CA2062092A1 - Mixtures based on polyamide-polyimide block copolymers - Google Patents

Abstract

Mixtures based on polyamide-polyimide block copolymers Abstract Mixtures comprising, based on 100 parts by weight of the mixture, (a) from 50 to 98 parts by weight of a polyamide-polyimide (PA-PI) block copolymer, (b) from 1 to 49 parts by weight of a polyarylene ether having a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25°C, and comprising, based on the total amount of structural units present in the polyether resin, from 5 to 100 mol% of a recurring structural unit of the formula Ia ?O - Ar1 - O - Ar2? (Ia) and from 0 to 95 mol% of a recurring structural unit of the formula Ib ?O - Ar3 - O - Ar2? (Ib) in which Ar1 is a carbocyclic-organic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms, Ar2 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups or C1-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO-units as bridging members, or is a cyanophenylene, pyridine or pyrazine radical, and Ar3 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms and is different from Ar1, and (c) from 1 to 40 parts by weight of an epoxy resin containing at least two glycidyl groups in the molecule, and (d) from 0 to 10 parts by weight of a further polymer from the group comprising polyamides, polyimides, polyether-imides, polyester-imides, polyhydantoin and polyparabanic acids, are suitable for the preparation of solvent-resistant coatings and adhesive bonds, in particular for the production of flexible laminates.

Description

20620~2 Mixtures based on polyamide-polvimide block copolvmers The present invention relates to mixtures comprising a polyamide-polyimide (PA-PI) block copolymer, a polyarylene ether and an epoxy resin, and to the laminates, coatings or adhesive bonds, in particular bonded metal foils, produced from these mixtures.

PA-PI block copolymers are materials having very good mechanical and thermal properties which can be used, inter alia, for coating metal foils giving laminates. As essential properties, flexible laminates must have good adhesion between the metal and the polymer layer, good chemicals resistance, good thermal and electrical properties and in panicular high flexibility, ie. the materials must be capable of being folded very often before fracture of the laminate takes place. Flexible laminates of this type are described, for example, in European Patent 48 219. The polymers processed therein are applied as a polyamide/polyamidic acid solution and are converted thermally into the insoluble polyamide-polyimidè form by elimination of water after the coating. However, this reaction step can be accompanied by undesired phenomena, such as bubble formation and molecular weight degradation. In addition, the polyamide/polyamidic acid solution employed does not have a long shelf life.

PA-PI block copolymers which are soluble in polar aprotic solvents and do not have the described disadvantages of processing of the polyamide/polyamidic acid solution have already been disclosed, for example in EP-A 324 315. However, some of these known PA-PI block copolymers which are soluble in polar aprotic solvents do not satisfy all the demands made of them, for example the chemicals resistance of these soluble block copolymers after application is not adequate for all applications.

It has now been found that, when mixed with polyarylene ethers and epoxy resins, PA-PI
block copolymers can be converted into laminates more simply and flexible laminates are obtained which have increased flexibility and good chemicals resistance.

The present invention thus relates to mixtures comprising, based on 100 parts by weight of the mixture, 2062~q2 (a) from 50 to 98 parts by weight of a polyamide-polyimide (PA-PI) block copolymer, (b) from I to 49 parts by weight of a polyarylene ether having a reduced viscosity of from 0.1 to 2.0 dVg, measured on a solution of I g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25C, and comprising, based on the total amount of structural units present in the polyether resin, from S to 100 mol% of a recurring structural unit of the formula Ia t- Arl - O - Ar2~ (Ia) and from 0 to 95 mo1% of a recurring structural unit of the formula Ib i O - Ar3 - O - Ar2~ (Ib) in which Arl is a carbocyclic-organic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms, Ar2 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups or Cl-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO-units as bridging members, or is a cyanophenylene, pyridine or pyrazine radical, and Ar3 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms and is different from Arl, and (c) from 1 to 40 parts by weight of an epoxy resin containing at least two glycidyl groups in the molecule, and (d) from 0 to 10 parts by weight of a further polymer from the group comprising polyamides, po1yimides, polyether-imides, polyester-imides, polyhydantoins and polyparabanic acids.

If desired, it is also possible to use a mixture of two or more PA-PI block copolymers andVor of two or more polyarylene ethers andVor of two or more epoxy resins.

The present invention preferably relates to mixtures comprising, based on 100 parts by weight of the mixture, (a) from 50 to 98 parts by weight of a polyamide-polyimide (PA-PI) block copolymer, (b) from 1 to 49 parts by weight of a polyarylene ether having a reduced viscosity of from 0.1 to 2.0 dVg, measured on a solution of I g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25C, and comprising, based on the total amount of 2062~2 structural units present in the polyether resin, from S to 100 mol% of a recurring structural unit of the formula la t - Arl - O - Ar2~ (la) and from 0 to 95 mol% of a recurring sLructural unit of the fo~nula Ib tO- Ar3 - O - Ar2~ (Ib) in which Arl is a carbocyclic-organic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms, Ar2 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups or Cl-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO-units as bridging members, or is a cyanophenylene, pyridine or pyrazine radical, and Ar3 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms and is different from Arl, and (c) from 1 to 40 parts by weight of an epoxy resin containing at least two glycidyl groups in the molecule.

If desired, it is also possible to use a mixture of two or more PA-PI block copolymers an~Jor of two or more polyarylene ethers and/or of two or more epoxy resins.

The mixtures according to the invention preferably contain the following proportions of the mixture components:
from 60 to 95 parts by weight of a PA-PI block copolymer, from 2.5 to 30 parts by weight of a polyarylene ether and from 2.5 to 30 parts by weight of an epoxy resin.

The mixtures according to the invention in particular contain from 70 to 90 parts by weight of a PA-PI block copolymer, from S to 20 parts by weight of a polyarylene ether and from S to 20 parts by weight of an epoxy resin.

The PA-PI block copolymers in the mixtures according to the invention are taken to mean compounds built up from polyamide and polyimide blocks, from polyamideimide and - 2~62~2 polyimide blocks, from polyamide and polyimideimide blocks or from polyamide, polyamideimide and polyimide blocks. Compounds of this type and processes for their preparation have been disclosed, for example in DE-A-2 342 464, DE-A-2 342 454, DE-A-2 366 273, EP-A-0 048 219 and EP-A-0 048 221. The block copolymers disclosed therein comprise recurring structural units of the formula [ PA - PI~

in which r is an integer from 1 to 500, PA is a polyamide block having a mean molecular weight of from 350 to 30,000, and PI is a polyimide block having a mean molecular weight of from 750 to 2000, and generally have an intrinsic viscosity of from 0.1 to 2.5 dl/g, in particular from 0.4 to 1.5 dUg, measured on a 0.5 % solution in N-methyl-2-pyrrolidone at 25C. The PA-PI block copolymers described in the abovementioned literature are obtained by cyclisation (imidisation) of the corresponding still-soluble polyamide-polyamidic acid block copolymers. The mixtures according to the invention preferably contain PA-PI block copolymers which are still soluble before applicatdon and give a solvent-resistant coating after application in a short time at relatively low reaction temperatures, with the good mechanical properties of the polymer simultaneously being substantially retained.

The term "soluble PA-PI block copolymer" is generally taken to mean a copolymer which is soluble in polar aprotic solvents and from which solutions containing at least 5 % by weight, in pardcular at least 10 % by weight, of PA-PI block copolymer, based on the solution, can be prepared.

Examples of aprotic solvents which are suitable for this purpose are N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone (NMP), N-acetyl-2-pyrrolidone, N-methyl-~-caprolactam, N,N,N',N'-tetramethylurea, dimethyl sulfoxide and ~-butyrolactone.

PA-PI block copolymers which are soluble in polar aprotic solvents have been disclosed, for example in EP-A-324 315. For the mixtures according to the invention, preference is given to block copolymers of type A having a mean molecular weight MnOf from 1000 to 50,000 and comprising recurring units of the formula II

2062~q2 tPA-PI~

in which PA is a polyamide block having a mean molecular weight MnOf from 300 to 20,000 and comprising at least one (recurring) unit of the formula III

O O
(III) ~ C-R,-C-NH-R2-NH~

in which Rl is a radical of the formula -CnH2n-, ~3, ~Q~3 ~3} ~3 or ~Q~3 and R2 is a radical of the formula ~CnH2n~~ CH2 ~3 CH2-(Ya) s CH2 (Yb) s --CH2~ . ~3Q~
Yd Yf ~3Q ~3 Q ~3 or ~3Q ~3 Q {3 Q ~} in which Q is a direct bond, -CH2-, 206~0q2 -CH2CH2-, -CH(CH3)-, -C(CH3)2-t -C(CF3)-, -O-, -S-, -SO2-, -CO- or--P--, and n is 2-12, Ya and Yb, independently of one another, are each C1-C4alkyl, and where s is zero or a number from 1 to 4, and Yc, Yd. Ye and Y~, independently of one another, are hydrogen, halogen or Cl-C4alkyl, and PI is a polyimide block having a mean molecular weight MnOf from 300 to 20,000 and comprising at least one (recurring) unit of the formula IV

~ O O

--N R3b/N--R2 ~ (IV) O O

in which R3 is ~, ~, ~ ~ , X~ ~or ~3 and Q and R~ are rs defined above, with the proviso that from 25 to 100 mol% of all the bridging members R2 are ~SO2~ andlor \~/ ~0/, and the (cyclo)aliphatic content of the bridging members R2 is not more tharl 10 mol%.

Preferred block copolymers containing the recurring unit of the formula 11 have a mean molecular weight Mn f from 4000 to 40,000.

In preferred block copolymers, the polyamide blocks and/or the polyimide blocks comprise more than one recurring structural unit of the formula III or of the formula IV.
For preferred polyamide blocks or polyimide blocks, this gives a mean molecular weight of from 500 to 20,000.

In the above formulae, Rl is, for example, 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,8-naphthylene, 3,3'-biphenylene, 4,4'-biphenylene, oxybisphenylene or sulfonylbisphenylene, preferably 1,3-phenylene.

In the formulae III and/or IV, 25-100 mol% and in particular S0-100 mol% of the bridging members R2 occurring in the copolymer are groups of the fort-nulae ~so2~3 and/or ~/ ~3/

It is not necessary for both polyamide and polyimide blocks to contain such bndging members.

-CnH2n- R1 or R2 is, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 2,9-decylene or 2-methyl-1,5-pentylene.

A ~ group Rl or R2 can be 1,2-cyclohexylene, 1,3-cyclohexylene or 1 ,4-cyclohexylene.

Further examples of specific cycloaliphatic groups R2 are H2C--~--CH2-- ,--H2C
{~ CH2~ ~ ~J ~ CH

~3 CH2 Q ~ or {~} CH2--.

C2Hs C2H5 Examples of speci~lc aromatic groups R2 are 1,2-phenylene, 1,3-phenylene, 20~q2 1,4-phenylene, methyl-2,4-phenylene, 1,3,5-trimethyl-2,5-phenylene, 2,5-xylylene, 4-chloro-1,3-phenylene, 2,5-dichloro-1,4-phenylene and the groups ~,}S~ ,~11~, r~,r~

0~

~30~' C2H5 c2~5 ~CH2~ ' ~CH2 2~6~q2 C2H5 C2Hs isoC~3H7 isoC3H7 ~3CH2~ ' ~ CH
isoC3H7 isoC3H7 ~} C ~, CH~ ~3 CF~ ~
~30~so2~o~

~o~3~o ~-~30 ~ ~ and in particular the groups 3~3~ ~3so2~

an(l \~ / for R2 in the formula 111, and the grouys 2~620q2 ~_, o ~--- ~ so2~ and \~/ \0/ for R2 in the forrnula IV.

A divalent radical Q in the bridging member R2 is, for example, -CH2CH2- or -S-, I

preferably -CH2-, CH3-CI-CH3, -O-, -SO2- or -C(O)-. If a bridging member R2 contains more than one radical Q, these radicals may be identical or different.

The tetravalent radical R3 is derived from a tetracarboxylic acid which is capable of forming a dianhydride, for example the groups ~, ~ and in particular ~ C(CF3,2~X ~ ~, Examples of possible combinations of polyamide and polyimide blocks to give PA-PI
block copolymers of type A are given in EP-A-O 324 315. These PA-PI block copolymers can be prepared as described in Example I of EP-A-O 324 315.

C)ther suitable PA-PI block copolymers of type B which are soluble in polar aprotic solvents and comprise recurring units of the formula II and have a mean molecular weight Mn of from 1000 to 50,000 have an amide:imide group ratio of from about 4:1 to 1:4 and 20~q2 contain at least 2 mol%, in particular at least 5 mol%, based on the content of all carbo~cylic acid radicals in the copolymer, of r~dicals of the fotmola ~X

(DMCD radicals) derived from 5-(2,5-diketotetrahydrofurfuryl)-3-methylcyclohexane-1,2-dica rboxylic acid, in the polyimide blocks. The content of DMCD radicals in the PA-PI block copolymers which can be used according to the invention is generally from 2 to 80 mol%, based on the content of all carboxylic acid radicals in the copolymers.

Preferred PA-PI block copolymers contain combinations of blocks of the formulae Vb with IVa and/or IVc or of the formulae IVb with Va and/or Vc o o o o Il 11 11 11 --NH--C--R~--C --NH--R2--NH--C--R I--C ---NH (IVa), e --N/ ~R3~ ~N R4 N~ ~R~ ~N (IVb), o oO o Il O o --NH--C--R5~ ~N-- R6--NH--C--R5~ \N (IVc) Il 9 11 o o o o --R2---NH--C--R~--C N~--R2--e (Va), 2 ~ 2 O O
Il 11 --R4~N~ ~R3~ ~N--R4~ (Vb), o o R6~ NH C R5 ~N R6~ (Vc), ll in which the indices e, f and g, independently of one another, are integers from 1 to 100, R1 and R2 are as defined in the formula Ill, R3 is a radical of the formula cH3 Q~' ~'~'~' ~(, ~or ~3 in which Q is a direct bond or -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, P
C6Hs -C(CF3)2-, -O-, -S-, -SO2- or -CO-, Rs is a radical of ~he formula ~, and R4 and R6, independently of one another, are as defined for R2, with the proviso that 25-100 mol% of all radicals R3 have the formula ~L~ .

In the formulae IVa and Va, Rl and R2 have the same preferred meanings as in theformula 111. The tetravalent radical R3 is derived from a tetracarboxylic acid which is capable of forming a dianhydride, and is preferably a radical of the formula (CF3)2~ ~ or ~3/ SO~ , very particularly ~.

The proportion of DMCD radicals in the polyimide blocks of the block copolymers to be used according to the invention is preferably from 50 to 100 mol%, based on the proportion of tetracarboxylic acid radicals in these blocks.

Rs is preferably a radical of the formula ~ .

Possible combinations of polyamide and polyimide blocks to give PA-PI block copolymers of type B are given in EP-A-0 381 619. These PA-PI block copolymers can be prepared as described in Example 1 of EP-A-0 381 619.

Other suitable PA-PI block copolymers of type C which are soluble in polar aprotic solvents and have a mean molecular weight MnOf from 1000 to 50,000 comprise a combination of blocks of the formulae IVa with Vb and/or Vc or of the formulae IVb with Va and/or Vc or of the formulae IVc with Va and/or Vb, with the other proviso that 10-100 mol%, preferably 25-100 mol%, in particular 50-100 mol%, of all the radicals R2, R4 and R6, based on the total amount of these radicals, have the formula ~ CH2~ in which p is 1 or 2, q is zero, I or 2, R7 and R~3 are each Cl-Cgalkyl, or in which each two radicals R7 and Rg in the ortho-positions to one another form an alkylene group having 2 to 10 carbon atoms.

20~20q2 An alkyl substituent R7 or R8 in the abovementioned forrnula may be branched or preferably straight-chain. Straight-chain Cl-C6alkyl is preferred. Examples of this are methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. Particular preference is given to methyl and ethyl.

An alkylene chain forrned by the radicals R7 or Rg is preferably trimethylene or in particular 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 mean molecular weights Mnin the polyamide blocks IVa and Va or in the polyimide blocks IVb ànd Vb or in the polyamideimide blocks IVc and Vc of PA-PI block copolymers C is generally from 300 to 20,000, preferably from 500 to 10,000.

In addition to the abovementioned combinations of two blocks, the PA-PI block copolymers C to be used according to the invention may alternatively contain three-block combinations of the formulae IVa, IVb and Vc or of the formulae IVa, IVc and Vb or of the formulae IVb, IVc and Va.

Preference is given to PA-PI block copolymers C which essentially comprise polyamide blocks IVa and polyimide blocks IVb or comprise polyamide blocks Va and polyimide blocks IVb.

Examples of possible combinations of polyamide and polyimide blocks to give PA-PI
block copolymers C are given in EP-A-0 381 620. These PA-PI block copolymers can be prepared as described in Example 1 of EP-A-0 381 620.

Other suitable PA-PI block copolymers of type D which are soluble in polar aprotic solvents and have a mean molecular weight MnOf from 1000 to 50,000, preferably from 5000 to 40,000, comprise a combination of blocks of the formulae IVa with Vb and/or Vc or of the formulae IVb with Va and/or Vc or of the formulae IVc with Va and/or Vb, with the other proviso that 25-100 mol% of all the radicals R2, R4 and R6, based on the total 2~62oq2 - ls -(E) amount of these radicals, have the formula _ CH2---~ CH2_ and/or (E) m ~ . .
~ cH2-- m whlch E IS Cl-C8alkyl or halogen, and m is a number from 0 tO 4.

The alkyl substituent E in the abovementioned formulae may be branched or preferably straight-chain. Preference is given to straight-chain Cl-C6alkyl. Examples of this are methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. Particular preference is given to methyl.

Halogen E is preferably chlorine or bromine, and m is preferably zero or the number 1.

The ratio between polyamide blocks and polyimide blocks or polyamideimide blocks in the block copolymers D to be used according to the invention is generally deterrnined by the desired solubility of the copolymers in polar, aprotic solvents. The respective proportions of these blocks and the content of the xylylenediamine units and/or of aminobenzylamine units is selected so that the block copolymer is soluble in polar, aprotic solvents.

'rhe preferred ratio between amide groups and imide groups in the PA-PI block copolymers D to be used is from 4:1 to 1:4.

'rhe mean molecular weights M"of the polyamide blocks IVa or Va or of the polyimide blocks IVb or Vb or of the polyamideimide blocks IVc or Vc in the PA-PI block copolymers D is generally from 300 to 20,000, prefeMbly from 500 to 1(),000.

In addition to the abovementioned combinations of two blocks, the PA-PI block copolymers D to be used according to the invention may also comprise three-blockcombinations of the forrnulae IVa, IVb and Vc or IVa, IVc and Vb or IVb, IVc and Va.

Particular preference is given to PA-PI block copolymers D which essentially comprise the recurring structural units of the formulae IVa and IVb or IVb and Va.

Very particularly preferred PA-PI block copolymers of this type only contain thexylylenediamine units or the aminobenzylamine units or a combination of 20~0q2 xylylenediamine units and aminobenzylamine units in the polyimide blocks IVb or Vb.

Examples of possible combinations of polyamide and polyimide blocks to give PA-PI
block copolymers D are given in EP-A-0 381 621. These PA-PI block copolymers can be prepared as described in Example 1 of said EP-A.

Polyarylene ethers comprising the recurring structural units of the formula Ia and, if desired, Ib have been disclosed, for example in the European Applications 383 725, 388 358 and 404 724, and some are also commercially available, for example under the trade name Victrex(~) from ICI.

The polyarylene ethers (b) to be used according to the invention generally have a reduced viscosity of from 0.1 to 2.0 dl/g, which corresponds to a molecular weight of from about 1000 to S00,000.

The polyarylene ethers (b) can be prepared by polycondensing, for example, one or more bisphenols of the formula A
HO-Arl-OH (A) or a mixture of a bisphenol of the formula A and up to 95 mol% of a carbocylic-aromatic dihydroxyl compound of the formula B
HO-Ar3-OH (B) in which Arl and Ar3 are as defined in the formulae Ia and Ib, which is different from the bisphenol of the formula A, in approximately stoichiometric amounts by means of one or more dihalogen compounds of the formula C

Hal-Ar2-Hal (C) in which Ar2 is as defined in the formula la or Ib, and Hal is a halogen atom, preferably a chlorine or fluorine atom, in the presence of alkali and in an aprotic solvent, until the polyarylene ether (b) obtained has a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of NMP at 25~C.

2062~q2 In this polycondensation, the bisphenol of the formula A or the dihydroxyl compound of the formula B is preferably employed in a slight stoichiometric excess, so that polyarylene ethers containing terminal OH groups are obtained.

Further specific terminal groups can be prepared direcdy during the synthesis by adding suitable monomer components or by subsequent reactions. Preferred terminal groups of this type are amino terrninal groups, which can be obtained, for example, during the polycondensation of the polyarylene ethers on addition of p-aminophenol or m-aminophenol.

The polyarylene ethers (b) containing the structural units of the formulae la and Ib and to be used according to the invention are preferably unsubstituted.

The radical Ar1 in the formula Ia can be, for example, a radical of the formula ~}' ~ ~3, ~3 ~3 ~3Y~3Y~

~} ~3 C Y ~3 or ~}Y~3Y~3Y ~3 2~2~q2 in whichY is -CH2-,-C(CH3)2-, -C(CH3)(C6Hs)-, -C(CF3)2-, -S-,-SO-, SO2, O o -CO-, and the aromatic rings are unsubstituted or monosubstituted or polysubstituted by alkyl, the alkyl radical containing 1-4 carbon atoms, or can be, for example, one of the following carbocyclic-aromatic radicals (1) Rg Rlo >~

R~, R12 in which Rg, Rlo, R1l and R12, independently of one another, are each a hydrogen atom or Cl -C4alkyl, (2) (3) or ~_ in which one of the radicals Rl3, Rl4, Rls and Rl6 is phenyl or phenyl which is substituted by one to three Cl-C4alkyl groups, and the other radicals Rl3, Rl4, Rl5 and Rl6,independently of one another, are hydrogen, Cl-C4alkyl, phenyl or phenyl which is substituted by one to three Cl-C4alkyl groups, 20B2~92 (4) ~o~3So2~3o~o~c~ , which is the radical of the product of the condensation of 4,4'-bis(4"-hydroxyphenoxy)diphenyl sulfone and 4,4'-difluorobenzophenone, (S) (R18) k ~ C ~ (Rl7) (R,7)~ ~ C

(Rl8) k in whieh Rl7 is Cl-C4alkyl, Cl-C4alkoxy, C6-C12aryl, C2-C4alkenyl or halogen, I is zero or a numbèr from I to 4, Rlg is Cl-C4alkyl, Cl-C4alkoxy, C6-CI2aryl or halogen, and k is zero or a number from I to 4, which radieal is derived from the corresponding dihydroxyl eompound, whieh can be prepared by the process described in the Journal of the Chemieal Society, C, 1969, 2388 ff, and in the Journal of the Chemical Soeiety, 1938, 1561 ff, (6) F\
{3_o~0~ or (7) ~}~}~

in whieh the aromatie rings are unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups, phenyl groups or halogen atoms, which radicals are derived from the eorresponding bis(hydroxyphenoxy)naphthalenes, whieh can be synthesised by methods known per se, as described, for example, in DE-A 3 636 561, by, for example, reacting a dihydroxynaphthalene of the formula 2062~92 HO~ OH or ~ OH

which is unsubstituted or substituted by one or more Cl-C4alkyl groups, C1-C4alkoxy groups, phenyl groups or halogen atoms, with a halobenzene of the formula Hal ~
R~g in which Hal is halogen, in particular fluorine or chlorine, and Rl9 is C1-C4alkyl, and which is unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups, phenyl groups or halogen atoms, in the presence of alkali to give a bis(acylphenoxy)naphthalene, which can be oxidised using a peracid to give a bis(acyloxyphenoxy)naphthalene, and can subsequently be hydrolysed under alkaline conditions to give bis(hydroxyphenoxy)naphthalene, (8) Q ~

~ C--Ar--C ~

in which the aromatic rings are unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms, and Ar is a divalent aliphatic, cycloaliphatic, araliphatic or aromatic radical having up to 50 carbon atoms, which radical (8) is derived from the corresponding diphenol, which can be prepared by reacting 1 mol of an aromatic dicarboxylic acid or of an aromatic dicarboxylic acid dichloride of the formula Hal-CO-Ar-CO-Hal in which X is a halogen atom, preferably a chlorine atom, and Ar is as defined above, with 2 mol of a 2-alkoxybiphenyl which is unsubstituted or substituted by one or moreCl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms, in the presence of FeCI3 as 2062~92 catalyst in the temperature range from 80- 160C, and reacting the resultant unsubstituted or substituted compound of the formula alkylO ~ C--Ar--C ~ Oalkyl in which Ar is as defined above, and alkyl is Cl-C4alkyl, with 2 to 6 times the amount by weight of AICI3, based on the amount by weight of the compound of the above formula, in the temperature range from 40 to 100C, giving the corresponding diphenol, (9) ~38~3C~3 in which the aromatic rings in the structural units are unsubstituted or substituted by one or more Cl-C4alkyl groups, Cl-C4alkoxy groups or halogen atoms, which radicals are derived from the corresponding diphenol compounds, which have been disclosed, for example in DE-A 3 804 159 and in US Patents 4 447 592 and 4 276 226, (10) (11) (12) / \
Q
~or which radicals are derived from the corresponding diphenols, which have been disclosed and whose preparation is described in Ind. J. Chem.,16B, 601 (1978), in Org. Synth. Coll.
Vol. II,573 (1943) and Coll. Vol. IV, 914 (1963), and radicals of the formula 20620q2 (13) in which Ql is a direct bond, -O-, -CH2- or -CO-, which radicals are derived from 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)xanthene, 9,9-bis(4-hydroxyphenyl)-9,10-dihydroanthracene or 10,10-bis(4-hydroxyphenyl)anthrone, which have been disclosed and can be prepared, for example, by the process described in Journal of Applied Polymer Science, Vol. 27, 3289-3312 (1982), 9,9-bis(4-hydroxyphenyl)fluorene also being commercially available, (14) ~,~SO

which are derived from 1,4-dihydroxy-2-naphthenyl phenyl sulfone or 2,5-dihydroxydiphenyl sulfone, which, according to Chemische Berichte 28, page 1316, can be synthesised from naphthoquinone and benzenesulfonic acid or, according toChemische Berichte 27, page 3259, can be synthesised from p-benzoquinone and benzenesulfonic acid, (15) ~ N N ~ and preferably ~ N~N ~.

N,N'-bis(3-hydroxyphenyl)piperazine being commercially available, 206~92 (16) which is derived from 10,10'-dihydroxy-9,9'-bianthryl, which can be synthesised, for example, according to Annalen der Chemie 379, page 58, from 9-anthrol by oxidative coupling by means of iron(III) chloride, (17) ~' which is derived from 2,5-dihydroxybenzoquinone, which is commercially available, (18) ~' which is derived from 3,6-dihydroxybenzonorbornane, which is commercially available, 2~62~q2 (19) and preferably CH2 or CH2 in which Z is a direct bond or -CH2-, -C(CH3)2-, -C(CH3)(C6Hs)-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-, said radicals being derived from the corresponding binaphthols, which can be synthesised, for example, from the corresponding naphthol by oxidative coupling of further iron(IlJ) chloride or are commercially available.

The radical Arl is preferably one of the radicals ~L ~ ~^~

2~2~G~2 ~30~ ~or ~COI~COl~

The polyarylene ethers (b) to be used according to the invention and in which Ar3 is a spirobiindane radical are disclosed in EP-A-O 383 725. Polyarylene ethers (b) containing a radical of 2,2'-dihydroxybiphenyl are described in EP-A-O 404 724 and those containing an unsubstituted or substituted phenylhydroquinone radical are described in EP-A-O 388 358.

Thc radical Ar2 in the formula la or Ib may be, for example, a radical of the formula CN
~X~a'~'~or ~3 ~b ~
in which a is 1, 2 or 3, b is 2 or 3, and X is -SO-, -SO2- or -CO-.
The radical Ar2 is preferably a radical of the formula O SO2~ or 2~62~q2 ~}so2~}S2{3 and in particular the radical ~ SO2~ .

The radical Ar3 in the formula Ib, which is different from the radical Arl, may be, for example, a radical of the formula ~ ~ ' {3~3 or ~Y~

in whieh Y is -CH2-, -C(CH3)2-, -C(CH3)(C6Hs), -C(CF3)2-, -S-, -SO2-, -O- or -CO-, The radical Ar3 is preferably one of the radieals ~ ~ ~X3 {~}C ~}, ~} ~3 ~ ~ ~_} C ~or ~3so2~, The polyarylene ethers containing the recurring structural units of the formulae la and Ib 20~2~2 in which Arl is a radical of the formula (14), (15), (16), (17), (18) or of the formula CH2 have not yet been described in the literature and likewise form the subject-matter of the invention.

The invention thus also relates to polyarylene ethers having a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25C, and comprising, based on the total amount of structural units present in the polyether resin, from S to 100 mol% of a recurring structural unit of the formula Ic ~0 - Arl' - O - Ar2 ] (Ic) and from 0 to 9S mol% of a recurring structural unit of the formula Ib ~ O - Ar3 - O - Ar2 ~ (Ib) in which Arl' is a radical of the formula ~,S02~ ~,so2~3 2~6~0q2 ~N N~, ~, C".

or ~ and Ar2 and Ar3 are as defined in the ionnulae la and Ib.
Ar, ' in the forrnula Ic is preferably a radical of the formula \ ~

~-The epoxy resins which can be employed in the mixtures according to the invention are generally those containing at least two glycidyl or ,B-methylglycidyl groups bonded directly to an oxygen, nitrogen or sulfur atom or atoms.

2062~92 Examples of such resins are polyglycidyl esters and poly(~-methylglycidyl) esters, which can be obtained by reacting a compound containing one or more carboxyl groups per molecule with epichlorohydrin, glycerol dichlorohydrin or ~-methyl epichlorohydrin in the presence of alkali. Polyglycidyl esters of this type 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, dimerised or trimerised linoleic acid, from cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid, or from aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid or terephthalic acid Further examples are polyglycidyl ethers and poly(,B-methylglycidyl) ethers, which can be obtained by reacting a compound containing at least two free alcoholic and/or phenolic hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions, or alternatively in the presence of an acid catalyst with subsequent alkali 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(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane-l,S-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol and polyepichlorohydrins, from cycloaliphatic alcohols, such as resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane and 1,1-bis(hydroxymethyl)-3-cyclohexene, and from alcohols containing aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. They can furthermore be prepared from monocyclic phenols, such as resorcinol and hydroquinone, and polycyclic 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, such as formaldehyde, acetaldehyde, chloral and furfurol, with phenols, such as phenol itself and phenol which is ring-substituted by chlorine atoms or alkyl groups, in each case having up to 9 carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.

Poly(N-glycidyl) compounds include, for example, those obtained by dehydrochlorinating the products of the reaction of epichlorohydrin with amines containing at least two amine 20~2~92 hydrogen atoms, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine and bis(4-methylaminophenyl)methane, triglycidyl isocyanurate, and N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethyleneurea and 1,3-propyleneurea, and of hydantoins, such as 5,5-dimethylhydantoin.

The cycloaliphatic epoxy resins employed can be, for example, bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane or 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate.

Examples of poly(S-glycidyl) compounds are the di-S-glycidyl derivatives of dithiols, such as ethane-1,2-dithiol and bis(4-mercaptomethylphenyl) ether.

Also suitable are epoxy resins in which the glycidyl groups are bonded to hetero atoms of different types, for example the N,N,O-triglycidyl derivative of 4-aminophenol or of 2,2-(4-aminophenyl-4'-hydroxyphenyl)propane, the glycidyl ether/glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane. The epoxy resins used may also be substituted by alkyl, alkenyl or aryl groups, halogen atoms or by aryloxy or alkoxy groups. A preferred example 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 and novolaks, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and bisphenol S diglycidyl ether, resorcinol diglycidyl ether or cyclohexanedimethanol diglycidyl ether, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-m-aminophenol, triglycidyl isocyanurate, tetraglycidyl-4,4'-diaminodiphenylmethane and tetra(p-glycidyloxyphenyl)ethane and 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate.

The epoxy resin used for the mixtures according to the invention is in particular bisphenol A diglycidyl ether, tetraglycidyl-4,4'-diaminodiphenylmethane, tetra(p-glycidyloxyphenyl)ethane and N,N,O-triglycidyl-p-aminophenol.

Very particular preference is given to N,N,O-triglycidyl-p-aminophenol.

2062~q~

It is furtherrnore possible to add to the mixtures according to the invention a further technical-grade polymer (d) from the group comprising polyamides, polyimides, polyether-imides, polyester-imides, polyhydantoins and polyparabanic acids, as are used for electronic and electrical purposes. These polymers are predominantly commercially available or can be synthesised by known processes. The following commercial products may be mentioned by way of example:
Ultem(~) from General Electric (polyether-imide), Matrimid 5218 from CIBA-GEIGY (polyimide).

The mixtures according to the invention have good processing properties and can be used, for example, as matrix resins, surface coatings, adhesives and coating compositions for the production of industrial products of all types, for example fibre-reinforced composites, laminates, adhesive bonds, foams, coatings, films, sheets or pressings.

Before the mixtures, in the form of powders, films or in particular solutions are processed, conventional additives, for example fillers, pigments, stabilisers or reinforcing agents, such as carbon fibres, boron fibres, metal fibres or glass fibres, or alternatively further polymers, eg. Teflon@), can be added. In particular, addition of flow-control agents, for example BYK~S 706 from BYK-Chemie, Wesel, may be advantageous. The mixtures according to the invention preferably additionally contain a flow-control agent.
As a consequence of the good solubility of the mixtures according to the invention in polar aprotic solvents, it being possible for these to be diluted with other conventional solvents, such as halogenated hydrocarbons or aliphatic hydrocarbons, the mixtures can advantageously be processed from a solution to give f~lms or used to produce coatings on substrates of all types.

A further important advantage of the mixtures according to the invention is that highly concentrated solutions of low viscosity can be used. Low-viscosity polymer solutions of polyamide-polyimides can usually only be prepared at low concentrations or usingpolymers of low molecular weight. However, high concentrations are desired in coating operations in order to keep the amount of solvents as low as possible. Since the properties of polymers are directly correlated with the molecular weight, it is generally not possible to employ polymers of low molecular weight. This would have the consequence of asignificant impairment in the properties. By contrast, however, it is possible in the case of the mixtures according to the invention to employ polymers of low molecular weight and 20~2~92 thus low solution viscosity which give coatings having very good properties.

Examples of 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, generally in a temperature range of from 150 to 300C, for example for 45 minutes at 1 80C with infra-red irradiation, the coating is resistant to solvents. The solvent-resistant coatings furthermore have good adhesion, preferably to metals, and high flexibility. It is thus possible, using the mixtures according to the invention, to produce coatings in which the good mechanical properties of the PA-PI block copolymers, such as high flexibility, are retained, no embrittlement due to the addition of epoxy resins is evident and good adhesive strength is achieved.

The invention also relates to monocoated laminates, for example metal laminates, in particular copper laminates, in which the coating is a mixture according to the invention.

It has furthermore been found that metal foils coated with the mixtures according to the invention can be bonded directly to multilayer laminates without the use of additional adhesion aids, for example acrylate adhesives, The present invention thus also relates to laminates, preferably metal lamina~es, and in particular copper laminates, in which the adhesive bond comprises the mixture according to the invention comprising a PA-PI block copolymer ~a), a polyarylene ether (b) and an epoxy resin (c), The adhesive bond is produced under pressure and at a temperature which allows at least slight flow of the PA-PI block copolymer/epoxy resin mixture, for example a temperature range of from 200 to 300C

Laminates of this type, which are very flexible and can be folded repeatedly without fracture, are preferably used in the electronics industry for the production of circuits, ln the mixtures according to the invention, the ratio between the individual components generally depends on the molecular weight of the PA-PI block copolymer and of the polyarylene ether, on the content of terminal groups and on the glass transitiontemperature of the polymers used, on the desired heat and solvent resistance of the finished laminate and on the desired processing temperature Thus, a relatively high 2062~F2 proportion of epoxy resin will be employed in the case of a block copolymer and a polyarylene ether of low molecular weight. Likewise, if a low processing temperature is desired, a mixture of polymer structures having a low glass transition temperature and simultaneously a high proportion of epoxy resin will be preferred. If, for example, a laminate having particularly high temperature stability is required, mixtures of PA-PI
block copolymers and polyarylene ethers having a high glass transition temperature and a relatively low proportion of epoxy resin are preferably employed.

The PA-PI block copolymers, polyarylene ethers (PAE) and epoxy resins (EP~ used in the examples below are prepared as follows or are commercially available.

PA-PI block copolvmer A: In accordance with the process described in Example 1 of EP-A-0 324 315, a polyamidic acid block is prepared from 80.56 g (0.25 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 25.90 g (0.1042 mol) of 4,4'-diaminodiphenyl sulfone and 25.90 g (0.1042 mol) of 3,3'-diaminodiphenyl sulfone and is reacted with 76.90 g (0.378 mol) of isophthaloyl dichloride,51.83 g (0.2084 mol) of 4,4'-diaminodiphenyl sulfone and 51.83 g (0.2084 mol) of 3,3'-diaminodiphenyl sulfone to give the polyamide-polyamidic acid block copolymer, which i9 subsequently cyclised. The intrinsic viscosity of the PA-PI block copolymer A
(0.5 g of polymer in 100 ml of NMP at 25C) is 0.35 dl/g.

PA-PI block coDolvmer B: In accordance with Synthesis Example I of EP-A-0 381 621, a polyamidic acid block is prepared from 80.56 g (0.25 mol) of 3,3',4,4'-benwphenonetetracarboxylic dianhydride, 12.96 g (0.0521 mol) of 4,4'-diaminodiphenyl sulfone, 12.96 g (0.0521 mol) of 3,3'-diaminodiphenyl sulfone and 14.20 g (0.1042 mol) of m-xylylenediamine and is reacted with 76.93 g (0.4693 mol) of isophthaloyl chloride,51.84 g (0.2084 mol) of 4,4'-diaminodiphenyl sulfone and 51.84 g (0.2084 mol) of 3,3'-diaminodiphenyl sulfone to give the polyamide-polyamidic acid block copolymer, which is subsequently cyclised to give PA-PI block copolymer B. The intrinsic viscosity (0.5 g of polymer in 100 ml of NMP at 25C) of the block copolymer is 0.51 dl/g.

PA-PI block coPolYmer C: In accordance with the process described in Example I of EP-A-0 324 315, a polyamidic acid block is prepared from 94.15 g (0.32 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 34.74 g (0.1400 mol) of 2~2~q2 4,4'-diaminodiphenyl sulfone and 34.74 g (0.1400 mol) of 3,3'-diaminodiphenyl sulfone and is reacted with 8.60 g (0.0424 mol) of isophthaloyl dichloride, 10.00 g (0.0403 mol) of 4,4'-diaminodiphenyl sulfone and 9.93 g (0.0400 mol) of 3,3'-diaminodiphenyl sulfone with addition of 6.18 g of butylene oxide to give the polyamide-polyamidic acid block copolymer, which is subsequently cyclised using 157.12 g (1.5526 mol) of triethylamine and 160.96 g (0.5780 mol) of acetic anhydride. The intrinsic viscosity of the PA-PI block copolymer C (0.5 g of polymer in 100 ml of NMP at 25C) is 0.36 dl/g.

PA-PI block coPolvmer D: In accordance with the process described in Example 1 of EP-A-0 381 620, a polyamidic acid block is prepared from 32.22 g (0.10 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 65.46 g (0.30 mol) of pyromellitic dianhydride, 108.02 g (0.4250 mol) of 4,4'-diamino-3,3'-diethyldiphenylmethane and is reacted with 21.10 g (0.1046 mol) of isophthaloyl dichloride and 19.25 g (0.0757 mol) of 4,4'-diamino-3,3'-diethyldiphenylmethane with addition of 15.66 g of butylene oxide to give the polyamide-polyamidic acid block copolymer, which is subsequently cyclised using 166.31 g (1.6435 mol) of triethylamine and 164.55 g (1.612 mol) of acetic anhydride. The intrinsic viscosity of the PA-PI block copolymer D (0.5 g of polymer in 100 ml of NMP at 25C) is 0.49 dl/g.

PA-PI block coPolYmer E: In accordance with Synthesis Example 12 of EP-A-0 381 621, a polyamidic acid block is prepared from 40.28 g (0.125 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 26.33 g (0.125 mol) of trimellitic anhydride chloride,36.28 g (0.146 mol) of 4,4'-diaminodiphenyl sulfone and 19.89 g (0.146 mol) of m-xylylenediamine and is reacted with 73.22 g (0.3610 mol) of isophthaloyl chloride,79.97 g (0.3210 mol) of 4,4-diaminodiphenyl sulfone with addition of 66.27 g of butylene oxide to give the polyamide-polyamidic acid block copolymer, which is subsequently cyclised using 94.86 g (0.9375 mol) of triethylamine and 95.70 g (0.9375 mol) of acetic anhydride. The intrinsic viscosity (0.5 g of polymer in 100 ml of NMP at 25C) of the block copolymer E is 0.46 dl/g.

PAE 1: Polyether sulfone Victrex(~) 5003 P (commercial product from ICI) containing the recurring structural unit ~o~SO2~0~S02~

20620ct~

and having a reduced viscosity (1 g of polymer in 100 ml of NMP) of 0.64 dl/g.

PAE 2: Polyether sulfone having the structure {o~So2~o~3so2~o~o~so2~ol5 and prepared from phenylhydroquinone, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone as described in Example 4 of EP-A-0 388 358, and having a reduced viscosity (I g of polymer in 100 ml of NMP) of 0.58 dl/g.

SYnthesis of the polYarvlene ethers Process A:

Synthesis of polyarylene e~her PAE 24 A mixture of 58.60 g (0.02047 mol) of 1,1'-bi-2-naphthol, 58.6 g (0.2142 mol) ofanhydrous potassium carbonate, 216 g of diphenyl sulfone and 100 g of xylene is heated under nitrogen to a bath temperature of 200C in a flask with ground-glass joints which is fitted with a stirrer, during which a xylene/water mixture distils off. This distillation operation is completed after about 1.5 hours by briefly (for about 10 minutes) applying a vacuum in the range of from 1 to 5 mbar.

57.45 g (0.2001 mol) of 4,4'-dichlorodiphenyl sulfone are subsequently added under nitrogen to the reaction mixture, and the temperature is increased to 251 C and maintained for I hour. The temperature is then raised to 271C for 3 hours. The reaction rnixture exhibits a significant increase in viscosity with reaction time.

Afser brief cooling, the reaction mixture is removed from the flask, allowed to solidify and powdered. In order to isolate the polymer, the mixture is extracted with water with addition of acetic acid, subsequently extracted a number of times with water and finally extracted with a water/acetone mixture (1:4). The polymer purified in this way is then 2062~72 extracted with a water/acetone mixture (1:4). The polymer purified in this way is then dried to a temperature of 240C in a vacuum drying cabinet.

A polyarylene ether sulfone copolymer prepared in this way has a reduced viscosity (determined on 1 g of polymer dissolved in 100 ml of N-methylpyrrolidone at 25C) of 0.30 dl/g.

The synthesis of the polyarylene ethers denoted by process A is carried out analogously.

Process B: The synthesis is carried out as for process A, but the polymer is dissolved in methylene chloride after the extraction step and, after filtration, is precipitated by pouring into isopropanol.

Process C: The synthesis is carried out as for process A, with the exception that the dihalogen component is added at the beginning and not after the diphenoxide formation.

Process D: The synthesis is carried out as for process C, with the exception that no entrainer (xylene) is ad~ed.

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b E-2~62~q2 EP I: Tetra(p-glycidyloxyphenyl)ethane (ERRA(~) 0163 from UCC) EP II: Bisphenol A diglycidyl ether (Araldit(~) MY 790 from CIBA-GEIGY) EP III: N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane having an epoxide content of 9.1 equivalents/kg EP IV: N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane having an epoxide content of 7.5-8.5 equivalents/kg EP V: N,N,O-Triglycidyl-4-aminophenone EP VI: 3,4-Epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate EP VII: Isomer mixture of bisphenol F diglycidyl ether (2,2-, 4,4- and 2,4-derivatives) EP VIII: Bisphenol S diglycidyl ether having an epoxide content of 5.3 equivalents/kg EP IX: Phenolnovolak polyglycidyl ether having an epoxide content of 5.6-5.8 equivalents/kg EP X: Solid bisphenol A diglycidyl ether having an epoxide content of 1.68-1.75 equivalents/kg EP X~: Resorcinol diglycidyl ether EP XII: O,O'-Diallylbisphenol A diglycidyl ether having an epoxide content of 4.6 equivalents/kg EP XIII: Cyclohexanedimethanol diglycidyl ether EP XIV: Liquid bisphenol A diglycidyl ether having an epoxide content of 5.2-5.4 equivalents/kg Udel(~)P 1800: Polysulfone from Amoco Ultem(~) 1000: Polyether-imide from General Electric Matrimid 5218: Polyimide from CIBA-GEIGY AC

Examples 1-8: Flexible two-layer laminates are produced by the process below:

A 25 % by weight solution in N-methylpyrrolidone (NMP) of the PA-PI block copolymer, the polyarylene ether (PAE) and the epoxy resin (EP) in the stated ratio is applied by means of a film applicator (200 ~,lm) to the treated side of a copper foil (35 llm, manufacturer Yates), and the film is dried in a circulating-air paint drying cabinet under 2062~q2 IR irradiation (conditions: air temperature: 180C, 45 minutes, IR lamp: Heraeus, model MMS 1200). Part of the coated foil is cut into strips 1 cm in width and the flex-life of the laminate is determined (flex-life = number of folds before the laminate fractures, determined using a universal model 2 FDF flex ductility tester with a weight of 224 g and a 2 mm mandrel). The solvent resistance is deterrnined on a further part of the foil measuring 8 x 8 cm by dipping into NMP at 20C for 1 hour. The properties are shown in Table 1.

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X~,~ _ C~ ~0 V~ ~ ~o ~ ~ l-3.~3~
C.~
o ~ ~ V~
~ 3 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~o o3 o o o o o o o o o o o o o ¢ o~

~C~ ~ ~ ~ ~ ~ ~ ~ ~ ~ o ~ V~ V~
~ o - ~
c 8 D ~ u~ ~ v~ ~
.~ E ~, _ ~ O O O o o o v~ ~ o u~ ~ o o c ~ ~x x x ~ x x x ~ >

O ¢ ~1~----________ ~i o _ ~ o --E- ~ ~ ~ ~ ~t 2062~42 1~ , o ~ _- o ,.. ~ Z o _' ~ o o ~ ~ C`~ o o ~,_,c + + + + ~ + + + + +

X~ ~ ~ o ~t LL'__ 1~
'~
o C: ~ , ~`, ~ ~ ~ ~ ~ ~ ~ ~

O ~ D O O O O O O ~ O O O O
¢ o~
,.

~ :_ 5~ ~ c ," v~ v~ c _ ~J ~ o '` ~ g ~ ~ ~`' ~ ~ u ~ 5 f:

, D O Dl~ DJ~ DJ) Dl~
~ C_C C C C:
D c:~ 0~ ~ ~ ) 20620q2 Example 60: PA-PI block copolymer A, polyarylene ether 1 and epoxide I are dissolved in N-methylpyrrolidone in a concentration of 20 % by weight in a ratio 90:5:5 parts by weight, and the solution is applied to a copper foil (thickness 35 ~m, NT-TW from Circuit Foils) in a thickness of 200 ~,lm, and the coating is subsequently dried in a circulating-air drying cabinet for 10 minutes at 50C, for 45 minutes at 150C and 45 minutes at 270C.
The adhesion is determined at various temperatures:

Room temperature 19.7 N/cm 150C: 18.5 N/cm 260C: 5.2 N/cm

Claims (19)

1. A mixture comprising, based on 100 parts by weight of the mixture, (a) from 50 to 98 parts by weight of a polyamide-polyimide (PA-PI) block copolymer, (b) from 1 to 49 parts by weight of a polyarylene ether having a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25°C, and comprising, based on the total amount of structural units present in the polyether resin, from 5 to 100 mol% of a recurring structural unit of the formula Ia ?O - Ar1 - O - Ar2? (Ia) and from 0 to 95 mol% of a recurring structural unit of the formula Ib ?O - Ar3 - O - Ar2? (Ib) in which Ar1 is a carbocyclic-organic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms, Ar2 is a carbocyclic-aromatic radicul which is unsubstituted or substituted by one or more C1-C4alkyl groups or C1-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO-units as bridging members, or is a cyanophenylene, pyridine or pyrazine radical, and Ar3 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms and is different from Ar1, and (c) from 1 to 40 parts by weight of an epoxy resin containing at least two glycidyl groups in the molecule, and (d) from 0 to 10 parts by weight of a further polymer from the group comprising polyamides, polyimides, polyether-imides, polyester-imides, polyhydantoin and polyparabanic acids.

2. A mixture according to claim 1, comprising, based on 100 parts by weight of the mixture, (a) from 50 to 98 parts by weight of a polyamide-polyimide (PA-PI) block copolymer, (b) from 1 to 49 parts by weight of a polyarylene ether having a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of N-methyl-2-pyrrolidone (NMP) at 25°C, and comprising, based on the total amount of structural units present in the polyether resin, from 5 to 100 mol% of a recurring structural unit of the formula Ia ?O - Ar1 - O - Ar2? (Ia) and from 0 to 95 mol% of a recurring structural unit of the formula Ib ?O - Ar3 - O - Ar2? (Ib) in which Ar1 is a carbocyclic-organic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms, Ar2 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups or C1-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO-units as bridging members, or is cyanophenylene, and Ar3 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms and is different from Ar1, and (c) from 1 to 40 parts by weight of an epoxy resin containing at least two glycidyl groups in the molecule.

3. A mixture according to claim 1, in which the PA-PI block copolymer (a) has a mean molecular weight ?n of from 1000 to 50,000 and comprises recurring units of the formula II
?PA-PI? (II), in which PA is a polyamide block having a mean molecular weight ?n of from 300 to 20,000 and comprising at least one (recurring) unit of the formula III

(III), in which R1 is a radical of the formula -CnH2n-, , ,, or and R2 is a radical of the formula -CnH2n-, ,, ,,, ,, or in which Q is a direct bond, -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)-, -O-, -S-, -SO2-, -CO- or , and n is 2-12, Ya and Yb, independently of one another, are each C1-C4alkyl, and where s is zero or a number from 1 to 4, and Yc, Yd, Ye and Yf, independently of one another, are hydrogen, halogen or C1-C4alkyl, and PI is a polyimide block having a mean molecular weight ?n of from 300 to 20,000 and comprising at least one (recurring) unit of the formula IV

(IV) in which R3 is ,,, ,, or , and Q and R2 are as defined above, with the proviso that from 25 to 100 mol% of all the bridging members R2 are and/or , and the (cyclo)aliphatic content of the bridging members R2 is not more than 10 mol%.

4. A mixture according to claim 1, wherein the PA-PI block copolymer (b) has an Mn of from 1000 to 50,000 and comprises recurring structural units of the formula II
?PA-PI? (II) in which the ratio between amide and imide groups in the polyamide block PA and in the polyimide block PI is from about 4:1 to 1:4, and the block copolymer has a content of at least 2 mol%, based on the content of all carboxyl radicals in the block copolymer, of radicals of the formula in the polyimide blocks.

5. A mixture according to claim 4, in which the PA-PI block copolymer comprises a combination of blocks of the formulae Vb with IVa and/or IVc or of the formulae IVb with Va and/or Vc (IVa), (IVb), (IVc), (Va), (Vb), (Vc), in whieh the indices e, f and g, independently of one another, are integers from 1 to 100, R1 is a radical of the formula -CnH2n-, ,, , or and R2 is a radical of the formula -CnH2n-,,, ,,, ,, or in which Q is a direct bond, -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)-, -O-, -S-, -SO2-, -CO- or , and n is 2-12, Ya and Yb, independently of one another, are each C1-C4alkyl, and where s is zero or a number from 1 to 4, and Yc, Yd, Ye and Yf, independently of one another, are hydrogen, halogen or C1-C4alkyl, R3 is a radical of the formula ,,,,, , or , in which q is as defined above, R5 is a radical of the formula , and R4 and R6, independently of one another, are as defined for R2, with the proviso that 25-100 mol% of all radicals R3 have the formula .

6. A mixture according to claim 5, in which the PA-PI block copolymer comprises a combination of blocks of the formulae IVa with Vb and/or Vc or of the formulae IVb with Va and/or Vc or of the formulae IVc with Va and/or Vb, with the other proviso that 10-100 mol%, preferably 25-100 mol%, in particular 50-100 mol%, of all the radicals R2, R4 and R6, based on the total amount of these radicals, have the formula in which p is 1 or 2, q is zero, 1 or 2, R7 and R8 are each C1-C8alkyl, or in which each two radicals R7 and R8 in the ortho-positions to one another form an alkylene group having 2 to 10 carbon atoms.

7. A mixture according to claim 5, in which the PA-PI block copolymer comprises a combination of blocks of the formulae IVa with Vb and/or Vc or of the formulae IVb with Va and/or Vc or of the formulae IVc with Va and/or Vb, with the other proviso that 25-100 mol% of all the radicals R2, R4 and R6, based on the total amount of these radicals, have the formula and/or in which E is C1-C8alkyl or halogen, and m is a number from 0 to 4.

8. A mixture according to claim 1, in which, in the polyarylene ether (b), Ar1 in the recurring structural unit of the formula 1a is a radical of the formula ,,, , or .

9. A mixture according to claim 1, in which, in the polyarylene ether (b), Ar2 in the recurring structural units of the formulae Ia and Ib is a radical of the formula ,,, or .

in which a is 1, 2 or 3, b is 2 or 3 and X is -SO-, -SO2- or -CO-.

10. A mixture according to claim 1, in which, in the polyarylene ether (b), Ar2 in the recurring structural units of the formulae Ia and Ib is a radical of the formula or .

11. A mixture according to claim 1, in which, in the polyarylene ether (b), Ar3 in the recurring structural unit of the formula Ib is a radical of the formula ,, or in which Y is -CH2-, -C(CH3)2-, -C(CH3)(C6H5)-, -C(CF3)2, -S-, -SO2-, -O- or -CO-.

12. A mixture according to claim 1, in which, in the polyarylene ether (b), Ar3 in the recurring structural unit of the formula Ib is a radical of the formula ,,, ,, , or ,

13. A mixture according to claim 1, in which the epoxy resin (c) is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, resorcinol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-m-aminophenol, triglycidyl isocyanurate, tetraglycidyl-4,4'-diaminodiphenylmethane or tetra(p-glycidyloxyphenyl)ethane.

14. A mixture according to claim 13, in which the epoxy resin (c) is bisphenol Adiglycidyl ether, tetraglycidyl-4,4'-diaminodiphenylmethane, tetra(p-glycidyloxyphenyl)ethane or N,N,O-triglycidyl-m-aminophenol.

15. A mixture according to claim 1, in which the further polymer (d) is a polyether-imide or a polyimide.

16. A monocoated laminate, preferably a metal laminate, in particular a copper laminate, in which the coating is a mixture according to claim 1.

17. A laminate, preferably a metal laminate, in particular a copper laminate, in which the adhesive bond comprises a mixture according to claim 1.

18. A solution comprising from 1 to 50 parts by weight, preferably from 5 to 40 parts by weight, of a mixture according to claim 1 dissolved in 100 ml of an organic solvent, preferably N-methylpyrrolidone or .gamma.-butyrolactone.

19. A polyarylene ether (b) according to claim 1, having a reduced viscosity of from 0.1 to 2.0 dl/g, measured on a solution of 1 g of polymer in 100 ml of N-methyl-2-pyrrolidone at 25°C, and comprising, based on the total amount of structural units present in the polyether resin, from 5 to 100 mol% of a recurring structural unit of the formula Ic ?O - Ar1' - O - Ar2? (Ic) and from 0 to 95 mol% of a recurring structural unit of the formula Ib ?O - Ar3 - O - Ar2? (Ib) in which Ar1' is a radical of the formula ,, ,,, or and Ar2 is a carbocyclic-aromatic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups or C1-C4alkoxy groups and contains one or more -CO-, -SO2- or -SO- units as bridging members, or is a cyanophenylene, pyridine or pyrazine radical, and Ar3 is a carbocyclic radical which is unsubstituted or substituted by one or more C1-C4alkyl groups, C1-C4alkoxy groups or halogen atoms and is different from Ar1.

FD 4.3/STA/hdr*