STORABLE LOESUNGEN OF HAERTBARER MIXTURES.

1. Storable solutions containing beside solvent hardenable mixtures of 1) imides or amide carbonic acids, which a remainder of the general formulas I and/or IL (i) HOCO D CO " NH, (II) contained a carbon carbon double bond containing remainder in those D a bivalent, meant, more einoder more times in the molecule, and 2) Homonomeren for the imides and/or amide carbonic acids, by the fact characterized that they contain additionally one or more connections, which exhibit at least a Furylrest in the molecule in such a quantity that on 1 ÁquivaBei of the production of copper-covered laminate plates, which are used in particular for printed circuits one uses epoxy resins today as synthetic resin predominantly and for technically less fastidious elements also phenol formaldehyde resins. A special criterion for the quality of the copper-covered plate is the adhesive strength between the Kupferfolie and the laminate plate. The border specification is with conventional plates on epoxy resin basis with 3,6 kp/in according to NEMA standard left 1-1971 (US Norm regulation 1 ₜ “national the Electrical Manufacturers ate”).

One manufactured also laminates on the basis of polymerized Polymaleinimiden, already copper-covered. During the production of the plates first the glass fabric with the melt or the solution of the hardenable mark A IMIDe and the Homonomeren and the polymerization catalysts or the Präpolymeren were impregnated if necessary and afterwards in such a way received material in several situations with the Kupferfolie was hot injected one above the other. In this connection is to be referred for example to the following publication: F.P. Darlent imide or amide carbonic acid quantity of 0.05 to 10 equivalents 1ù mory et al. “Polyimide laminating resin for more multylayer printed these at least a Furylrest in the molecule exhibiting connection kommen.

2. Solutions according to requirement 1, by the fact characterized that they contain the imides or the amide carbonic acids and the Comonomeren in such a quantitative proportion that on 1 equivalent imide of the formula I or amide carbonic acid of for, mel II 0.1 to 1.5 equivalents Homonomer kommen.

3. Solutions according to requirement 1, by the fact characterized that the concentration of the solved solids and/or to solved solids leading the original substances between and 90 Gew. - %, preferably between 50 and 70 Gew. - %, related to the entire solution, beträgt.

4. Solutions according to requirement 1, by the fact characterized that it as lmide or amide carbonic acids of the formulas I and/or II mark A TIMe or mark A AMIDE CARBONIC ACIDs enthalten.

Solutions according to requirement 1, by the fact characterized that it as Homonomere a polyprimäres amine or a multi-valued phenol or a multi-valued alcohol or a Polycarbonsäure or an alkenyl phenol or an alkenyl phenol ether or a Azomethin or a mixture of several of these substances enthalten.

6. Solutions according to requirement 1, by the fact characterized that the connections, which contain at least a Furylrest in the molecule are liquid and the solvent to 0.5 to 100 Gew. - % ersetzen.

7. Solutions according to requirement 6, by the fact characterized that it as solvent Furfurylalkohol enthalten.

8. Solutions according to requirement 1, by the fact characterized that it only organic solvents enthalten.

511 9th solutions according to requirement 1, by the fact characterized that the hardenable mixtures the imides or amide carbonic acids of the formulas I and/or II and the Homonomeren totally or partly in the form of Präpolymeren enthalten.

, Interlaced polymers, thereby characterized exhibiting use from solutions to requirement 1 for the production of groups of imides, that one moistens a substrate or the surface of a body with a solution in accordance with requirement 1, afterwards the solvent it evaporates and finally hardens and vernetzt.

The invention concerns storable solutions, which hardenable mixtures of in particular Polymaleinimiden and Comonomeren contained and which use of these solutions for the production of interlaced groups of imides of exhibiting Polymeren.

wiring board” Insulation/Circuits, Octobér 1974, 25-29.

Opposite the conventional copper-covered laminate plates on epoxy resin basis those advantages large on Polymaleinimidharzbasis exhibit. They are more heat resistant and exhibit a substantially larger dimensional stability. So far such copper-coated laminate plates on Polymaleinimidharzbasis found however still no large entrance into the electrical industry, because the copper laminate disk adhesion did not meet the requirements. The adhesive strength is with these well-known plates, with which the Kupferfolien are superficially modified after a well-known brass Treatment, between 1,5 and 2,4 kp/in.

In the CSU patent 345,156 a procedure for the production of adducts of the Furfurylalkohols with aromatic Dimaleinimiden is stressed. The gefällten adducts can be before-condensed heavily with other Homonomeren to Präpolymeren, so that useful impregnation solutions are not realizable. As attempts showed, no sufficient firm copper adhesion leave themselves erzielen.

by application of the adducts for the production of copper-covered laminates, stressed by the CSU patent The large demands of the adhesion are made by the industry for the following reasons:

Perfect punching, bending and soldering and purposeful, clean corroding succeed only in case of outstanding adhesion to the Kupferfolie at the laminate plate. A replacement of the Kupferfolie of the plate (in particular due to the warmth when soldering) leads inevitably to the fact that the thin lines on the plate evade and/or “away-swims”. That makes the production of the printed circuit boards serving as carriers of electronic construction units unmöglich.

A further reason for it that such PolyimidLaminate found still no large entrance into the technology, is the fact that the appropriate Imprägniedösungen is a cause for disturbances with the processing. In the case of use of the usual solvents, like methyl glycol, dimethylformamide, N-Methylpyrrolidon, acetone and methylethylketone, a very bad shelf-life of the impregnation solution results also here. A duplication of the viscosity enters at ambient temperature already within to three days. In addition the Polymaleinimide or the Präpolymere already crystallizes aus.

in many cases after short storage With the given state of the art the procurement of storable impregnation solutions on PolymaleinimidBasis, whose employment makes the production of copper-covered laminate plates possible with sufficient large Hafffestigkeit between Kupferfolie and baseplate, was a special request of the electrical industry and its suppliers. The task in such a way placed became by the invention in simple and elegant way gelöst.

The subject of the invention storable solutions are containing beside solvent hardenable mixtures of 1) imides or amide carbonic acids, which a remainder of the general formulas I and/or II (1) HO. CO-D-CO. NH, (II) contained a carbon carbon double bond containing remainder in those D a bivalent, meant, more einoder more times in the molecule, and 2) Homonomeren for the imides and/or amide carbonic acids, by the fact characterized that they contain additionally one or more connections, which exhibit at least a Furylrest in the molecule in such a quantity that on 1 equivalent imide or amide carbonic acid quantity of 0.05 to 10 equivalents of these at least a Furylrest in the molecule exhibiting connection comes. '619,251 ten, which were already enumerated in the FR-patent 1,555,564. The remainder of the formula I containing mark A IMIDEs are particularly well suitable, with those D the bivalent remainder of the formula 11I q R/\ C IL CH (III) lo meant, whereby R hydrogen or methyl darstellt.

Solutions with Polyimiden, which the remainder, place an advantages form of the invention of the formula (1) more zweioder three times in the molecule, and thus in particular Bisund Trismat of flax imides containing solutions contain dar.

As particularly well suitable until mark A IMIDEs connections of the formula IV are the remainders of the formulas 1 or 1I are preferably twice contained in the imides or amide carbonic acids. Additionally polymerization catalysts can be contained. On 1 Åquivalent Imidoder amide carbonic acid come vorzugsm point 0.1 to 0.5 equivalents at least at least a Furylrest in the molecule exhibiting Verbindung.

Since so far with the production of copper-coated laminate plates neither by use of solutions and melts by Polymaleinimiden and Comonomeren or by appropriate Präpolymeren still by use of FurfurylalkohoI Maleinimid adducts in accordance with CSU patent 345,156 the requirements of the technology sufficient copper adhesion could be realized, the elegant solution, which makes a outstanding copper adhesion possible, had to really surprise. Amazing it is also that with the solutions according to invention practically no disturbances by insufficient stability in storage, i.e. viscosity rise and crystallizations after short storage time, auftreten.

With the solutions according to invention it in most cases concerns colloids l_, Ssungen, which can to be been present as emulsions as as suspensions. In some cases, in particular with a little far advanced Präpolymerbildung, can concern it totally or partly also molekulardisperse (thus genuine) solutions. “ù in accordance with the invention lies the concentration of all solids and the original substances leading to the solids in the solution generally between 5 and 90 Gew. - %, preferably between 50 and 70 Gew. - %, whereby itself the Gew. - %-data to the entire solution refer. 5 the imides or the amide carbonic acids and the Comonomeren is present in the solution according to invention in such a quantitative proportion that on an equivalent lmid the formula I or Amidearbonsäure of the formula II preferably 0.1 to 1.5 equivalents Homonomer come. 0 most applicable of the according to invention imides and amide carbonic acids is in detail descriptive in the literature. Their production can according to in the US patent specification 3 the,010,290 and,137,592 methods descriptive in the GB-patent specification 1 by conversion of the appropriate diamines “, 5 with the insatiated dicarbonic acid anhydrides erfolgen.

The solutions according to invention can do all the Polyimide (and the appropriate PP carbonic acids) enthalR (IV), in A a bivalent organic remainder with 2 to 30 CAtomen meant, too nennen.

The remainder of A in formula IV preferably corresponds to the formula (V), CH3 I .m whereby RI one of the remainders - CH2 -, - C -, - SO2 -, - THEN, - Sund I CH3 - Odarstellt and n 0 or 1 ist.

As examples of well-known Polyimide, which are suitable for the solutions according to invention, are the following substances mentioned:

N, N' hexadecimal hexadecimaluntil mark a imidehexadecimal until mark A IMIDe N, N' p-Phenylen-to-maleinimid N, N'-4,4' Diphenylmethan to maleinimid N, N'-4,4'-3,3' Dichlor diphenylmethan to maleinimid N, N'-4,4' Diphenyläther to maleinimid N, N'-4,4' Diphenylsulfon to maleinimid the N, N' until mark A IMIDe the 4.4 ' - Diamino triphenylphosphats, ° the N, N' until mark A IMIDe the 4.4 ' - Diamino triphenylthiophosphats, the N, N', N' “- trichloroethylene mark A IMIDe of the trichloroethylene (4-aminophenyl) - of phosphate, the N, N”, N” - trichloroethylene mark A IMIDe of the trichloroethylene (4-aminophenyl) - thiophosphats.

One can use mixtures of two for the solutions according to invention also or several all Poly imides mentioned above. According to invention naturally also the pre-products all above in detail mentioned mark A IMIDEs can in the solutions, i.e. the remainder of the formula II containing mark A AMIDE CARBONIC ACIDs, uses werden.

619,251 as Homonomere contains the solutions according to invention the well-known reaction partners for until mark A IMIDEs or mixtures the same. Here for example following substances are to be specified:

polyprimäre amines, multi-valued phenol, multi-valued alcohols, Polyearbonsäuren, alkenyl phenol, alkenyl phenol ether and Azomethine. Preferred the solutions contain polypñmäre amines, alkenyl phenol or alkenyl phenol ether, Azomethine or mixtures of several this Substanzen.

As suitable amines aromatic or araliphatic, more dioder tripñmäre amines with 2 to 40 C-atoms are used in the molecule. Diamines of the formula 112N are particularly well suitable in that g 1 and n the meaning indicated above have. In principle also all are the polyamine applicable, which in the FR-patent 1,555,564 was already enumerated. In detail the following polyamine are to be called as examples: it tri aminobenzene, Melamin, Tetraaminodiphenylmethan, 1,4-Diamino-cyclohexan, the Phenylendiamine, 4.4 ' - Diaminodiphenyl methane, 4.4 ' - Diamino diphenyl ethers, 4.4 ' - Diaminodiphenylsulfon and 4.4 ' - Diaminotñphenyiphosphat.

As alkenyl phenol or alkenyl phenol ether in particular Allylund Methallylphenole or the ethers the same is used. Both in-full of seeds and more-full of seeds, preferably two-fulls of seeds, alkenyl phenol and/or alkenyl phenol ether are applicable. Preferentially at least one core contains both a group of alkenyls and a phenolisehe, if necessary verätherte OH-Gruppe.

Alkenyl phenol are manufactured as well known by thermal relocation (Claisen) the alkenyl ether of Phenolen (e.g. the allyl ether of phenol). At these alkenyl ethers one arrives likewise after well-known procedures by conversion of Phenolen and e.g. AUylchlorid in presence of alkali hydroxide and solvents. As well known condensation (alkali chloride withdrawal) steps ein.

A typical two-full of seeds alkenyl phenol applicable in accordance with the invention is such the formula VIII CHz • CH = CHz (VIri) CH2-- CHCH2 in the RI and n the above meaning haben.

Also the use of Gemisehen of more-full of seeds Alkenylphenolen and/or alkenyl phenol ethers provides good results in-full of seeds Alkenylphenolen and/or alkenyl phenol ethers in accordance with the invention. As alkenyl phenol ethers prefers such substances begun, which the molecule remainder of the formula IX - O-R2, into the R2 an alkyl residue with 1 to 10 C-atoms, an aryl residue or an alkenyl residue, preferably allyl or a Methallyl, means, once or several times contained, whereby the O-atom in formula IX the phenolic ether bridge darstellt.

- A further execution form of the invention places the use of mixtures of such substances, yields only a OHGruppe and only one group of alkenyls at the aromatic core contained, with substances, which contain several OH-groups and/or several groups of alkenyls at the aromatic core ten, or of mixtures of the appropriate Phenoiäther of these substances dar.

As examples of alkenyl phenol, yield for the solutions according to invention are applicable, are the following substances to be enumerated:

0,0 ' - Diallyl bisphenol A 4.4 ' - Hydroxy-3,3' allyl diphênyl until (4-hydroxy-3-allyl-phenyl) methane 2,2-Bis (4-hydroxy-3,5-diallyl-phenyl) propane Eugenol 2ù likewise are the appropriate Methallylverbindungen usable. In place of the alkenyl phenol mentioned also the appropriate ethers these phenols, in particular the methyl ethers, are einsetzbar.

The solutions the according to invention can do such of of the general as Azomethine in particular formulas RI i R°-C =NR " (x) R' R' i I R°C =N-E-N=C-R° (xI) or R° R° i I R " - N=C-R' C =NR " (XII) contained, in those R° a hydrogen atom, a linear or branched aliphatisehen hydrocarbon remainder with up to 12 carbon flavours, a eycloaliphatischen or eycloaliphatisch aliphatic hydrocarbon remainder with up to 12 carbon atoms, an aromatic remainder with 6-12 carbon atoms, a araliphatisehen hydrocarbon remainder with up to 20 carbon atoms or a hetero-cyclic or heterocyclisehaliphatischen remainder means, R' and R " with exception of the meaning for a WasserOB material atom the same meaning as R° to have, whereby R' as well as R° under inclusion those both substituents of basic C-atom also a cyclo-aliphatic ring system to mean know and E a bivalent organic remainder with at least 2 and at the most 30 carbon atoms bedeutet.

As special Azomethine are mentioned: 1,6-Benzylidenhexamethylendiamin, N, N' Benzyliden p phenylendiamin, N, N' Benzyliden diaminodiphenylmethan, Benzyliden butylamin, Benzalanilin.

When multi-valued phenol know, multi-valued alcohols and Polycarbonsäuren the solutions according to invention all well-known phenol, alcohols and carbonic acids, which for s the production of plastics (phenolic resins, epoxy resins, polyester, PP) generally to be used, enthalten.

It is unnecessary therefore, here in more detail on this Comono (IX) meren for the mark A IMIDEs einzugehen.

619,251 as polymerization catalysts can contain the solutions according to invention ionische and radical catalysts. They should in the reaction mixture generally in a concentration from 0,05 to 10 Gew. - %, preferably from 0,1 to 5 Gew. - %, related to the entire quantity of the reacting components, vorliegen.

Under the ionischen catalysts particularly tertiary, secondary, primary amines or amines are suitable, yield several different amino groups contained (tertiary-secondary amines e.g. mixed) and quaternäre ammonium compounds in accordance with the invention. These amine catalysts can be both mono amines and polyamine. In case of a) of the use of primary and secondary amines b) mono amines are to be preferred. As examples of such amine Katalyt “are the following substances satoren to be enumerated: Diäthylamin, Tributylamin, tri ethyl amine, tri amyl amine, benzyle amine, Tetramethyldiaminodiphenylmethan, N, N-Diisobutylaminoacetonitril, N, N-Dibutylaminoacetonitril, hetero-cyclic bases, like Chinolin, N-Methylpyrolidin, Imidazol, Benzimida: l c) zol and their homologous one, and also Mercaptobenzothiazol. As suitable quaternäre ammonium compounds are for example benzyle tri methyl caustic ammonia and Benzyltrimethylammoniummethoxid too nennen.

Further suitable ionische catalysts are alkali metal compounds, like alkali alcoholates and - hydroxides. Natriummethylat.<br is particularly well suitable/> As radical polymerization catalysts are suitable well-known organic peroxides and hydraulic peroxides as well as Azoisobutyronitril. The preferential concentration amounts to also here 0.1 to 5.0 Gew. - %.

• CH-- Cil IL IL CIl C --R (xIII) to be characterized, whereby also Furan to include ist.

The remainder of R in this formula can have for instance the following BedeuùJ do towards:

- CHO - C H-Y I OH 2 “d) - CH2 OX (Y = H or an aromatic remainder) (of Y1 and Y2: aromatic remainders) of O (X = - C2 H5, - CH2 - C H--CH2, - CO' CH3, - CO " CH = CH2, - CO " C = CH2, - CO " CH = CH " CH = CH " CO, I CH3 - OZi e) - CH< 0 z2 further ones for the solutions according to invention usable polymerization catalysts are acetyl acetonate, insbeson3 the dere acetyl acetonate of the transition metals. The appropriate vanadium connection particularly is herauszustellen.

This special Polymerìsationskatalysatoren becomes also in the already above-mentioned concentration eingesetzt.

411 the solutions according to invention contains predominantly organic solvents as solvents. In principle all organic solvents are suitable, which are chemically indifferent opposite the mark A IMIDEs and/or mark A IMIDE CARBONIC ACIDs and opposite the Comonomeren. Of course the same may not also if necessary change contained catalysts in the solution unfavorably. Preferably as organic solvents acetone and methylethylketone are used. Also the use of for example water as solvents, if necessary in the mixture with organic 5 solvents, is into the invention with eingeschlossen.

Those at least a Furylrest in the molecule exhibiting connections can be in accordance with the invention firm or liquid substances. Preferably liquids are used, 5 which in the solution then practically components of the respective solvent are. They know the solvent to 0.5 to 100 Gew. - % replace; i.e. such, at least a Furylrest exhibiting, liquid substances, can do also exclusive (di and Z2 -- it predominantly concerns aliphatic remainders) with the connections stated under b) and c) substances, which by accumulation of Furfurol at phenol, in particular at until phenol or dialkyl bisphenol, producible sind.

At least a Furylrest in the molecule exhibiting connections in accordance with the invention are, as above explanation shows, also Furfurylderivate allgemein.

The solutions according to invention are predominantly used as impregnation solutions. In principle however also a use for the surface coating, i.e. in particular in the lacquer sector, is conceivable. As impregnation solutions they serve all kind for example for the production of prepregs, in particular from chopped glass fiber prepregs for plastic molding compounds. As impregnation solutions they are also favourable with the Filamentwinding procedure einsetzbar.

Both during the use and impregnation solution and with the employment effected in the lacquer sector after the evaporation of the solvent the hardening via for instance 1bis 5stündiges heating up on 100 to 300° C. thereby the groups of imides exhibiting, interlaced polymers in an educated manner • the use of the solutions for the production of such polymers is likewise article of these Erfindung.

If one wants to come to a detention-firm gluing of metals and substrates, then one proceeds in the way that one the solvent its. That meets in particular for Furfurylalkohol, 6o substrate and if necessary the surface of the body from which in the solutions according to invention is contained preferably, too. If Furfurylalkohol is used alone as solvent, then here exceptionally not the above-mentioned requirement of the chemical Indifferenz is valid opposite the mark A IMIDEs and/or mark A IMIDE CARBONIC ACIDs. “5 simplest that at least a Furylrest the connections exhibiting in the molecule can by the formula XIII metal, vorzugsweisê from copper, with a solution in accordance with the invention impregnated and afterwards under pressing both bodies together and under heating up on 100 to 300° C the polymers herstellt.

Preferably one proceeds in the way that one as substrate fibers, fabric, Nonwovens or such a thing, preferably from glass, with the solution according to invention impregnated and afterwards the received prepregs in several Schich619 251 ten one above the other stacked with the Kupferfolie hot verpresst.

In addition, as substrate can fibers, fabrics and non-woven cloths from mineral materials (quartz, Steinwolle, asbestos etc.), boron, coal and temperature-firm plastics assigned werden.

In principle the substrate can both above and down (i.e. reciprocally) with a metal foil stuck together werden.

Concerning the fibers, fabrics and non-woven cloths from glass, which with these applications of the according to invention one receives a tough, mechanically high-quality, heat resistant Schichtpressstoff.

Beispiel2 1.0 mol of N, N'-4,4' Diphenylmethan to maleinimid, 1.0 mol of Diallylbisphenol A and 2.0 mol Furfurylalkohol are brought with 120° C in solution. The solution during 4 hours with 120° C one before-reacts and one dilutes afterwards with 705 parts of Methylglycol and to ambient temperature abgekühlt.

Solutions to be used can, are to be still noticed that m the finished impregnation solution used for the production of generally in the available case also such Glasfasersubkupferbeschichteten laminate plates, whereby the just as strate best products supply, which one of the today usual finish exhibits. This finish become as well known by surface treatment of the glass fibers with substances, like Methacrylat chrome (III) - complex and Vinyl trichloroethylene (2-methoxyt äthoxy) - silane attached. In this connection “new one of glass fabric finish” is of F. Hörsch into PLASTICS 55 (1965), 909-912, hinzuweisen.

on a publication As far as copper plates with glass fiber prepregs are converted to copper-covered laminate plates, in particular for printed Schaltun2ù towards, one sets electrolytic Kupferfolien, which are modified by a Messingschicht applied superficially by means of Galvanisation, ein.

Further article are laminate plates from groups of imides exhibiting polymers and glass fiber substrates, also copper-covered, which by adhesive strengths between Kupferfolie and laminate plate (after NEMA left 1-1971) characterized from 3,0 to 5.0 sind.

Beispiet 1,1.0 mol of N, N'-4,4' Diphenylmethan to mA [in imide and 1.15 mol of D iallylbisphenol A is brought with 120° C to the melt. By addition of Furfurylalkohol at a temperature of 120° C a 50% are manufactured a ige solution. The solution is cooled down on ambient temperature. The desired 3s impregnation viscosity becomes by addition of little Furfurylalkohol on 200 cP/25° C eingestellt.

Afterwards this solution becomes the impregnation of a glass fabric with a m2-Gewicht of 280 g and Atlas connection, which as adhesion mediator a chrome III Methaerylatkomplex .m the formula che= í-% odC 0 'I Gl2 r CrCl2 • 0 ..

I ti as proceeded in example 1 wird.

Example 3,1.0 mol of N, N'-4,4-Diphenylmethan-bis-maleinimid and 0.4 mol of Diaminodiphenylmethan diluted with 80° C by means of Furfurylalkohol to a 30% igen Imprägniedösung. In such a way manufactured lmprägnierlösung is used for the production of copper-covered laminate plates. As in the example 1 it will proceed, only with the difference that minutes in the Umlufttrockensehrank it getroeknet and before-condenses wird.

Beispiel4 1.0 mol of N, N'-4,4' Díphenylmethan to maleinimid is solved with 80° C in 500 g Furfurylalkohol and cooled down on 25° C. 0.4 mol of Diaminodiphenylmethan is solved with 25° C in 200 g Methylglyeol. Both solutions are combined, mixed well and in accordance with example 3 of the production of copper-covered laminate plates verwendet.

311 example 1.3 mol of N, N'-4,4' Diphenylmethan to maleinimid, 0.4 mol of Diaminodiphenylmethan and 0.3 mol until azomethins of the N, N' Benzyliden diaminodiphenyimethan converted by means of Furfurylalkohols to a 55% igen solution. The solution is heated up 4 hours long on 1 l0° C and cooled down thereafter, the production of copper-covered plates using this solution effected completely similar to the Verfahren.<br described in example 3/> ço comparison example Diphenylmethan to maleinimid and I, 15 Moi Diallylbisphenol A with 120° C to the melt are brought to 1,1.0 mol of N, N'-4,4'. The melt is used without further additives from solvent to the impregnation of a glass fabric, as it is used in example 1. In addition the glass fabric in the dipping process is impregnated with 180° C. The developing, impregnated fabric course is long dried on it, for the reaching of a favorable flow behavior with following injecting, in a Umluftofen at a temperature of 180° C 9 minutes. The coating with Kupferfolien under simultaneous laminate disk production takes place exactly the same as in example l beschrieben.

contains, used. In addition the glass fabric in the Tauehverfahren is impregnated with 25° C and dried afterwards in a Umluftofen 8 minutes long with 180° C. 14 layers of the impregnated fabric between two 35 Micron strong Kupferfolien, which were pre-treated by superficial electrolytic Messingbesehichtung, become subsequently, hot verpresst.

The press is held afterwards first during 2 minutes under easy Kontaktdruek and the pressure on 30 kp/cm2 is increased. The Vorreaktion in the drying furnace comparison example 2,1.0 mol of N, N'-4,4' Diphenylmethan to maleinimid and 1.15 mol of Diallylbisphenol A is brought with 120° C in a reaction container to the melt. The melt during 4 hours with 120° C one before-reacts. The product “cm before-reacted is solved with 120° C in as much methyl glycol that the solution exhibits a viscosity of 200 with 25° C eP. This solution is used for the production of kupferkasehierten Lamínatplatten, whereby in accordance with the method described in example 1 proceed wird.

can be gone around by an accordingly longer time of contact in the press ùs. Vergleichsbeispiel3 after-after further 6 hours in the furnace after one hour examine bodies of the press entnom1,0 mol of N, N'-4,4' Diphenylmethan to maleinimid and men and with 240° C. 0.4 mol of Diaminodiphenylmethan reaches with 25° C by means of N619 251 Methylpyrrolidon a 50% igen impregnation solution verdünnt.

This solution is used for the production of copper-coated laminate plates, whereby in accordance with the method described in example 1 proceed wird.

Comparison example 4,1.0 mol of N, N'-4,4' Diphenylmethan to maleinimid and 0.4 mol of Diaminodiphenylmethan one determines in each case with 80° C by means of measurement of the stability in storage of the lmprägnierlösungen described in the examples and the characteristics of the copper-covered laminate plates stability in storage the time, in that itself the viscosity lmprägnierlösung with 25° C and with 40° C verdoppelt.

Bending strength in kp/mm2 the regulation takes place after ISO/R 178.

Methylglycol to a 50%igen impregnation solution dilutes. The time copper adhesion developed solution in accordance with in example the 1 describe-measured with 25° C with 150° C after NEMA left 1-1971.

nen procedures for the impregnation of glass fabrics benutzt.

The drying time amounts to in the available example however minutes. Also the subsequent treatment to copper-covered plates takes place in accordance with example 1.

Comparison example 1.3 mol of N, N'-4,4' Diphenyimethan to maleinimid, 0.4 mol of Diaminodiphenylmethan and 0.3 mol until azomethins of the N, N' Benzyliden diaminodiphenylmethan converted by means of J of methyl glycol to a 55% igen solution. The solution is heated up 4 hours long on 110° C and cooled down thereafter. The production of kupferkasehierten plates using this solution takes place completely similar to the Verfahren.<br described in example 3/> Comparison example 6 it is solved as much N, N' Diphenylmethan to maleinimid in Furfurylalkohol that a 30%ige solution vorliegt.

Water absorption in Gew. - % after 24 hours with 23° C and after 6 hours with 100° C. the measurements take place at bending inspection pieces of the VSM standard 77,103. (VSM is the abbreviation “for association of Swiss machine industrialists.) Dielectric dissipation factor (tan 8/50 cycles per second) measured with 23° C; in accordance with DIN 53 483.

Dielectric constant (E/50 cycles per second) measured with 23° C; in accordance with DIN 53 483.

The results of measurement are in the table zusammengestellt.

The values show clearly that the copper adhesion in all the cases reaches and/or exceeds 3 kp/in, in which the according to invention lmprägnierlösung are used. Is simultaneous: to recognize “that the stability in storage of these solutions sufficient largely ist.

Comparison example 6 points that the use of impregnation solutions, only one until mark A IMIDe yields, against it none thereafter as in the preceding examples impregnated ù Comonomer contains, even when using Furfurylalund with copper plates covered, kohol as solvent to no good copper adhesion führt.

¢3 table example and comparison example resin formulation 3* 4* BI (2 Ä) DADP (0.8 Ä) used solvent NMP mg duplication of the viscosity bending strength (kp/mm2) copper adhesion (kp/in) water absorption (Gew. - %) (days) with 250 C (days) with 40° C with 25° C with 150° C 24 h/23° C 6 h/100° C 12 49.8 1.9,1.4 0.18 0.38 < 1 41.0 2.6,2.7 0.28 0.32 dielectric dissipation factor tan 5,10z (50 cycles per second) 23° C 0.55 dielectric constant e 5.3 legends NMP mg FFA THF BI DADP DENT BD comparison N-Methylpyrrolidon methyl glycol Furfurylalkohol Tetrahydrofurfurylalkohol until mark A IMIDe Diaminodiphenylmethan Diallylbisphenol A N, N' Benzyliden diaminodiphenylmethan 0.55 5.1 FFA > 30 > 10 57.6 3.4,3.6 0.33 0.44 0.38% FFA % MG [!GT!] 6 > 6 62.8 3.4,3.3 0.30 0.38 0.49 1 " 2 BI (2 Ä) DENT (2.3 Ä) melt 2* 30%FFA mg % mg FFA - 200 2 233 34.9 53.0 42.5 51.5 1.95 3.0,2.3,3.2 1.45 3.6,1.9,3.1 0.19 0.24 0.24 0.14 0.44 0.37 0.33 0.37 0.42 0.36 0.57 0.42 5.4,5.5,4.3,4.9,4.7,5.1 BI DADP BD FFA > 70 5 ' (2.4 Ä) (0.8 Ä) (0.6 Ä) MG 3 51.1 2.0,2.4 0.27 0.56 0.39 4.9 6* BI FFA [!GT!] 120 > 20 37.3 2.2,2.4 1.02 1.53 0.44 5.0 O t, o oo