CA1143084A - Soluble aromatic polyamide-imide compositions for electrical use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An article for electrical use such as insulative substrates, electrical circuit boards and electrical elements, wholly or partly consisting of an aromatic polyamide-imide having a reduced viscosity of from about 0.3 to 1.5, and a composition comprising 100 parts by weight of said polyamide-imide and about 20 to 200 parts by weight of a polar organic solvent selected from the group consisting of N,N-dimethyl-formamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphoramide.

Description

BACKGl~OUND 0l~ Tl]E INV~TION
Field of the Invention This invention relates to articles for electrical use, wholly or partly consisting out of a composition comprlsing an aromatic polyamide-imlde and having excellent thermal resistance, humidity resistance, storage stability and electrical characteristics.
Description of the Prior Art .
~ ecently, large integration and high reliability have been particularly required of electronic parts, and the development of materials having excellent the Dal resistance, humidity resistance, adhesion and electrical characteristics which can be applied to the construction electronic parts has been desired, primarily because most of the known synthetic resins used for this purpose become unstable at temperatures above 250~C as their softening points are exceeded or thelr decomposition points approached. As such materials, the use of thermal resistance polymers may be considered. In general, howevert thermal resistance polymers are insoluble in most solvents and must be used in the form of their precursors. ~or example, aromatic polyamide acids which are k~own as them~al resistance polymers are susceptible to hydrolysis and inferior in storage stability or must be converted by heat treatment into aromatic polyimides or aromatic polyamide-imides having thermal resistance at a temperature around 300~C. Accordingly, these aromatic polyamide acids cannot be applied to electronic parts which are affected by heat treatment. ~urther, contamination is caused by the low molecular weight compounds formed upon heat trentment.
'

- 2 - ~

f3,4 Altlloug~ olyimldes and polyamide-imides which arc partially soluble in solv~nts are also ~nown, the practical ~eatures of most o the polylmides and po.lyamide~imides, such aq thermal resistance, humidity resistance and adhesion are inferior. Also, those polylmides and ~ 5 polyamide-imides synthesized at a temperature above 150~C are subject to partial hydrolysis and crosslinking, and it is difficult to obtain linear polymers having a reduced viscosity sufficien~ for producing the above described practical features.
Furth~r, compositions comprising silver particles and glass frits are known as compositions possessing electrical charactexistics.
However, these compositions finally require firing at a high temperature of about 500 to 1000C. Consequently it is difficult to obtain high accuracy and cost becomes high. Moreover, these compositions cannot be applied to substrates except thermal resistance substrates such as ceramics, nor to substrates mounted with electrical elements.

` SUk~RY OF THE INVENTION
An obJect of this invention is to provide articles comprisillg aromatic polyamide-imide and having electrical characteristics such as electrical conduction, electrical resistance, dielectric or insulation whose accuracyand reliability are hlgh.
According to this invention a variety of substrates are provided such as insulative substrates, boards for circuits, electrically conductive circuit boards, electrically resistanct circuit .

~ 3 -8~a boards, multi~ yer circuit ~oa)-ds, hybrld circuit boards, moun~ing circu:Lt boards and a variety of electrical elements ob~ained by using a composition comprising an aromatic polyamide-imide as an electrically conductive material, an electrically resistant material, a dielectric or insulative material, a protective material or a bonding material.
Accordingly, the present inventi.on in one embodiment provides all article for electrical use, wholly or partly consisting out of an aromatic polyamide-imide having a reduced viscosity of from about 0 3 to 1.5 and repeating units of the formula, ~ N - Ar - NU - CO ~ -CO -t NH ~ N - Ar' or Ar" - N

t Nll - Ar or Ar' - NH - CO~-CO - Nl~ T~5-3_ ~-NH ~ NH - CO ~ CO ~ N Ar' or Ar"' - N ~ ~ CO
l~ ~L~o ~ ~col~ ~ .

or 15 ~NH - A~" or Ar' - NN _ ~o~CO N~N ~CO~-CO-~

~ 4 --wherein Ar is a divalellt residue reprcrlented by the formula, ~3 ~ X--R R R R X
~X~x~x~

Ar' ls a divalent residue represented by the formula, s ~ ~ or ~t~ ~ ;
R R R R R

Ar" is a divalent residue represented by the formula, , ~ ~ or ~ ~ X

R R R
and Ar"' is a divalen.t:.residue represented by the formula, -~ X~ ~X ~ X~ X ~

R R
whereln X moieties may be the same or different and represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms;
X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a carbonylo~y groupJ a methylene group, an ethylene group or a dimethylmethylene group.

_ 5 _

3 ~ ~3 4 ~ le present invention in allot1ler embodiment provides a composition comprising 100 parts by wci~nt of an aromatic polyamide-imide as described above and about 100 to 4,000 parts by we~gllt of a granular material uniformly dispersed therein whi.ch imparts electrical characteristics S as desired to the article.
In a further embodiment, the invention provides a composltion co~prising 100 parts by weight of an aromatic polyamide-imide as described above, about 10 to 10,000 parts by weight of at least one polar organic solvent selected Irom the group consisting of N,N-dimethylformamide~
N,~-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphoramide and about 100 to 4,000 parts by weight of a granular material as described above.
~ n an even further embodiment, the invention provide various substrates such as insulative substrates, boards or circuits, lS electrically conductive circuitboards, electrically resistant circuit boards, multi-layer circuit boards, hybri.d circuit boards, mounting circuit boards and various electrical elements such as condensers and electronic elements like integrated circuits, passive elemellts, active elements and conversion elements obtained by using a composition as described above.
Of the aromaticpolyamide-imides as used in this invention, preferred ones are those in which Ar in the formulae as described above is:

~3~

or R R R R R
Ar' is:
~ ' { 1 ~ ~ or ~ X
R R R R R
Ar" is:

~ or R
Ar"' is:
~X~

R R
wherein R is a ilydrogen atom or a methyl group; and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group or an ethylene group.
10 More preferred polyamide-imides are those in which Ar in the formulae as descrlbed above is Ar' i5 ~ or ~ ~ ~ - snd Ar" is ~

~ le aromatic polyamide-imides employed in thi.s invention are preferably prepared in an organic solvent at a temperature below about 150C. When the preparation of the aromatlc polyamlde-imides is conducted at temperat:ures abovc 150CJ partial hydrolysi~ and cross-linking occur and as a resul~ linear polymers having sufficient reduced viscosity for practical use cannot be obtained. Accordingly, the preferred aromatic polyamide-imide employed in this invention are linear S polymers having a reduced viscosity of from about 0.3 to 1.5, preferably from about 0.4 to 1.3 which have been prepared at a temperature belo~
about 150C, preferably below about 130C. When the reduced viscosity of the aromatic polyamide-imides is l~ss than 0.3, the strength of a laminate or a coating used as a protective material or an encapsulation material is low and other practical features are ~lso insufficient and~
most important of all, reliability is reduced. When the reduced viscosity is higher than 1.5, it becomes difficult to obtain a solution of a high concentration and thus the workability is decreased.
The reduced viscosity of the aromatic polyamide-imide as used throughout this specification is measured at a concentration of 0 05 g of the aromatic polyamide-imide per 10 mQ of N,N-dimethylformamlde at 30C.
More specifically, the aromatic polyamide-imides used in this invention can be prepared by (a) reacting an aromatic diamine of the formula, 2 ~ 2 ~ H2N ~ ~ -NU2 ~ H2N ~ X ~ NH

R R R R

or II ~N~ X ~ X ~J X ~I~H~

' ~1~3g~

witll trimel].i.tic nnhydride monoacid chloride in a polar organic solvent at a temperature rangin~ from about 0C to about 150C in the presence of a dehydrochlorination agent and a dehydration agent such as acetic anhydride-pyridine; (b) reacting a bi~imidedicarboxylic acid ~f the formula, ~ CO N ~ ~N ~ CO ~
HOOC ~ CO''' ~ \ CO ~ COOH

~ CO - N ~ _ ~ -N ~ CO ~ ~
HOOC ~ CO'' ~ R CO ~ -COOH

~ - N~ ~ _ X ~ N ~ CO ~ `
BOOC ~ CO - ~ ~ \ CO ~ -COOH
R R

HOOC ~ CO N ~ \ CO ~ COOH ~r ~ 10 ~ CO ~N ~ X -N ~ CO ~
HOOC ~ CO'' ~ ~ \ CO ~ -COOH

R R

~ith diphenyl-3,3'-dilsocyanate or m-pilenylene diisocyanate in a polar organic solvcnt at a temperature ranging from abo~t 100C to about 150C
or (c~ r~acting an aromatic diisocyanate of the formula, . ~ ~
.

OCN -~- Ar, Arl or Ar" 3 - NCO
with a bisi.midedicarboxylic acid of the formula, ~ ~ -CO ~ N ~ ~ CO ~
HOOC ~ CO ~ ~ ~ CO ~ -COOH

or ~ CO - N ~ ~ ~ CO ~
HOOC ~ CO '' ~ CO ~ -COOH

in an organic solvent at a temperature rang~ng from about 100C to about 150C.
In the abo~e described formulae, R, X, Ar, Ar' and Ar" are the same as defined above.
The polar organic solvents which can be employed in the preparation of the aromatic polyamide-imides to be used in this invention by the above described methods (a), (b) and ~c) include N,N-dimethylform-amide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, hexame'thylphosphoramicle and any mixtures thereof.
lS Suitable dehydrocllorination agents employed in the above described method (a) include aliphatic tertiary amines such as tri~
methylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-6ec-propylamine, allyldiethylamine~ dimethyl-n-butylamine, diethyl-isopropylamine, benzyldimethylamine, di-n-octylben~yl~mine, di-n-octyl-chlorobenzylamine, dimethylcyclohexylamine, dimethylphenethylamine, ~S~3~

ben~ylmethylcthylamine, (cl-lorophenethyl~bromobenzylam5.ne, l-dimethyl-amino-2-phenylpropane and 1-dlmethylamino-4-pentane; cycllc tertiary amines such as pyridine, qui--acridines, N-methylpyrrole, N-methylpyrrolidine, N-methylpiperidine, quinoline, isoquinoline~ N-me~hyltetrahydroquinoline, N-methyltetrahydroisoquinolille and N-methylmorpl-oline~ aromatic tertiary amines such as N,N-dimethylaniline and methyldiphenylamine; and any mixtures thereof. These dellydrochlorination agents can be used in an amount suffi~ient to neutrali~e the hydrogen chloride formed.
The total amount of the reactants based on the weight of the polar organic solvent which can be preferably employed in these methods (a), (b) and (c) ranges fro~ about l to ~bout 20 % by weight.
The reduced viscosity of the aromatic polyamide-imides can be control]ed by the a~ount of the reactants to be reacted. In order to obtain a higher reduced viscosity the reactants are used ln an equimolar amount. When one reactant is used more than the other reactant, polymerization is suppressed, and accordingly the reduced viscosity of the aromatic polyamide-imide thus obtained can be controlled. Further, it is possible to control the reduced viscosity by capping the terminals of the aromatic polyamide-imide ~ith a terminating agent such as phthalic anhydride.
The aromatic polyamide-imides used in this lnvention are soluble in N,N-dimethylformamide, N,N-dimethylacetamide~ dimethyl ~ulfoxide, N-methyl-2-pyrrolidone, hexamethylphosplloramide and any mixtul~e thereof Of these polar organic solvents, N methyl-2-pyrrolidone, he~amethylpllosplloramide and nny ml~ed solvent eontaining at least about 5 percent by wcight of N-methyl-2-pyrrolidone or hexamethylpllosphoramide are preferred from the standpoint of practical features such as thermal resistance, humidity resistance, adhesion, electrical characteristics, as well as workability such as storage stability, coatabllity, laminat-ability and printability due to the crystallinity and internal stress of the aromatic polyamide-imides and the wettability of the compositions to articles to be applied therewith.
The a~.ount of the polar organic solvent which can be employed in this invention typically ranges from about 10 to 10,000 parts by weight per 100 parts by weight of the aromatic polyamide-imide.
A preferred amount of the polar organic solvent ranges from about 20 to 2,000 parts by weight per 100 parts by weight of the aromatic polyamide-imide. When the amount of the polar organic solvent is less than 10 parts by weight, the processability and the adhesion of the composition are reduced. When the amount is more than 10,000, the workability and the adhesion of the composition are reduced and pinholes are easily produced.
Especially when the amount r~nges from about 20 to 200 parts by weight per 100 parts by weight of the aromatic polyamide-imide, the composition thus obtained becomes solld or semi-solid and can be melted by heating and, as a result, can be shaped, molded and bonded by heating. The temperature of heating for shaping~ mo]ding or bonding such a composition is typically from about 50 to 300C and preferably from abou~ 100 to 200C.

4~34 .
In the present invention the granular materials which can be dispersed in thc aromatic polyamide-imide or in a composltion comprising - ~ tlle aromatic polyamide-imide and the polar organic solvent to impart electrical characterfstics thereto as specified include ~ny materials capable of rendering the aromatic polyamide-imide or the composition - electrically conductive, electrically resistant and dielectric or insulative In general, the shape or form of these granular materials may be spherical, square, needle-shaped or flaky if they are fine particles.
The particle size Df the granular materials typically ranges from about 20 R to 500 ~.
Suitable granular materials which can be employed in this invention include ~etals, metal oxides, metal nitrides, metal carbides, metal ~ilicides, silicon, silicon oxide, silicon nitrides, silicon carbides, boron, boron nitrides, carbon and mixtures thereof.
Specific examples of sui~able granular materials include Au, Ag, Pd, Ru, Pt, Rh, Ir, Tl, Mo, Zn, Mn, Mg, Cd, Cr, Nb, Ge, Zr, Cu, Ni, Al~ Sn, Pb, Bi, ID, Fe, Co, Ti, l~, Ta, Hf, Zr, Y, Ba, Be, Si, C, B, alloys thereof, oxides, nitrides, carbides and silicides thereof and mixtures thereof.
Of these ~aterials, the materials which are preferably used a5 electrically conductive granular materials, used in tllis invention include, Au, Ag, Pd, Pt, Cu, Ni, Al, Sn, ~o, Mn, Co, W, alloys thereof and mixtures thereof. Of these electrlcally conductlve granu1ar materials~ Au, Ag, Pd, Pt, Cu, Ni, Al, Sn, alloys thereof and mixtures ~ 13 _ ~14~

thereof are more preferred.
The electrically resistant granular materials which can be ` preferably used in this invention include, Ag-PdOJ A~~PdO-rd, NiO2-Ag, C-B-Ag, Ag-Pd0-S~203~ C-B, Cu2O-CuO, In2O~, In2O3-Sb2O3, T12O3, SnO2, 2 Sb2O3~ SnO2-Ta2O5, MoO3-B, ZnO, CdO-ZnO, IrO ~IO RuO TaN
TiN, TiN-Ti, TaN-Ta, WC, WC-W, C, CoSi, ZrSi, TaSi, MnSi, MoSi, NiSi, TiSi and mi~tl~res thereof.
The electrically insulative or dielectrical granular materials which are preferably used in this invention include, SiO, SiO2, Si3N4, 2 3' 2 3' Ti2' HfO2~ Zr2~ Y203, Ba~io3, BN, BeO CoO PdO
B2O3, Bi2O3, BaO and mixtures thereof. Of these materials, SiO, Si02, Si3N4, SiC, Ta2O3, A12O3, TiO2, BaTiO3, BN, BeO9 CoO, PdO~ B2O3~ Bi2O3, BaO and mixtures tllereof are more preferred.
l~e amount of the granular material which can be employed in this invention typically ranges from about 100 to 4,000 parts by weight per 100 parts by weight of the polyamide-imide. A preferred amount of the granular material ranges from about 200 to 2,000 parts by weight per 100 parts by weight of the polyamide-imide. ~len the amount of the granular material is less than 100 parts by weight, desirable electrical properties such as conductivity, resistance and the desirable dielectric properties cannot be obtained. On the other hand, when the amount of the granular material is morc than 4,000 parts by weight in the case where the solvent is not employed, cracks are disadvantageously formed.
If necessary or desired, the compositions of this inventjon may additionnlly contain a silane coupl:ing agent and/or an epoxy resin for improvin~ dispersihility of the ~ranul~r material and adhesion ` of the compositlons to articles to be applied therewith.
A fiUi table amount of the silane coupling agent is fro~ about 2 to 60 parts by welght per 100 parts by weight of the aromatic polyamide-imide and a suitable amount of the epoxy resin is from about 2 to 100 parts by weight. If the amount of the silane coupling agent or the cpoxy resin is less than 2 parts by weight, the effect of using these materials cannot be observed. With amounts larger than 60 parts by ~eight of the coupling agent or 100 parts by weight of the epoxy resin~
the thermal resistance is decreased.
The epoxy resins which can be used in this invention include any of the epoxy resins canventionally used for this purpose. Suitable examples of epoxy resins whicll can be used include those as disclosed in Hiroshi Kakiuchi as editor, Epoxy Resins, Chapters 3 & 4, Shokodo (1970~.
Such epoxy resins have at least two epoxy groups on the average per molecule and, as the residue or main chain, a carbon chain through an - ether bond, an ester bond or an amino bond.
Suitable epoxy resins are obtained by reaction of a polyhydric alcohol such as ethylene glycol, glycerin, trimethylolpropane; a polyhydrlc pl~enol such as resorcinol, hydroquinone, catechol, fluoro-glycinol; a polyphenol such as 2,2-bis(4-hydroxyphenyl)propane~
4,4'-dihydroxydiphenylmethane, novolak resi~; a polycarboxylic acid such as p-hydroxyben~oic acid, terephtllalic acid; or an amine such as o-toluidine; and excess amount of an cpoxide such as epichlorohydrin, an alkylene oxide.

~3~f.~3~84 ~ fany examples of thes~ epoxy resins are descrlbed i~ U.S.
Patcnt 2,592,560, More specifically, the epoxy resin obtuined by reaction of Bisphenol ~ and epichlorollydrin and represented by the formula:

Cl~-CI~_Cll2 ~ o ~ C ~ OU ~ ~ C ~ 2 \ 5 2 - m wherein ml is a number of 0 to 20, and a novolalc-type epoxy resin obtained by reaction of a novolak resin and epichlorohydrin, represented by the formul~:

1 2 \ & 2 ~ ~ 2 \O~ 2 O O
~C112~ 2~

wherein m2 is a number of 0 to 5, are preferably employed in this invention.
The composition of this invention comprising the granular material capable of imparting electrical characteristics thereto can be prepared by mixing the granular materlal obtained by pulverization, vacuum evaporation or chemical precipitation with the aromatic polyamide-imide ~nd the polar organic solvent and disp~rsing the granular material into the polyamide-imide by stirring until the polyamide-imide i8 completely dissolved in the polar organic solvent. A ball mlll can - 16 _ ~3~8~

: be used for disperslnr,. In thls invention the granular material sl-ould be uniformly dlspersed in the aroma~ic polyamide-imide and the polar organic solvent in such a manner as not to form lumps of the granular material.
If necessary, when thc solvent is removed from the composition thu~
obtained by evaporation, heat treatment or other methods, composition -comprising the uniformly dispersed granular material will be obtained.
All of the compositions of this invention or to be used in this invention can be prepared at a temperature as low as around 100C.
According to this invention, boards for circuits, electrically conductive circuit boards, electrically res:istant boards, insulative substrates, multi-layer circuit boards, hybrid circuit boards, mounting circuit boards, coDdensers and electrical elements such as integrated circuits, passive elements, active elements and conversion elements can be prepared using the compositions of this invention.
The term "board for circuits" as used in the description of this invention denotes a base material whose entire surface is formed of a metal foil.
The term "circuit board" denotes a base material havIng only circuit thereon.
~le term "electrically conductive circuit board" used herein denotes a base material on which an electrically conductive circuit is -Eormed.
The term "electrically resistant circuit board" used herein denotcs a base material having an electrically resistant clrcuit thereon.
The term "multi-layer circuit board" used herein denotes - ' ' ' .
- ~7 -a base materlal having at least two clectrically conductive circults or at lcast two electrically resistant circuits througll an insulation layer thereon.
The term "electrical element" used herein denotes an IC, a passive element, an active element and a conversion element, such as a monolithic IC, a hybrid ~C, a reslstor~ a condenser, a coil, a diode, a transistor, a galvanomagnetic element, a photoelectric element, thermoelectric element, a piezoelectric element and a display element.
The term "mounting circuit board7' used herein denotes a circuit board mounted with at least one electrical element thereon.
The term "hybrid circuit board" used herein denotes a base material having at least one electrically conductive circuit and at least one electrically resistant circuit thereon.
The insulative substrate can be prepared, for example, by impregnating a sheet of paper or a base material formed of glass fibers, glass cloth or carbon fibers with a composition comprising the aromatic polyamide-imide and the polar organic solvent or the composition additionally comprising an insulative granu]ar material and laminating a plurality of the impregnated base materials together, or by coating the composltion over the entire surface of a base material such as a metal, plastics, glass or ceramic or coating or printing the composition pattern-wise on the base materlal, or by laminating a film obtained by removing the polar or~anic solvent from the composition over the entire - surface of the baGe material or pattern-wise on the base material; or by moldlng the composition in ~ dPsired mold ~ 18 -3L~Lt~

~lc board for clrclllts can be prepared, for example, by adhering a metal foil capable of bclng etched (e.g.~ copper foil) to the entire sur~ace of a basc material (e.g., a plastic film like a polyimide film) with the composition comprising the aromatic polyamide-imide and the polar organic solvent or the composition of thls invention additionally comprising the insulative granular material. By etching the metal foil thus adhered in a desired pattern, there can be obtained a circuit board.
By adhering a metal foil such as copper foil already cut in a circuit pattern to the base material witil the composition there can also be obtained a circuit board.
~le electrically conductive circuit board can be prepared, for example, by printing a composition comprising the aromatic polyamide-imdie, the polar org2nic solvent and the electrically conductive granular material on the insulative substrate in a circuit pattern and removing the polar organic solvent from the composition containing the conductive granular material by heating, or by laminating a film obtained by removing the polar organic solvent irom the composition containing the conductive granular material on the insulative substrate in a circuit pattern.
'~le electrically resistallt circuit board can be prepared, for example, by printing a composition comprising the aromatic polyamide-imide, the organic polar solvent and the electrically resistant granular ~aterial on the insulative substrate in a circuit pattern and removing - the organic polar solvent from the composition by heating, or by 2S lamillating a film obtained by removing the polar organic solvent from 3~4 the composition on the insulative substrate in a clrcuit pattern.
The multi-layer circuit board can be prepared, ~or ~xample, by coating or printing a composition comprising the aromatic polyamide-imi.de and the pol~r organic solvent or the composition additionally comprising the insulative granular material over the entire sur~ace of the electrically conductive circuit or the electrically resistant circuit or on the areas thereof to be multi-layered or pattern-wise on the electrically conductive circuit or the electrically resistant circuit in the case of through-hole connections and removing the polar organic solvent from the composition by ~leating, or by lamlnating a film obtained by removing the polar organic solvent from the composition over the entire sur~ace of the electrically conductive circuit or electrically resistant circuit or pattern~wise on selected areas thereof to be laminated and further ~orming an electrically conductive circuit or an electrically resistant circuit thereon in the same manner as in preparing an electrically conductive circuit board or an electrically resistant board.
The hybrid circuit board can be prepared by forming an electrically conductive circuit and an electrically resistant circuit on an insulative substrate in the same manner as in preparing the multi-layer circuit board.
The circuit board having a protective layer thereon can be prepared by coating or printing a composition comprising the aromatic polyamide-imide and the polar organic solvent or the composition additionally comprising ttle insulative granular material on at least - 20 _ .

3~4 part of the sllracc of ~lle c.l.ectrically collductive circuit board, the - clectri.cally rcsistant circuit board, tl,e multi-layer circuit board or the hybrid circuit board and removing the polar organlc solvent from the composition by heatlng, or by laminating a film obtained by removing the polar organic sol.vent from the composition over the entire surface of the aforementioned circuit board or pattern-~ise on the surface of the above described circuit board.
l~e mounting-circuit board can be prepared by bonding electrical elements to the circuit of the circuit board with a composition comprising the aromatic polyamide-imide, the polar organic solvent and the electrically conductive granular material by a method such as die bonding, or by bonding the electrical elements to the insuiative ~ubstrate with a composition comprising the aro~atic polyamide-imide, the polar organic solvent and the insulative granular material snd then lS bonding the electrical elements to a circuit on the insulative ~ubstrate by a method such as wire bonding.
The condenser can be prepared by coating or printing a composition comprising the aromatic polyamide-imide, the polar organic solvent and the dielectric granular material unifonnly dispersed therein on an electrode such as a metal and then providing another electrode thereon and removing the po].ar organic solvent from the composition by heating, or by laminating a film obtained by removing the polar organic solvent from the composition on an electrode and then providing another elcctrode thereon, or by cvaporating or spattering.a metal on both surfaces of ~. film obtained by removing the polar organic solvent from _ 21 -.
the compositioll, or by coating or prin~ g a compositioll comprising tlle aromati.c po].yamide-imide, the pol.ar organic solvent and the electrically conductive granlllar materlal uniformly dispersed therein on both surfaces of the film and removing the polar organic solvent S from t1-e composition by heating~ .
The electrical element having a lead wire can be prepared by bcnding the electrical elements such as integrated circuits, passive elements,.active elements and conversion elements to a lead ~ire such as a metal frame with a composition comprising the aromatic polyamide-imide, the polar organic solvent and the electrically conductive granular material and re;noving the polar organic solvent from the composition ~y heating.
~he encapsulated electrical elements can be prepared by . iT~ersing-integrated circuits, passive elements, active elements and conversion elements in a composition comprising the aromatic polyamide-imide and the polar organic solvent or the composition additional~y comprising the insulative granular material uniformly .
~ dispersed therein and removing the polar organic solvent from the composition by heating The compositions as described have excellent thermal resistance, humidity resistance, adhesion, storage stability and electrical characteristics, and also the various substrates, circuit boards and electrical elements obtained by using the composi.tions have excellent thermal resistance, humidity resistance and higll accuracy and reliability Especially thermal resistance and humidity resistance .

are important to clectronic parts from the standpoint of rcliability.
'rhe following Examples arc given to illustratc the present invention more specifically. All parts in these Examples are by weight.
Electrical resistances in these Examples are measured by "Universal Digital Meter 2502" (tradename, manufactured by Yokogawa Electric Works Ltd.).
Example 1 & Comparative Example 1 Each o various base materials as set forth in Table 1 was im~regnated with a composition of 100 parts of an aromatic polyamide-imide as set forth in Table 1, 600 parts of N-methyl-2-pyrrolidone and 400 parts of N,N-dimethylacetamide, and then subjected to heat treatment firstly at 100C for 3 hours and secondly at 150C for 2 hours.
Ten sheets of the resulting impregnated base màterial were superimposed and press-molded at 200C and 100 Kg/cm for 30 minutes to form a thermally resistant substrate having a size of 30 cm x 30 cm x 1.6 mm.
The substrate thus obtained was subjected to a thermal resistance test at 400C for 30 minutes. The substrate had excellent thermal resistance and dimensional stability with very small reduction in weight as ~set forth in Table 1 and was obtained without warping. Further, the substrate withstood die-bonding at 400C. Reduction in weight was calculated fron the following equatioll~

, Weight of Substrate before Weight of Substrate after Reduction in Thermal Resistancc Test Tllermal Resistance Test x 100 Weight of Substrate before Thermal R~sistancc Test ' o~
v ~ ~ o~ u~ o ~ ~
O Q~ i~
C~ a _~ ~ ~
~a rl O r~ o ~ 00 o ~n O ~1 O ~1 0 0 C~ P
o~ ~

o oC~ C~ o o ~
r oO O ~ O

.~ ~I h ) I JJ
~ U ~ ~
~ V I V S~ CJ E3 4~ Q\
a a hO
o o d ~ ~0 -- 2l~

R ~
~ ~
bO ~_ ,_~ 1~ ~ ~ O .
, 2 b~
'rJ ~_ rl ~ ~U b~ ~
~ C~ ~ 00 ~ O ~
~ b'') C~ . O ~i ~ O
~ P ~
' ' ' . ' o ~4 ,t, ~ I ~ 1 ~ 3 ~ ~ 3 ~z~
V >~ b'~ /=-\ ~Z; ~ I I 'i:3 _, ~o ~ \
~ ~ ~b ,~ o ol ~ ~
~ ~ .~ , ~ o .. ~ , ~ ~ Z o ~, rJ ~ / /
~d E~ ~ O O ~ / ~ I
~ O b--J t~ t~ O O ~ a) ~ ~ 3 b--J t~ *
QJ 'r~ r~ O O O O
V JJ ~ ~ _ ~4 ~ ~
f~
' ~ .

1~

.- 2S .-3~34 Exam~le 2 On each of various base materials wa.s coated a composition of100 parts of an aromatic polyamide-imide as set forth in Table 2, 600 parts of ~-methyl-2-pyrrolidone and 400 parts of N,N-dimethylacetamide S and dried in vacuum at 100C for 3 hours to form an aromatic polyamide-imide laminate whose surface was smooth. h~hen the aromatic polyamide-imide surface of the laminate was contacted with melted solder at 260C
for 20 seconds or immersed in a 1 % potassium hydroxide aqueous solution for 24 hours, no change such as swelling was o~served and the thermal resigtnace, the adhesion and the alkali resistance of the aromatic polyamide-imide coating were good. Further, the surface resistance of ~he aromatic polyamide-imide side of the laminate after treatment at 50C and a relative humidity of 90 % for 3 days was measured in accordance with the procedure of JIS C6481-1968.
The results are shown in Table 2.

- 2~ _ a) ~ I ''~ ~D
~d 'J ^ ~ ~ X P:
:~ a) o - .~ o ~ U~
U~ O
a~ ~o .
.~ ,~ ô ~ o~ ~ ~
~ C7 . , ,~

3 , ~ .i ~;`ô ~ ~, a~ ~ ~ ~ a p~ 3 ~ ~ a~
d a~

~ Z~

~o ~o ~c~ ~o x ~q x x -~ ~ o o u~

al oo ~ _, u~ ~1 ô

'~ r ~

a U ~ c 2~ -~ D
a) ~ o~
~ u~ c~
u) n ~ ~ ~J . ' ~aq ~3 ô o C) o ~J a. ~ ~
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3~34 Example 3_& Comparative Example 2 A polyimide film having a thickness of 75 1l (trademark "Kapton", made by E. I, du Pont de Nemours and Company) was adhered to an electrolytic copper foil having a thickness of 35 ~ whose sl~e was the same as the polyimide film in Run Nos. 1 to 5 and in Comparative Example 2 and which was punc1led in a circuit pattern in Run Nos. 6 to 10 using a solid or a semi-solid composition of an aromatic polyamide-imide and a polar organic solvent as set forth in Table 3 by heat pressing firstly at 150C
for 30 minutes and secondly at 200~C for 30 minutes. Then the article was subjected to thermal resistance test at 400C for 30 minutes. The copper foil peeling strength after the thermal resistance test is shown in Tab~e 3.
The article thus obtained had excellent thermal resistance and adhesion strength. The peeling strength was measured in accordance with the procedure of JIS C6481-1968. Also the inflammability resistance was measured in accordance with the procedure of JIS C6481-19689 and the results were excellent.

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- 33 _ Ex~mple 4 & Comparative Example 3 -A copper plate was bonded to a copper wire having a diameter of 1 mm using a compositions of an aromatic polyamide-imide and a polar organic solvent as set forth in Table 4 at 150C for one hour. Then S the article thus bonded was subjected to a thermal resistance test at 400C for 30 minutes. The adhesion strength after the thermal resistance test is sho~ in Table 4.
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_x mplc 5 A sol~d or semi-601id composition was prepared from an aromatic polyamide-imide and a polar or~anic so]vent as set forth in- Table 5, tllen press-molded.firstly at 150C for 30 minutes and secondly at 200C
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The results are sho~m in Table 5. The film had excellent electrical properties and humidity resistance.

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Example 6 To 240 parts of N-mcthyl-2-pyrrolidone and 1~10 parts of N,N-dimethylacetamide werc added 100 parts of an aromatic polyamide~imide havlng a reduced viscosity of 0.5 synthesized from m-phenylenediamide and S trimellitic anhydride monoacid chloride and dissolved therein. Then to the solution were added 400 parts of super-fine silver particles having an average diameter of 700 g prepared by vacuum evaporation and uniformly dispersed therein by a ball mill to give a paste. In order to test its electrical conduction the paste was screen-printed on an alumina base plate to form 20 electrically conductive lines having a width of 1 mm, a length of 2 cm and a thickness of about 50 ~ and subjected to heat treatment at 100C for 30 minutes to sufficielltly remove the solvents.
The electrical resistance of one line of the pattern thus formed was -~
0.2 Q or less and its adhesion to the base plate was good.
~urther, in order to test the thermal resistance of the line, the resulting article was subjected to heat treatment at 400C for one hour. The electrical resistance of the line thus treated was 0.3 Q
or less ar.d hardly any change was observed after the heat treatment, and the lines did not peel off from the base plate and their adhesion was excellent.
Example 7 To 500 parts of N-methyl-2-pyrrolidone were added 100 parts by weight of an aromatic polyamide imide having a reduced viscosity of 0.7 synthesized from 4~4~-di(m-aminop1lenoxy~dipllenyl ether and trimellitic anhydride monoacid chloride and dissolved therein. Then to the solution , were nddecl 250 par~s of a fine metal ml~ture of super-fine sllver ~articl.es havin~ an average diametcr of 700 A prepared by vacuum evaporation and palladium particles havil1g an average diameter of O.S
at a l : l wei.ght ratio and uniformly dispersed therein by a ball mill to give a paste The paste thus obtained was treated in the same manner as in ~xample 6. The electrical resistance of the line thus prepared was 0 3 Q or less and its adhesion was good. Furi:her, the resulting article was subjected to the same heat treatment as in Example 6.
The clectrical resistance of the line was 0.4 Q or less, and the lines did not peel off from the base plate and their adhesion was excellent.

~ o 400 parts of N,N-dimethylacetamide were added 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.4 synthesized from 3,3~-diaminodiphenyl and trimellitic anhydride monoacid chloride and lS dissolved therei11. Then to the solution were added 400 parts of fine ruthenium oxide particles havin~ an average diameter of 0.8 ~ and uniformly dispersed therein by a ball mill to give a paste. In order to test its electrical resistance the paste was screen-printed on an alumina base plate to form 20 electrically resistant lines having a width of l mm, a les1gth of 2 cm and a thickness of about S0 ~ and subjected to heat treatment at 100C for 30 minutes to suffici.ently remove the solvent. The electrical resistance of one line of the pattern thus formed was 20 KQ and its adhesion to the base plate was good.
Further, in ordcr to test tl1e therD1al resistance of the line, the resulting article was subjected to heat treatment at 400C for - 43 _ 30 m.inutes '111c electrical resistance of the line thus tr~ate;d was 20 K~ and no change was observed after the heat treat:ment, and the llnes did not peel off from the base plate and their adhesion was excellent.
. xample 9 S A paste was prepared by uniformly dispersing b~oO parts of fine copper particles having an average particle diameter of 10 ~ in a solution of 100 of an aromatic polyamide-imide having a reduced viscosity of 0,3 synthesized from 2,4-tolylenediamine and trimellitic anhydride monoacid chloride, 10 parts of an epoxy resin (trade naMe "AER-669", manufactured by Asahi Chemical Industry Co., Ltd.) and 500 parts of N~methyl-2-pyrrolidone. The paste was screen-printed pattern-wise on a glass-epoxy laminate and then subjected to heat treatment at l50DC for 30 minutes to give a print circuit substrate. The electrical conductor thus obtained had a resistivity of 2.0 x 10 4 Q-cm and withstood soldering lS at 270C for 60 seconds and its adhesion was also good.
Example 10 . A paste was prepared by unifonnly dispersing 350 parts of fine silver particles having an average particle diameter of 1.8 ~ in a solution of 100 parts of an aromatic polyamide-imidc having a reduced vlscosity of 0.8 synthesized from a bisimidedicarboxylic acid having been prepared froM 4,4'-diaminodibenzyl and trimellitic anhydride monoacid chloride and 3,3'-diisocyanate diphenyl, 240 parts of N-methyl-2~pyrro].idone and 160 parts of N,N-dimethylacetanide. The paste was screen-printed pattern-wise on a polyimide film and then subjected to heat treatment at lOODC for 30 minutes to give a print circuit board.

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~hc electrical conductor thlls ob~aille(l had n reslstivity of 4,5 x lO Q,cm And wlthstood thermal resistance ~est at 400C for 30 minutes and its adhesion was also good.
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S A paste was prepared by uniformly dispersing 200 parts of fine carbon particles having an average particle diameter of lO ~ and 200 parts of fine boron particles having an average par~icle diaMter of 20 ~ in a solution of lO0 parts of an aromatic polyamide~imide having a reduced viscosity of 0.6 synthesized from a bisimidedicarboxylic-acid having been prepared from p-phenylenediamine and trimellitic anhydride and 3,3'-di-isocyanate dlphenyl, 240 parts of N-methyl-2-pyrrolidone and 160 parts of N,N-dimethylacetamide. The paste was screen-printed on a glass plate to form lines having a width of l ~n, a leng~h of 2 cm and a thickness of about S0 ~ and then subjected to heat treatment at lOO~C for 30 minutes to give an electrical resistance circuit. The resistor thus obtained had a resistance of 500 Q and withstood thermal resistance test at 270C
and its adhesion was also good.
x~nple 12 A paste was prepared by uniformly dispersing 450 parts of fine indium oxide having an average particle diameter of 20 ~l in a solution of lO0 parts of an aromatic polyamide-iMide having a reduced viscosity of 0.5 synthesized from a bisimidedicarboxylic acid haYing been prepared from 3,3'-diaminodiphenyl and trimellitic anhydride and 4,4'-diisocyanate dip}lenyl methane and 300 parts of N,N-dimethylacetamide.
Tlle paste was screen-printed on a polyimide film to for~ lines having a .

width of 1 mm, a length of 2 cm nnd a thiclcness of about 50 ~ and then subjec~ed to hea~ treatment at 100C for onc hour to give an electrical resistance circuit. The resistor thus obtained had a resistance of 10 KQ
withstood thermal resistance test at 270G and its adhesion WaS also good.
S ExamRle 13 100 parts of an aromatic polyamide-im~de having a reduced viscosity of 1.5 synthesized from a bisimidedicarboxyLic acid having been prepared from 3,3'-diaminodiphenyl and trimellitic anhydride and 294-toluylenediisocyanate were added with 240 parts of N-methyl-2-pyrrolidone and 160 parts of N~N-dimetllylacetamide and dissolved therein. Then to the solution were added 300 parts of tantalum nitride having an avarage particle diameter of 20 ~ and uniformly dispersed by a ball mill to give a paste. The paste thus obtained was treated in the same manner as in Fxample 6 and the resistance was 50 KQ and the adhesion was good~
Further, in order to test its thermal resistance the resulting article was subjected to heat treatment at 400C for 30 minutes. The resistance and the adhesion did not change Example 14 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0 5 synthesi~ed from m-pl-enylenediamine and trimellitic anhydride monoacid chloride were added with 300 parts of N,N-dimethyl-acetamide and dissolved therein. Then to the solution were added 450 parts of tungsten carbide having an average pnrticle diameter of 20 and uniformly dispersed thcrein by a ball mill to givc a paste The paste thus obtained was screen-printed in the same manner as in Example 6 and subjected to heat treatment at 100C for onc hour, ~le resistancc was 10 ~Q and the adllesion was good.
Xn order to test its thermal resist:ance the resultin~ article was subjected to heat treatment at 400C for 30 minutes. The resistance and the adhesion did not change.
Example 15 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.8 synthesized from m-phenylenediamine and trimellitic anhydride monoacid chloride were added w;th 240 par~s of N-methyl-2-pyrrolidone and 160 parts of N,N-dimethylacetamide and dissolved therein.
Then to the solution were added 300 parts of fine particles having an average particle diameter of 20 u prepared by heating 270 parts of tantalum silicide and 30 par~s of aluminium at 1200C for one hour in a nitrogen atmosphere and uniformly dispersed by a ball mill to give a thermal resistance resistor paste. ~len the paste was treated in the same manner as in Example 6, the resistance was 10 KQ.
Then, in order to test its thermal resistance, the resulting - article was suojected to heat treatment at 400C for 30 minutes. ~le resistance did nOt change after the heat treatment and the lines did not peel off from the base plate and their adhesion was excellent.
Example_16 A paste was prepared by uniformly dispersing 400 parts of fine aluminium oxide part-icles having an average particle diameter of 0.8 ~
in a solution of 100 parts of an aromatic polyamide-imide having a reduced ~iscosity of 1.0~synthesized from a bisimidedicarboxylic acid havillg`bee~

prcpared from 4,4'-dlaminodiphenyl c~llcr and trimellitic anhydride and 3,3'-diisocyallate diphenyl, 2 parts of a silane coupling agent (tradc name "A-llO0", manufac~ured by Nippon Unicar Co., Ltd.)~ 10 parts of an epoxy resin (trade name "~ER-669", manufactured by ~sahi Chemical Industry Co., Ltd.? and 500 parts of N-methyl-2-pyrrolidone. The paste thus obtained was coated on the entire surface of an alumina base plate at a thickness of 5 ~ and then subjècted to heat treatment at 150C for 30 minutes to give an insulative substrate. The insulative substrate thus obtained withstood thermal resistance test at 400C and the adhesion was good.
Example 17 A comporision was prepared by uniformly dispèrsing 400 parts -of silicon dioxide having an average particle diameter of 10 11 in a solution of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 1.2 synthesized from m-phenylenediamine and trimellitic anhydride monoacid chloride and 500 parts of N,N-dimethylacetamide.
The composition thus obtained was poured in a mold and tllen subjected to heat treatment firs,tly at lOO~C ~or one llour and secondly at 200C for one hour to give an insulative substrate llaving a size of 30 cm x 30 cm x 0.5 mm. ~he insulative substratP withstood thcrmal resistance test at 400C for 30 minutes, and no warping was observed and dimensional accuracy was good.
Example 18 100 parts of an aromatic polyam;de-imide having a reduccd viscosity of 0.7 synthesized from a bisimidedicarboxylic acld prepared from ~ 48 _ 3l~4~

~dlaminodipllenyl sulonc and trimcllltic anllydride and 3,3~-diiso-cyanatodiphenyl were added wiLh 5 parts of a silane coupling a~ent (trade name "A-llO0", manufactured by Nippon Unicar Co., Ltd.) and 400 parts by weight of dimethyl sulfoxide and dissolved therein. Then to the S solution were added 500 part.s of fine gold particleshaving an average particle diam~terof 5 ~ and uniformly dispersed by a ball mlll to give a paste. The paste thus obtained was screen-printed in the same manner as in Example 6 and then subjected to heat treatment at 150C for 30 minutes.
The resistance was 0.2 Q or less and the adhesion was good.
When the thermal resistance was tested in the same manner as in Example 6, the resistance was 0.2 Q or less, and the lines did not peel from the base plate snd their adhesion was excellent.
Exam~
100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.5 synthesized from a bisimidedicarboxylic acid having been prepared from ben~idine and trimelLitic anhydride and 3,3'-diisocyanate diphenyl were added to 500 parts by weight of N,N-dimethylformamide and dissolved therein. ~len to the solution were added 500 parts of fine nickel particles having an average particle diameter of 3 ~ and uniformly dispersed by a ball mil:L to give a paste The paste was thus obtained was screen-printed in the same manner as in Example 6 and then subjected to heat treatment at 100C for 30 minutes. The resistance was 0.3 Q or less and the adhesion was good.
~len the thermal resistance was tested in the sa~ne manner as in Example 6, the resistallce was 0.4 Q or less, and the lines did not peel - _ 49 _ ~3~4 from the base plntc and their adhesion was excellent, Example 20 100 part~ of an aromatic polyamide~imide havillg a reduced viscosity of 1,0 synthesized from 3,3'-diaminodiphenyl methane and trimellitic anhydride monoacid chloride were added to 400 parts of hexamethylphosphoramide and dissolved therein, Then to the solution ware added 400 parts of fine t n particles having an average particle diameter of 5 ~ and uniformly dispersed by a ball mill to give a paste, The paste thus obtained was screen-printed in the same manner as in Example 6 and subjected to heat treatment at 150C for 30 minutes, The resistance was 0,3 Q or less and the adhesion was good.
When the thermal res;stance was tested in the same manner as in Example 6, the resistance was 0,3 Q or less, and the lines did not peel from the base plate and their adhesion was excellent.
Example 21 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0,4 synthesized from a bisimidedicarboxylic acid prepared from 3,3'-diaminodiphenyl and trimellitic anhydride and 3,3~-diisocyanato-diphenyl were added to 400 parts by weight of N,N-dimethylacetamide and dissolved therein, l~len to the solution were added 500 parts of fine SnO2 particles having an average particle diameter of 10 ~ and uniformly dlspersed therein by a ball mill to givc a paste, The paste thus obtained was screen-printed in the same manner as in Example 6 and then subjected to heat treatment at 100C for 30 minutes. The resistance was 10 KQ. ~le resulting article withstood thermal resistance test at 4C0C

. - 5Q -fox 30 minut:es ~nd the adhesiorl was ~ood.
E.xaml)le 22 100 parts of an aromatic poly~l~lde-imide having a reduced viscosity as set fortll in Table 6 synthesized from m-phenylenediamine and trimellitic anhydride monoacid chloride were added to 400 parts of N-methyl.-2-pyrrolidone and dissolved therein. Then to the solution were added 400 parts o~ fine particles having an average particle diameter of S ~ as set forth in Table 6.and uniformly dispersed there.in by a ball m_ll to give a paste. The paste thus obtained was screen-printed in the same manner as in Example 6 and then subjected to heat treatment at 150C for 30 minutes The resistance, the heat resistance test at 400C for 30 minutes and the adhesion are set forth in Table 6.
Table 6 Reduced Viscosity of Thermal Run Polyamide- Fine Resistance No. imide. Particles Resist~nce TestAdhesion . ~
15 1 1 5 T1203 20KQ No challge Good 2 0.8 C 300Q -ditto- -ditto-3 0.5 TiN 40KQ -di-.to- -ditto-4 0.7 MoSi lSKQ -ditto- -ditto-Example 23 .20 100 parts of an aromatic polyamide-imide havin~ a reduced viscosity ~s set forth in Table 7 syntllesi~cd from m-phenylenediamine and trimellitic anhydride monoacid chloride were added to 400 parts $~

N,N-dimetllylacetamide and dissolved therein. ~len to the solution were added 400 parts of fine particles havlng an average particle diametcr of 10 1l as set forth in Table 7 and uniformly dispersed by a ball mill to give a paste. The pastc thus obtained was treated ln the same manner as in Example 17. The thermal resis~ance test at 400C for 30 minutes and the dlmensional accuracy are set forth in Table 7.
Table 7 Reauced Viscosity of Thermal Run Polyamide- Fine Resistance Dimensional No. im e Particle Test Accuracy 1 0.5 TiO2 No change Good 2 0.4 BeO -ditto- -ditto-3 1.0 Si3N4 -ditto- -ditto-4 0.8 BaTiO3 -ditto- -ditto-Example 24 .

Various pastes were prepared in the same n~anner as in Example 6 lS except that 100 parts of an aromat:ic polyamide-imide synthesized from an aromatic diamine as set fortll in Table 8 and trimellltic anhydride monoacid chloride and granular materials for giving electrical characteristics as set forth in Table 8 were used. The results of evaluatlon of these pastes ln the same manner as in Example 6 are set ~0 forth in Table 8, and the lines thus formed-had excellent thermal resistance and adl~esion.

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Pxamp]e ~5 Various pastes were prepared in the same manncr as in ~xamplc 17 except that 100 parts of an aromatic polyamide-imide syntllesized from a bisimidedicarboxylic acid obtained from an aromatic diamine as set forth ln Table 9 and trimellitic anhydride and 3,3'-diisocyanate diphenyl and 400 parts by weight of granular materials for imparting electrical characteristics having an average particle diameter of 10 ~ as set forth in Table 9 were used. The results of evaluation of these paste in the fiame manner as in Example 17 are set forth in Table 9 and the insulative substrates thus obtained had excellent thermal resistance and adhesion.

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Variou~ pastes were obtained in the same manner as in Exaulple 6 ~except that 100 parts of an aromatic polyamide~ lide synthesi~ed Irom a bisimidedlcarboxylic acid prepared from 3,3'-diaminodiphenyl and trimellitlc S anhydride and an aromatic diisocyanate as set forth in Table 10 and granular materials for giving electrical. cha~.acteristics as set forth in Table 10 were used. The results of evaluation of these pasLes in the same manner as in Example 6 are set forth in Table ]0, and the lines had excellent tl-ermal resistance and adhesion.

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al l lll , ~d -- 58 _ ~xample 27 On a circuit board having a circuit of tlle first layer obtained by etching a copper-clad laminate where tlle thickness of the copper layer was 3S ~ was screen-printed a composition of 100 parts of an S aromatic polyamide-imide having a reduced viscosity of 1.0 and repeating units of the formula, ~ ~ NII-CO- ~ CO ~

600 parts of N-methyl-2-pyrrolidone and 400 parts of N,N-dimethylacetamide at a dry thickness of 50 ~ and then subjected to heat treatment at 150~C
for one hour to form an insulative layer for crossover. On the insulative lay~r was screen-printed a composition of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.5 and the same repeating units as described above, 30G parts of N-methyl-2-pyrrolidone, 200 parts of N,N-dimethylacetamide and SOO parts of fine silver particles h2ving an average particle diameter of 1.8 ~ at a dry thickness of 30 ~ and then subjected to heat treatment at 150C for 30 minutes to form an electrically conductive circuit of the second layer whose resistivity was 1.6 x 10 Q-cm.
The insulative resistance of the insualtive layer measured by impressing a voltage of 100 V to the circuits of the first and second layers was 2 x 106 ~iQ, On the resulting circuit board havillg two layers of circuits was screen-printed a composition consisting of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 1.0 and the same repeating ~mits as described above, 600 parts of \-meLhyl-2-pyrrolidone ancl 400 parts of N,N-dime~hylaceLamide at a dry thickness of 100 ~ and then subJected to heat treatment a~ 150~C for one hour to form a protective layer. The multi~layeL- clrcuit board thus obtained after the stability test at 70C at a relative humidity of 90 % for 1,000 hours showed excellent stability without any change in the resistivity of the electrically conductive layer and the insulatlve resistance of the insulative layer.
Exc~ple 28 On a glass-epoxy laminate was screen-printed a composition of 100 parts of an aromatie polyamide-imide having a reduced viscosity of 0,6 and repeating units of the formula, ~ N ~ ~-CO ~ CO -~-300 parts of N-methyl 2-pyrrolidone, 200 parts of N,N-dimethylacetamide and 500 parts of fine silver particles having an average particle diameter of 1.8 ~ at a dry thicklless of 40 ~, and subjected to heat treabnent at 150C for 30 minutes to form an electrically conductive circuit whose resistivity was l.S x 10 Q.cm. Then on the electrically conductive circuit thus obtained was screen-printed a composition of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.8 and the same repeating units as described above, 400 part.s of N-methyl-2-pyrrolidone and 400 part~s of fine particles of carbon having an avera~e diameter of 5 ~ at a dry thiclcness of 40 ~ and a size of 1 m~ (width) x 2 cm (lengtll) and subjectecl to heat treatment at 150C for 2 I-ours to form a resistant circult whose resistance was 400 Q. Further~

on the resultlng hybri(l circui.t board was screen-printed a composition of lO0 parts of an aromatic polyamide-imide having a rcduced viscosity of 1 0 and the same repeating units as describcd above, 600 parts o N-metllyl-2-pyrrolidone and 400 parts of N,N-dimethylacetamide at a S dry thickness of 100 ~ to form a protective layer. The hybrid circuit board thus obtained after the stability test at 70C at a relative humidity of 90 % for 1,000 hours showed excellent stability without any change in the resistivity of the conductive ci.rcuit and the resistance of the resistant circuit Example 29 A GaPAs light emission diode was bonded to a lead wire of a - metal frame with a composition of lO0 parts of an aromatic polyamide-imide having a reduced viscosity of 0 4 and repeating units of the formula, _X== ~ ~ -N~l-C0 ~ C ~ .

2S parts of an epoxy resin (trademark "AER-331", made by Asahi Chemical Industry Co., ~td ), 400 parts ol N-methyl-2-pyrrolidone and 500 parts of fine sllver particles havillg an average diameter of 1 8 ~I by heat treatment at 150C for 30 minutes The article thus bonded withstood the wire bonding at 350C for 2 minutes.
Example 30 A silicon-tantalum resistor was immersed in a composition of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 1.0 and repeat~ng units of the formula~

_~ N~N~-cO~co )~

600 parts of N-metllyl-2-pyrroli(1One and 400 parts of N~N-dimet:hylacctamide and then subjectcd to heat t~reatment a~ 150C for 30 minutes. The ratc o change in resistance of the resistor thlls obtaincd after the stability test at 70C and a relative humidity of 90 ~ for 1,000 hollrs was at most O.l ~, and thus the resistor showed excellent stabili,ty.
Example 31 A composition of 100 parts of an aromatic polyamide imide having a reduced viscosity of l.O, 1,200 parts of N-methyl-2-pyrrolidone and 800 parts of N,N-dimethylacetamide was subjected to heat treatment firstly at 150C for one hour and secondly at 200C for one hour to form a film having a thickness of 10 ~. On both surfaces of the film silver was spattered to a thickness of 1 ~ at a si~e of 1 cm x 1 cm to prepare electrodes. The condenser thus prepared had a capacity of 4 x 10 ~IF
and withstood the thennal resistance test at 400C for 30 minutes.
lS ~xample 32 A composition of 100 parts of an aromatic polyamide-imide having a reduced viscos:ity of 0.5 and repeating units of the formula, D N ~ -NII-CO ~ CO ~

300 parts of N-methyl-2-pyrrolidone; 200 parts of N,N-dimcthylacetamide and 500 yarts of fine silver particles having an average particle diameter of 1.8 1I was adllered to a s,ilicon chip. The chip thus obtained was bonded to an alumina ceramic board with the same camposition as described above, and then subjccted to heat treatment at 150C for one hour.
When the resulting article ~as placed on a llot ylate at 400~C and jerked by .~ pull gallge at a forcc of 50 g, the artlcl.e did not peel off and had excellent thermal resistance and adhesion.
Example 33 An alumina ceram~c circuit board obtained by firing a Ag-Pd paste for preparing thick film~s by firing at high temperatures was bonded to a light emission diode with a co~position of 100 parts of an aromatic polyamide-imide having a reduced viscosity of 0.6 and repeating units of the formula, N~ _co~CO ~

300 parts of N-methyl-2-pyrrolidone, 200 parts of N,N-dimethylacetamide and 500 parts of fine silver particles having an average particle diameter of 1.8 ll by heat treatment at 150C for one hour. The article thus bonded withstood the wire bonding at 350C for 2 minutes.
W~ile ~he invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one ~illed in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
This application is a division of copending Canadian application Serial No. 321,623, filed February 16, 1979.

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Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A solid or semi-solid composition comprising 100 parts by weight of an aromatic polyamide-imide soluble in a polar organic solvent and having a reduced viscosity of from about 0.3 to 1.5 and repeating units of the formula, , , , , , , , or , wherein Ar is a divalent residue represented by the formula, , , or :

Ar' is a divalent residue represented by the formula, , or ;

Ar" is a divalent residue represented by the formula, , or and Ar"' is a divalent residue represented by the formula, or wherein R moieties may be the same or different and represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms; X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group or a dimethylmethylene group and about 20 to 200 parts by weight of at least one solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphoramide.

2. The composition of Claim 1, wherein the solvent comprises at least about 5 % by weight of N-methyl-2-pyrrolidone or hexamethylphosphoramide.

3. The composition of Claim I , wherein Ar in the formula of the aromatic polyamide-imide is , or ;

Ar' is , or ;

Ar" is or ;

and Ar"' is , wherein R is a hydrogen atom or a methyl group; and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group or an ethylene group.

4. The composition of Claim 1, wherein Ar in the formula of the aromatic polyamide-imide is or ;

Ar' is or ; and Ar" is .

5. The composition of Claim 1. wherein the aromatic polyamide-imide has a reduced viscosity of from about 0.4 to 1.3.

6. The composition of Claim l, wherein the polyamide-imide additionally comprises about 2 to 100 parts by weight, based on 100 parts by weight of the aromatic polyamide-imide, of an epoxy resin.

7 . The composition of Claim 6 , wherein the epoxy resin is a compound of the formula, wherein m1 is a number of 0 to 20.

8. The composition of Claim 6, wherein the epoxy resin is a compound of the formula, wherein m2 is a number of 0 to 5.

9. The composition of Claim 1 or 6, wherein the polyamide-imide additionally comprises about 2 to 60 parts by weight based on 100 parts by weight of the aromatic polyamide-imide, of a silane coupling agent.

10. An insulative substrate comprising an impregnated base material formed of paper or fiber with the composition as described in claim 1.

11. An insulative substrate comprising a base material printed, coated or laminated over the entire surface of the base material or in a pattern with the composition as described in claim 1.

12. A board for electrical circuits comprising an insulative base material and a layer of metal foil, said metal foil being adhered to the surface of the base material with the composition as described in claim 1.

13. An electrical circuit board comprising an insulative base material and circuit on the base material, at least a portion of the circuit being coated with the composition as described in claim 1.

14. A multi-layer circuit board comprising the circuit board of claim 13 and circuit on the composition-coated surface of the circuit board.

15. A mounting electrical circuit board comprising an insulative surface and at least one electrical element selected from the group consisting of integrated circuits, passive elements, active elements and conversion elements, the electrical element being bonded to the insulative sub-strate with the composition as described in claim 1.

16. A condenser comprising two electrodes united through a film obtained by removing the polar organic solvent from the composition as described in claim 1.

17. An electrical element selected from the group consisting of integrated circuits, passive elements, active elements and conversion elements and being encapsulated with the composition as described in claim 1 from which the polar organic solvent has been removed.