0.25 mol~ of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride, 21.57 g (0.0695 mol) of 3,3',5,5'-tetraethyl-4,4'-diaminodiphenyl-
methane, 17.28 g (0.0695 mol) of 3,3'-diaminodiphenylsolfone and 17.28 g (Q.0695 mol)
of 4,4'-diaminodiphenylsulfone and a polyamide block is synthesised from 76.90 g(0.379 mol) of isophthalic acid dichloride, 43.04 g (0.1389 mol) of 3,3',5,5'-tetra-
methyl-4,4'-diaminodiphenylmethane, 34.56 g (0.1389 mol) of 4,4'-diaminodiphenyl-
sulfone and 34.56 g (0.1389 mol) of 3,3'-diaminodiphenylsulfone. The inherent viscosity
(0.5 % by weight polymer in NMP at 25C) is 0.45 dl/g.
PA-PI block copolymer L: In accordance with Example 1 of EP-A 0 381 620, a polyirrude
- 32 -
block is synthesised from 120.84 g (0.375 mol) of 3,3',4,4'-benzophenonetetracarboxylic
acid dianhydride, 38.88 g (0.156 rnol) of 4,4'-diarninodiphenylsulfone and 38.88 g
(0.156 mol) of 3,3'-diarninodiphenylsulfone and a polyamide block is synthesised from
38.56 g (0.1877 mol) of isophthàlic acid dichloride, 31.10 g (0.125 mol) of 4,4'-diamino-
diphenylsulfone and 31.10 g (0.125 mol) of 3,3'-diaminodiphenylsulfone. The inherent
viscosity (0.5 % by weight polymer in NMP at 25C) is 0.46 dl/g.
Examples 1 to 65: Preparation and properties of two-layer laminates made from PA-PI
block copolymer/epoxy resin compositions
The PA-PI block copolymer in question is dissolved in NMP and when it has dissolved
completely the epoxy resin in quesdon is added in the ratio given, yielding a 25 % by
weight solution in NMP. The soludon is applied to a 35 ,um copper foil in a thickness of
200 ,um using a coating roller system and dried in a circulating-air surface-coating drying
cabinet with IR irradiation (condidons: ~emperature of circulating air: 180C, 45 minutes,
IR larnp: Heraeus Model MMS 1200). A pordon of the coated foil is cut into strips 1 cm
wide and the "flex life'' of the laminate is determined ("flex life" = number of dmes
laminate can be folded before breaking, determined using a Universal Model 2 FDF Flex
Ductility Tester having a tensile load of 224 g and 2 mm mandrel). The stability to
solvents is deterrnined by immersing a further portion of the laminate (~approxirnately 8 x 8
cm) in NMP at 20C for one and two hours.
Table 1 below gives the properties of ~he laminates according to the invention.
2~¢2~
Table 1: Properlies of Qe~ible Isminstes bssed on PA-PI blOck
copolymer/epoxy resin compositions
Exa- PA-PI blOCk epo~y tatio nex l~e wcight 81~S9
mple copolymer rcsin PA-PI/cpo~y rcsin changcill % ttsns. temp.
_ ts by wcight] s~tct NnUP stg. (DSC) I-C]
1 A I 97.5/2.5 391 0.8 0~3 275
2 A l 95/5 350 1.6 1.9 271
3 A I 92.5/7.5 406 0.8 1.8 266
4 A I 90/10 380 1.0 1.7 260
A ll 97.5/2.5 378 1.0 0.2 274
6 A lll 97.5/2.5 433 0.5 3.8 272
7 A lll 95/5 378 1~4 1.4 278
8 A IV 97.5/2.5 354 0.1 0.9 274
9 A IV 95/5 367 1.1 1.1 277
A V 97.5/2.5 407 0.7 1.4 278
11 A Vl 97.5/2.5 383 0.6 0.7 265
12 A Vl 95/5 447 1.2 1.5 259
13 B I 97.5/2.5 419 0.0 2.0 271
14 B I 92.5/7.5 385 0.8 2.8 273
B I 90/10 385 2.1 5.6 256
16 B lll 97.5/2.5 368 1.6 3.7 275
17 B IV 97.5/2.5 382 0.1 -1.4 276
18 C I 97.5/2.5 395 -0.4 0 272
19 C 95/5 335 4.5 5.3 272
2~2~3
- 34^
Table 1 ~continuation)
Exa- PA-PI block epoxy ratio flex lile weight glass
mple copolymer resin PA-PI/epoxy resin chango in qo trans. temp.
[parts by weight] 1 h 2 h (DSC) ['C]
A l 85/15 414 1 ~0 2.8 251
21 A l 80/20 399 4.61.2 242
22 A l 70/30 418 3.12.6 225
23 A lll 90/10 367 1.42.0 254
24 B I 80/20 403 3.03.0 238
B Vl 90/10 386 1.41.8 252
26 B Vll 95/5 378 0 45.8 256
27 B Vll 90/10 341 3.06.2 252
28 B Vlll 97.5/2.5 364 0.2 -0 7 278
29 B Vlll 95/5 378 3.4 3.5 285
B Vlll 90/10 409 1.0 4.1 275
31 C l 80/20 422 2~45.0 249
32 E l 80/20 458 1.14.5 190
33 F l 95/5 353 1.24.2 216
34 F Vl 95/5 330 0.40.8 249
A IX 99/1 348 1.01 7
36 A IX 98/2 370 1.93.0
37 A IX 9S/5 342 1.83.9
38 A X 95l5 344 2.83.4
- 2 ~
- 35 -
Table 1 (continuation)
E~a- PA-PI bhCk epo~y ratio nex life weigh~
mple copolymer resin PA-PI/epoxyresin change in %
[parts by weight] nftelr h P2'gh
39 A X 90/10 347 2.3 3.7
A X 75/25 376 3.0 3~4
41 A Xl 95/5 358 0.9 2.2
42 G I 95/5 335 2.1 3.6
43 G l 75/25 357 2.0 3.0
44 G IX 99/1 344 1.1 1.2
G IX 98/2 337 2.4 2.0
46 G IX 95/5 361 3.3 4.2
47 H 11 98/2 384 0.9 1.4
48 I I 90/10 344 0.0 0.2
49 F I 97.5/2.5 360 0.2 0.4
F Vll 95.5/5 369 0.4 0.8
51 J IX 95/5 459 1.3 1.6
52 J IX 90/10 430 1.2 1.5
53 A Xll 95/5 371 2.7 1.6
54 A Xll 90/10 411 1.0 2.1
~VG Vl 47.5147.5/5 340 2.0 2.3
56 A/H IV 47.5147.515 388 1.2 1.8
57 A/H Vl 47.5147.515 327 1.7 3.8
2 ~ ~ 2 ~ ~?
- - 36 -
Table 1 (continuation)
Exa- PA-PI block cpo~y ratio flex IHe wci~ h~
mplc copolymer rcsin PA-PI/cpo~y rcsin changc in %
[parts by weight] aftcr NMP stg.
58 A/G lll 47.5147.5/5 325 1.7 2.0
59 A I/X 90/515 400 1.6 1.3
AIG III/IV 451451515 364 1.2 2.4
61 A I/VII 901515 390 2.6 2.5
62 A I 941511~) 415 0.7 1.5
63 H I 941511 ') 441 1.1 2.0
64 A I 95/5~') 426 0.6 2.1
A 95/5-~') 418 1.5 2.5
^) The mixture compriscs 1 % by weight BYK(~)S 706 as flow conlrol agent,
bascd on the total amount of PA-PI, epo~y resin and flow control agent
'~) drying: circulating-air tcmperatuTc=240C; IR irradiation = 45 minutes
~) drying: circulating-air tcmpcraturc=1 80C; IR irradiation = 60 rninutes
Example 66: Preparation and properties of a three-layer laminate made from PA-PI block
copolymer/epoxy resin compositions
25 g of PA-PI block copolymer D, 20 % by weight solution in NMP, are weighed into a
beaker and heated in an oil bath to from 120 to 140C. When the solution has reached the
temperature, 0.5 g of epoxy resin I is added and the reaction mixture is stirred until the
epoxy resin has completely dissolved.
Using equipment supplied by Messrs Gockel, Munich (table with standard blade), 150 ',
coatings of the above-described solution cooled to from 50 to 60C are applied to a 35 ',
copper -foil.
The coated foils are fixed at the corners while still damp and left for 30 minutes in a
c*culating-air drying cabinet heated to 18QC. After that drying period, the resin-coated
foils are cooled at room temperature. A 25-30 ~L resin layer remains on the copper foil.
The resin-coated copper foil~ are cut into 16 x 16 cm pieces using a paper-cutting
machine. The cut, coated foils are placed with their resin sides together and the foils are
subjected to compression moulding between two pads at a temperature of frotn 240 to
260C and under a pressure of 40.8 bar. After 6 mimltes, demoulding takes place at the
compression moulding temperature. After cooling, the flexible laminate is ready for the
determination of properties.
In order to determine the electrical properdes, the copper foils at the top and the bottom
are removed by etching in an etching bath. The plastics film that remains is washed
several dmes in distilled water and dried in a vacuum furnace until its weight is constant.
The electrical properties measured for that foil are:
rupture strength (50 Hz) = 150 kV/mm tel quel
Volume resistivity Q (DIN 53482)
3.8 x 10l5 Ohm x cm tel quel
3.8 x 10l5 Ohm x cm after storage for 1 hour in boiling water
Dielectric loss factor tan ~ and dielectric constant ~ (DIN 53483)
Hz tan ~ Epsilon
0.02 4 tel quel
100 0.016 4 tel quel
1000 0.011 3.9 tel quel
10000 0.012 3.9 tel quel
100000 0.024 3.8 tel quel
0.017 S.7 boilingwaterfor 1 hour
100 0.017 6.7 boilingwaterforlhour
1000 0.017 6.6 boilingwaterfor 1 hour
10000 0.013 6.5 boilingwaterforlhour
100000 0.031 6.3 boilingwaterforlhour
Example 67: Copper foils - 35 ~,1 ED copper - are coated on the trea~nent side with a wet
200 ~ lm of the following composition: PA-PI block copolymer K, 22 % by weight
soludon in NMP, 10 % by weight epoxy resin VI, based on solid PA-PI block copolyrner,
and 0.15 % by weight BYK~S 706, based on the total solution.
2~2~
- 38 -
After evaporation of the solvent at room temperature for from 2 to 3 minutes, the coating
is dried for 10 minutes at 100C ancl for 30 minutes at 220C
Two copper foils coated in that manner are compression moulded with ~he polymer layers
next to one other for 2 minutes at 280C under a pressure of from 39.23 to 49.04 bar, and
cooled under pressure to room temperature.
The following values are determined for the adhesion of the copper foil: at roomtemperature = 16.9 N/cm; at 150C = 16.9 N/cm and at 250C = 7.7 N/cm.
Example 68: Analogously to Example 66, 1 g of epoxy resin I is added to 50 g of PA-PI
block copolymer L, 25 % by weight soludon in NMP.
The resin-coated copper foils are compression moulded at a temperature of from 220 to
240C and under a pressure of 39.23 bar for 6 minutes and the following properties are
determined:
rupture strength (50 Hz) = 143 kV/rnm (tel quel), volurne resistivity
IEC 93 = 5.3-10150hm x cm (tel quel).
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