JPS5811899B2 - polyamideimide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions having excellent heat resistance, moisture resistance, adhesion and electrical properties, particularly for application in electronic components.

In recent years, electronic components are particularly required to be highly integrated and highly reliable.

Along with this, there is a desire to develop materials for electronic components that have excellent heat resistance, moisture resistance, adhesive properties, and electrical properties.
The current situation is that this has not been achieved.

The main reason for this is that most of the synthetic resins known so far either exceed their softening point at temperatures above 250°C, or
As it approaches the decomposition point, it becomes unstable.

To solve this problem, it is possible to use heat-resistant polymers, but since common heat-resistant polymers are insoluble in most solvents, they must be used as precursors in this case.

For example, aromatic polyamic acid is well known, but it is prone to hydrolysis and has poor storage stability. In order to convert it into heat-resistant aromatic polyimide or aromatic polyamide-imide, it is necessary to heat it at around 300°C. Since it requires heat treatment, it has drawbacks such as not being applicable to electronic components that are adversely affected by heat treatment, and contamination caused by low molecular compounds generated during this heat treatment.

Polyimides or polyamideimides that are partially soluble in solvents are also known, but most of these are heat resistant,
It has poor properties such as moisture resistance and adhesiveness.

Further, when synthesized at a temperature higher than 150° C., some hydrolysis and crosslinking occur, making it difficult to obtain a linear polymer having a reduced viscosity sufficient to obtain the above-mentioned practical properties.

In addition, as a composition having electrical properties, for example, a composition consisting of silver particles and glass frit is known.

This composition needs to be fired at a high temperature of 500 to 1000 degrees Celsius, making it difficult to obtain high precision and expensive, and is not suitable for substrates other than heat-resistant substrates such as salami. There were drawbacks such as the fact that it was not possible, and that it could not be applied to devices equipped with other parts.

An object of the present invention is to relate to a composition that has excellent heat resistance, moisture resistance, adhesiveness, and storage stability and is applicable to electronic components.

The present invention also relates to a highly accurate and highly reliable composition having electrical conductivity, resistance, or insulation.

The present invention consists of 100 parts by weight of a specific aromatic polyamideimide having a bond at the 1°3 position of the aromatic nucleus which is soluble in a polar organic solvent, and 10 to 10,000 parts by weight of a solvent that can substantially dissolve this aromatic polyamideimide. 100 parts by weight of a specific aromatic polyamideimide having bonds at the 1 and 3 positions of the aromatic nucleus soluble in polar organic solvents, and metals, metal oxides, metal nitrides, and metals. Granules 100 to 40 that are at least one selected from carbides, metal silicides, silicon, silicon oxides, silicon nitrides, silicon carbides, boron, boron nitrides, carbon, and mixtures thereof
00 parts by weight of the composition, and 100 parts by weight of a specific aromatic polyamideimide having a bond at the 13 position of the aromatic nucleus which is soluble in a polar organic solvent, and this aromatic polyamideimide is substantially dissolved. Vine solvent 10-10000
Parts by weight and granules that are at least one member selected from metals, metal oxides, metal nitrides, metal carbides, metal silicides, silicon, silicon nitrides, silicon carbides, boron, boron nitrides, carbon, and mixtures thereof. 100-40
00 parts by weight.

1 of the aromatic nuclei soluble in the polar organic solvent used in the present invention
．． A specific aromatic polyamideimide having a bond at position 3 has the general formula (wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X is an oxygen atom, a sulfur atom, or a sulfonyl atom). a divalent residue represented by a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group, or a dimethylmethylene group, which may be the same or different; n is 2 or more; An integer having a reduced viscosity of 0.3 to 1.5 is used.

Preferably, Ar in the above general formula is a divalent residue represented by the formula (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). The base polyamideimide is used.

More preferably, the aromatic polyamide-imide used in the present invention, in which Ar of the general formula is 15
Those synthesized at a temperature of 0° C. or lower are preferred.

If the polymer is synthesized at a temperature higher than 150° C., some hydrolysis or crosslinking will occur, and therefore the linear polymer will not have a reduced viscosity sufficient to provide practical properties.

Therefore, in the present invention, the reduced viscosity is 0.3, which is synthesized in an organic solvent at a temperature of 150°C or lower, preferably 130°C or lower.
~1.5, preferably 0.4-1.3 linear polymers are desirable.

If the reduced viscosity is less than 0.3, the strength of the film when used as a protection material, encapsulation material, etc. will be weak, and other practical properties will be insufficient, and reliability will be particularly poor.

Furthermore, if the reduced viscosity is greater than 1.5, it becomes difficult to obtain a highly concentrated solution, resulting in poor workability.

These aromatic polyamideimides are, for example, todiphenyl-3 bisimidodicarboxylate represented by the general formula
, 3'-diisocyanate, bisimidodicarboxylic acid of the general formula and metaphenylene diisocyanate, or bisimidodicarboxylic acid of the general formula and 0CN-
It can be produced by reacting a diisocyanate represented by Ar or A'r-NCO in an organic solvent at a temperature of 150 DEG C. or lower.

However, A, A'r and A''r in each of the above formulas have the same meanings as described above.

These aromatic polyamideimides are dissolved in at least one solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide. Therefore, the above-mentioned solvents are used in the present invention.

Further, when the solvent used is a single solvent or a mixed solvent system containing at least 5% by weight of N-methyl-2-pyrrolidone or hexamethylphosphoramide, the practical properties of the composition of the present invention are further improved. .

This is thought to be related to crystallinity, internal stress, and wetting, and improves practical properties such as heat resistance, moisture resistance, adhesiveness, and electrical properties.

Furthermore, pot life, coating properties, lamination properties,
It also gives favorable results in terms of workability such as printability.

The blending amount of the solvent is 10 to 10,000 parts by weight, preferably 20 parts by weight, based on 100 parts by weight of the aromatic polyamideimide.
~2000 parts by weight is preferable.

If this amount is less than 10 parts by weight, workability and adhesive properties will be reduced, and if this amount is more than 10,000 parts by weight, workability and adhesive properties will be reduced and pinholes will likely occur.

In addition, especially those containing 20 to 200 parts by weight of a solvent to 100 parts by weight of the above-mentioned aromatic polyamide-imide exhibit a solid or semi-solid state and are melted by heating, making it possible to perform heat molding, heat bonding, etc. Become.

The heating conditions are 50 to 300°C, preferably 10
The temperature is preferably 0 to 200°C.

The aromatic polyamide-imide and the granules dispersed in the composition comprising the aromatic polyamide-imide and a solvent impart electrical properties such as conductivity, electrical resistance, electrical insulation, or dielectricity to the composition of the present invention. At least one selected from metals, metal oxides, metal nitrides, metal carbides, metal silicides, silicon, silicon oxides, silicon nitrides, silicon carbides, boron, boron nitrides, carbon, and mixtures thereof. are used.

Generally, the shape thereof may be fine particles, and may be any shape such as spherical, angular, acicular, flake, etc.

The particle size is usually selected in the range of 20 Å to 500 μ.

Specific examples include Au, Ag, Pd, Ru, and Pt. Rh
, Ir, TI, Mo, Zn, Mn, Mg, Cd, Cr,
Nb.

Ge, Zr, Cu, Ni, AI, Sn, Pb, Bi, I
n, Fe.

Co, Ti, W, Ta, Hf, Y, Ba, Be, Si,
It may be C, B, alloys thereof, oxides, nitrides, carbides, silicides thereof, or mixtures thereof.

Among these, Au is used as the conductive particulate material.

Ag, Pd, Pt, Cu, Ni, Al, Sn, Mo, M
n, Co.

W, alloys thereof and mixtures thereof are preferred; Au
, Ag, Pa, Pi, Cu, Ni, Al, Sn, alloys thereof, and mixtures thereof.

As a resistive granule, 5n02-Ta205゜Mo0
3-B, ZnO, CdC-ZnO, Ag-Pd0°Ag
-Pd0-Pd, Ni02-Ag, C-B-Ag.

Ag-Pd0-8b203. C-B, Cu2O-CuO
.

In203yIn2035b20a, Tt203,5n
02゜5n02-8b20syIro2pRhOyRu
02#TaNjjTiN, TiN-Ti, TaN-Ta
, WC, WC-W.

C, CoSi, ZrSi, Taxi, MnSi, MoS
i.

Preferably, it is selected from NiSi, TiSi, and mixtures thereof.

SiO is used as the insulating or dielectric granule.

5102.51sN42SICITa20s)At20
3tTi02. Hf02tZr02. Y2O5tBaT
ioa.

BN+Be01COOtPbOtB20atB120a
tBaO and mixtures thereof are preferred, SiO,5
i02°Si3N4. SiC, Ta2O3, Az2o,
, TlO2+BaTi0a, BN, Bed, Cod,
More preferably it is selected from PbO, B203tB1203tBaO and mixtures thereof.

The blending amount of these granules is 100 to 400 parts by weight per 100 parts by weight of aromatic polyamideimide soluble in polar organic solvent.
0 parts by weight, preferably in the range of 200 to 2000 parts by weight.

If the amount is less than 100 parts by weight, desired electrical properties such as conductivity and resistance cannot be obtained, and if it exceeds 4,000 parts by weight, undesirable phenomena such as cracking may occur when the composite does not contain a solvent. .

The composition of the present invention exhibits sufficient properties even without the addition of other components other than those described above, but if desired, adhesive properties,
In order to further improve the dispersibility of fine particles, a silane coupling agent, epoxy resin H fat, etc. can also be added.

In this case, the amount added is preferably 2 to 100 parts by weight in the case of an epoxy resin, and 2 to 60 parts by weight in the case of a silane coupling agent, relative to 100 parts by weight of the aromatic polyamideimide soluble in the organic polar solvent. range.

If the amount is less than the above range, no effect will be observed, and if it is too much, the heat resistance will deteriorate.

The epoxy resin used in the present invention may be any known epoxy resin.

For example, it is described in Chapters 3 and 4 of "Epoxy Resin" published by Shokodo in 1970, edited by Hiroshi Kakiuchi.

This epoxy resin has an average of at least two epoxy groups per molecule, and the remainder of the molecule is characterized by carbon chains or carbon chains interrupted by ether bonds, ester bonds, or amine bonds.

Suitable epoxy resins include polyhydric alcohols such as ethylene glycol, glycerin, and trimethylolpropane, polyhydric phenols such as resorcinol, hydroquinone, catechol, and phloroglycitur, and 2,2-bis-(4-hydroxyphenyl)-propane. , 4.4'-
Obtained by contact reaction of polyphenols such as dihydroxydiphenylmethane and novolak resins, polycarboxylic acids such as p-hydroxybenzoic acid and terephthalic acid, and amine compounds such as o-toluidine with an excess amount of epoxides such as epihalohydrin and alkylene oxide. There is something.

These epoxy resins are described in U.S. Patent No. 2,592,
Many of them are described in the specification of No. 560.

More specifically, it is obtained by the reaction of bisphenol A and epichlorohydrin, and is expressed by the formula (where m1 has an average value of 0 to several tens).

), or a reaction product of a novolac resin and epichlorohydrin, and m2 has an average value of 0 to about 5.

) are particularly suitable.

To produce the granule-containing composition of the present invention, first, granules obtained by a pulverization method, vacuum evaporation method, chemical precipitation method, etc. are mixed with the aromatic polyamide-imide and a specific solvent, Stir until the polyamideimide is completely dissolved in the solvent to disperse.

As a means for dispersing, a ball mill or the like is used.

What does it mean to uniformly disperse granules? This means that there is no large deviation in the dispersion of the granules.

In the manner described above, a composition in which granules are dispersed in polyamideimide and a solvent is obtained.

Next, if necessary, the solvent is completely removed from this composition by evaporation, heat treatment, or other method to obtain a composition in which granules are dispersed in polyamideimide.

All of the compositions of the present invention can be sufficiently prepared by low temperature treatment at around 100°C.

A conductor circuit board, a resistor circuit board, which has excellent heat resistance and moisture resistance, has high precision and high reliability, using the composition of the present invention,
Insulating substrates, circuit boards, multilayer circuit boards, hybrid circuit boards, capacitors and other IC1 active elements,
Electrical elements such as passive elements and conversion elements
element(s) can be obtained.

Here, the conductor circuit board refers to a board on which a conductor circuit is formed.

A resistive circuit board is a board on which a resistive circuit is formed.

A circuit board is a board with metal foil formed on the entire surface of the board.

A multilayer circuit board refers to a board in which two or more conductor circuits or resistance circuits are formed with insulating layers interposed therebetween.

A hybrid circuit board is one that has at least a conductor circuit and a resistance circuit on the board.

A circuit board refers to a board having only circuit wiring on the board.

Electrical element refers to IC1 passive elements, active elements, and conversion elements such as monolithic ICs, hybrid IC1 resistors, capacitors, coils, diodes, transistors, magnetoelectric conversion elements, photoelectric conversion elements, thermoelectric conversion elements, piezoelectric elements, and display elements. .

A mounted circuit board is a circuit board with electrical components mounted on it.
A device equipped with element(s).

As a method for obtaining an insulating substrate, a composition comprising the aromatic polyamideimide and the solvent or a composition in which insulating particles are dispersed is prepared from paper or fibers such as glass fiber, glass cloth, and carbon fiber. or by coating or printing the entire surface or pattern on a substrate made of plastic, metal, glass, or ceramic, or by removing the solvent from the above composition and using it as a substrate. There are methods such as laminating the entire surface or pattern on the surface, or molding it in a desired mold.

As a method for obtaining a circuit board, a composition containing the aromatic polyamide-imide and the solvent as main components or a composition in which insulating particles are dispersed is used to coat the entire surface of a substrate such as a polyimide film. There are methods such as bonding metal foil such as etched copper foil.

A circuit board can be obtained by etching the metal foil of the circuit board thus obtained into a desired circuit pattern.

Furthermore, in the method for obtaining a circuit board, a circuit board can be obtained by punching out a metal foil such as a copper foil into a circuit pattern and adhering it onto a board using the composition.

The conductive circuit board is a film obtained by printing a composition consisting of the aromatic polyamide-imide, the solvent, and conductive particles on an insulating substrate in the form of a circuit pattern, or by removing the solvent from the composition. A resistive circuit board can be obtained by laminating materials in a pattern, and a resistive circuit board can be obtained by printing a composition consisting of the aromatic polyamide-imide, the solvent, and the resistive granules on an insulating substrate in a circuit pattern, or by laminating the above composition into a circuit pattern. It is obtained by laminating a film-like material obtained by removing the solvent from a material in a pattern.

The multilayer circuit board is a conductor circuit board or a resistor circuit board, and the aromatic polyamide-imide and the solvent or a composition in which insulating particles are dispersed therein are applied on the entire surface or only in a multilayered part or through holes. When making a connection, it is coated or printed in a suitable pattern, or a film obtained by removing the solvent from the above composition is laminated on the entire surface or in a pattern in the same way as above. Furthermore, a conductor circuit or a resistance circuit can be formed in the same manner as in the case of obtaining a conductor circuit board or a resistance circuit board.

The hybrid circuit board is manufactured using a method similar to that described above.
It can be obtained by forming a conductor circuit and a resistance circuit on an insulating substrate.

The circuit board having a protective layer is prepared by applying the aromatic polyamide-imide and the solvent, or a composition in which insulating particles are dispersed therein, to the entire surface or at least of a conductor circuit board, resistance circuit board, multilayer circuit board, or hybrid circuit board. It can be obtained by coating or printing on a circuit, or by laminating a film obtained by removing the solvent from the above composition on the entire surface or in a pattern.

The mounted circuit board has an IC1 active element on the circuit of the circuit board,
Passive elements, conversion elements electrical elc-
ment(s) using a composition consisting of the aromatic polyamide, the solvent, and the conductive particles, by bonding them by a method such as die bonding.

Alternatively, the electrical elements (s) of the IC1 active element, passive element, and conversion element may be adhered onto an insulating substrate using the aromatic polyamide-imide and the solvent, or a composition in which insulating particles are dispersed therein. It will be done.

In this case, connection to the circuit is performed by a method such as wire bonding.

The capacitor can be made by coating or printing a composition in which the aromatic polyamideimide and the solvent or dielectric particles are dispersed therein on an electrode such as a metal, and further providing an electrode thereon, or by forming an electrode from the above composition. Either the film obtained by removing the solvent is laminated on the electrode and an electrode is further provided on it, or the metal is vapor-deposited or sputtered on the top and bottom of the film obtained by removing the solvent from the above composition. , can be obtained by printing the composition of the present invention in which conductive particles are dispersed to form an electrode.

electrical element with lead wire
t(s) is the electrical connection between lead wires such as metal frames, IC1 active elements, passive elements, and conversion elements.
It is obtained by bonding element(s) with a composition consisting of the aromatic polyamideimide, the solvent and the conductive particles.

embossed electrical e
le-ment(s) is IC1 active element, passive element,
electrical element(s) of the conversion element
) is obtained by immersing the aromatic polyamide-imide in the solvent or a composition in which insulating particles are dispersed.

The composition of the present invention has excellent heat resistance, moisture resistance, adhesiveness, and electrical properties, and furthermore, insulating substrates, circuit boards, conductive circuit boards, and resistive circuit boards obtained using this composition. , multilayer circuit boards, hybrid circuit boards, mounted circuit boards, capacitors and other IC1 active elements,
Passive elements, conversion elements electrical elements
ent(s) also has excellent heat resistance and moisture resistance, and has high precision and high reliability.

Not only heat resistance but especially moisture resistance is important in relation to the reliability of electronic components.

The composition of the present invention has a wide range of applications other than those mentioned above.

EXAMPLES Next, Examples will be described to more specifically explain the present invention, but the present invention is not limited to these Examples.

In addition, in the examples, all resistance values were measured using a universal digital meter 2502 (manufactured by Yokokawa Denki Co., Ltd.).

Examples 1 to 6 and Comparative Example 1 The base materials shown in Table 1 were replaced with aromatic polyamideimide 1 of Table I.
00 parts by weight, 600 parts by weight of N-methyl-2-pyrrolidone, and 400 parts by weight of N,N-dimethylacetamide.

10 sheets of the obtained impregnated material were stacked and heated at 200°C for 30 minutes.
Pressure molded under the condition of 00kg/-, 30cm x 30c
A heat-resistant substrate of m×1.6 mm was prepared.

As a result of a heat resistance test of the obtained heat-resistant substrate at 400°C for 30 minutes, the weight loss rate was very small as shown in Table 1, and no warpage was observed, indicating that it had excellent heat resistance and dimensional stability. was.

Furthermore, the obtained substrate could sufficiently withstand die bonding at 400°C.

In addition, the weight reduction rate is Calculated from the formula.

Examples 7 to 12 100 parts by weight of aromatic polyamideimide as shown in Table 2, 600 parts by weight of N-methyl-2-pyrrolidone and 400 parts by weight of N,N-dimethylacetamide were used as solvents on various substrates. Coat the composition and apply 10
Vacuum drying was performed at 0° C. for 3 hours to obtain an aromatic polyamideimide laminate.

The surface of the obtained laminate was smooth, and the aromatic polyamide-imide side of the obtained laminate was brought into contact with molten solder at 260°C for 20 seconds, or immersed in a 1% potassium hydroxide aqueous solution for 24 hours. No abnormalities such as blistering were observed, and heat resistance, adhesion, and alkali resistance were good.

The surface resistance of the aromatic polyamideimide side of the obtained laminate was 1. after being treated at 50° C. and 90% RH for 3 days.
Measured according to JISC6481-1968.

Examples 13 to 18 and Comparative Example 2 Polyimide film “Kapton” manufactured by DuPont (film thickness 7
5μ) and electrolytic copper foil (film thickness 35μ, Examples 13 to 15 are the same size as the above polyimide film, Example 1
6 to 18 are punched into circuit patterns) at 150°C for 30 minutes and then at 200°C using a solid or semisolid composition consisting of aromatic polyamideimide and a solvent shown in Table 3. The adhesive was bonded by heating and pressing for 30 minutes.

Next, a heat resistance test was conducted at 400°C for 30 minutes, and the peel strength of the copper foil after that was as shown in Table 3.
It had excellent heat resistance and adhesive properties.

In addition, the peel strength is JIS C6481-1968.
Measured according to.

Furthermore, the flame resistance was measured according to JiS C6481-1968 and the results were also excellent.

Examples 19 to 24 A solid or solid composition consisting of aromatic polyamideimide and a solvent shown in Table 4 was prepared, and this was heated using a heat press at 150°C for 30 minutes, then at 200°C for 30 minutes.
After pressure molding under the conditions of 100 kg/cm2,
A 200μ film was prepared by heat treatment at ℃ for 2 hours.

Volume resistivity was measured according to JIS C6481-1968, and moisture permeability was measured according to JIS Z0208.

The results are shown in Table 4, and it was found that it had excellent electrical properties and moisture resistance.

Example 25 Bisimidodicarboxylic acid obtained from metaphenylene diamine and trimellitic anhydride and diphenyl-3,3'-
240 parts by weight of N-methyl-2-pyrrolidone and 16 parts by weight of NN-dimethylacetamide were added to 100 parts by weight of polyamideimide (reduced viscosity 0.5) synthesized from diincyanate.
0 parts by weight were added to dissolve the polyamideimide, and then 400 parts by weight of ultrafine silver particles prepared by vacuum evaporation with an average particle size of 700 Å were added and uniformly dispersed using a ball mill.

The composition thus obtained was in the form of a paste.

Next, to test whether this could be used in a conductive resin paste, this composition was deposited on an alumina substrate with a width of 1 mm.
20 conductor lines with a length of 2 cm and a thickness of about 50 μm were screen printed.

After heat treatment at 100°C for 30 minutes to sufficiently remove the solvent,
When the resistance of one line of this pattern was measured, it was 0.2Ω or less, and the adhesion to the substrate was also good.

Next, in order to test heat resistance, heat treatment was performed at 400° C. for 1 hour.

The resistance value after that was 0.3Ω or less, almost unchanged from before the heat treatment, and there was no peeling from the substrate and excellent adhesion.

Example 26 Polyamideimide (reduced viscosity 0
．． 7) N-methyl-2-pyrrolidone 4 to 100 parts by weight
30 parts by weight and 70 parts by weight of toluene were added to dissolve the polyamideimide, and then ultrafine silver particles with an average particle size of 700 Å prepared by vacuum evaporation method and palladium with an average particle size of 0.5 μ were mixed in a weight ratio of 1:1. 250 parts by weight of the metal fine particle mixture mixed in Step 1 was added and uniformly dispersed using a hole mill to obtain a base-like composition.

The composition thus obtained was treated in the same manner as in Example 25.

The resistance value was 0.3Ω or less, and the adhesiveness was also good.

Next, when the heat resistance was tested in the same manner as in Example 25, the resistance value was 0.4Ω or less, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 27 N, N- 400 parts by weight of dimethylacetamide was added to dissolve the polyamideimide, and then 500 parts by weight of fine particles of ruthenium oxide having an average particle size of 0.8 μm were added and uniformly dispersed using a ball mill.

In order to test whether the paste-like composition thus obtained could be used as a resistive resin paste, this composition was applied to a 1-width and 2-length strip on an alumina substrate.
20 cm resistance lines were screen printed (approximately 50 μm thick).

After sufficiently removing the solvent by heat treatment at 100°C for 30 minutes,
When the resistance of one of the patterns was measured, it was 15.OMEGA., and the adhesion to the substrate was also good.

Next, in order to test heat resistance, heat treatment was performed at 400° C. for 30 minutes.

The resistance value after that was 15KQ, which was unchanged from before the heat treatment, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 28 Polyamideimide obtained from bisimido dicarboxylic acid obtained from metaphenylene diamine and trimellitic anhydride and metaphenylene diisocyanate (reduced viscosity 0.
3) 100 parts by weight, epoxy resin (AER manufactured by Asahi Kasei Co., Ltd.
-669j) 10wt N-methyl-2-pyrrolidone 43
A paste composition consisting of 500 parts by weight of fine copper particles having an average particle size of 10 μm uniformly dispersed in 0 parts by weight and 70 parts by weight of toluene was screen printed in a predetermined pattern on a glass epoxy laminated substrate, and then 150 parts by weight A printed circuit board was obtained by heat treatment at ℃ for 30 minutes.

The resistivity of the conductor thus obtained is 1.5×10−
It had a resistance of 4 Ω·cm, was sufficiently resistant to soldering heat at 270° C. for 60 seconds, and had good adhesion.

Example 29 100 parts by weight of polyamideimide (reduced viscosity 0.8) manufactured from bisimidodicarboxylic acid synthesized from metaphenylene diamine and trimellitic anhydride and paraphenylene diisocyanate, 240 parts by weight of N-methyl-2-pyrrolidone. Department, N.

To 160 parts by weight of N-dimethylacetamide, an average particle size of 1
．． A paste composition prepared by uniformly dispersing 400 parts by weight of 8μ fine silver particles was screen printed on a polyimide film in a predetermined pattern, and then heated at 100°C for 3
A printed circuit board was obtained by heat treatment for 0 minutes.

The specific resistance of the conductor thus obtained was 4.0×10−
It had a resistance of 4 Ω·cm, sufficiently withstood a heat resistance test at 400° C. for 30 minutes, and had good adhesion.

Example 30 Polyamideimide (produced from bisimidodicarboxylic acid synthesized from metaphenylenediamine and trimellitic anhydride and 4°41-diisocyanatodiphenyl)
reduced viscosity 0.6), 240 parts by weight of N-methyl-2-pyrrolidone, 160 parts by weight of N,N-dimethylacetamide, 250 parts by weight of carbon fine particles with an average particle size of 10 μm, and boron with an average particle size of 20 μm. Using a paste composition in which 250 parts by weight of fine particles were uniformly dispersed, a line with a width of 1 rft 1 nm and a length of 2 cm was screen printed (approximately 50 μ thick) on a glass substrate, and then heat treated at 100° C. for 30 minutes. , a resistor circuit was obtained.

The resistor thus obtained had a resistance of 400Ω, sufficiently withstood a heat resistance test at 270° C., and had good adhesive properties.

Example 31 Bisimidodicarboxylic acid synthesized from 3.3'-diaminodiphenyl ether and trimellitic anhydride and 3,3
'-100 parts by weight of polyamideimide (reduced viscosity 0.5) produced from diphenyl diisocyanate, N, N
- 300 parts by weight of dimethylacetamide, average particle size 20
Using a paste-like composition in which 400 parts by weight of indium oxide microparticles of μ μ are dispersed, a line with a width of 2 cm and a length of 2 crrL is screen printed (approximately 50 μ thick) on a polyimide film, and then heated at 100° C. for 1 hour. A resistance circuit was obtained by heat treatment.

The resistor thus obtained had a resistance of 10Ω, sufficiently withstood a heat resistance test at 270° C., and had good adhesive properties.

Example 32 100 parts by weight of polyamideimide (reduction degree 1.5) produced from bisimidodicarboxylic acid tomethphenylene diisocyanate synthesized from 3.3'-diaminodiphenylmethane and trimellitic anhydride was added with N. -Methyl-
240 parts by weight of 2-pyrrolidone and 160 parts by weight of N,N-dimethylacetamide were added to dissolve the polyamideimide, and then 300 parts by weight of tantalum nitride with an average particle size of 20 μm was added.
Parts by weight were added and uniformly dispersed using a ball mill.

The composition thus obtained was in the form of a paste.

When this composition was treated in the same manner as in Example 25, the resistance value was 45Ω, and the adhesiveness was also good.

Next, when the heat resistance was tested by heat treatment at 400° C. for 30 minutes, no change was observed in the resistance value and adhesiveness.

Example 33 N, 300 parts by weight of N-dimethylacetamide was added to dissolve the polyamideimide, and then 400 parts by weight of tungsten carbide having an average particle size of 20μ was added and uniformly dispersed using a ball mill to obtain a paste composition. .

This composition was screen printed in the same manner as in Example 25, and 1
Heat treatment was performed at 00°C for 1 hour.

The resistance value was IOKΩ, and the adhesiveness was also good.

Next, when the heat resistance was tested by heat treatment at 400° C. for 30 minutes, no change was observed in the resistance value and adhesiveness.

Example 34 Polyamideimide (reduced viscosity o, 5) prepared from 4.41-di(m-aminophenoxy)diphenyl ether, bisimidodicarboxylic acid obtained from trimellitic anhydride, and 3,31-diisocyanate diphenyl (reduced viscosity o, 5) ioo parts by weight 240 parts by weight of N-methyl-2-pyrrolidone and 160 parts by weight of N-N-dimethylacetamide were added to
The above polyamide-imide was dissolved, and then 270 parts by weight of tantalum silicide and 30 parts by weight of aluminum were heat-treated at a temperature of 1200°C for 1 hour in a nitrogen atmosphere.The average particle size was 20μ.
350 parts by weight of the fine particles were added and uniformly dispersed using a ball mill.

The heat-resistant resistance material composition thus obtained was in the form of a paste.

When this composition was treated in the same manner as in Example 25, the resistance value was IOKΩ.

Next, in order to test heat resistance, heat treatment was performed at 400° C. for 30 minutes.

The resistance value after that was unchanged from before the heat treatment, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 35 100 parts by weight of polyamideimide (reduced viscosity 1.0) obtained from bisimido dicarboxylic acid synthesized from 2,4-toluylene diamine and trimellitic anhydride and 3,3'-diisocyanatodiphenyl , 2 parts by weight of silane coupling agent ("A-1100" manufactured by Nippon Unicar Co., Ltd.), 10 parts by weight of epoxy resin ("AER-669" manufactured by Mukasei Co., Ltd.), 430 parts by weight of N-methyl-2-pyrrolidone, 70 parts by weight of toluene. Using a paste composition in which 400 parts by weight of aluminum oxide fine particles with an average particle size of 0.8 μm were uniformly dispersed, it was applied to the entire surface of the alumina substrate to a thickness of 5 μm, and then heat-treated at 150° C. for 30 minutes. , an insulating substrate was obtained.

The thus obtained insulating substrate sufficiently withstood a heat resistance test of 400° C. and had good adhesion.

Example 36 Polyamideimide prepared from bisimidodicarboxylic acid obtained from metaphenylene diamine and trimellitic anhydride and 4,4'-diisocyanate benzophenone (
Reduced viscosity 1.2) A composition in which 400 parts by weight of silicon dioxide having an average particle size of 10 μm was uniformly dispersed in 100 parts by weight and 500 parts by weight of N,N-dimethylacetamide was poured into a mold and heated at 100°C for 1 hour. Then, heat treatment was performed at 200° C. for 1 hour to obtain an insulating substrate of 30 cm x 30 cm x 0.5 mm.

This insulating substrate sufficiently withstood a heat resistance test at 400° C. for 30 minutes, and had good dimensional accuracy without warping.

Example 37 100 parts by weight of polyamideimide (reduced viscosity 0.7) obtained from bisimidodicarboxylic acid tomethphenylene diisocyanate synthesized from 4.4'-diaminodiphenyl sulfide and trimellitic anhydride was subjected to silane coupling. 5 parts by weight of agent ("A-1100" manufactured by Nippon Unicar Co., Ltd.) and 400 parts by weight of dimethyl sulfoxide were added to dissolve the above polyamideimide, and then the average particle size was 5 μm.
500 parts by weight of fine gold particles were added thereto and uniformly dispersed using a ball mill to obtain a paste-like composition.

The composition thus obtained was screen printed in the same manner as in Example 25, and heat treated at 150° C. for 30 minutes.

The resistance value was 0.2Ω or less, and the adhesiveness was also good.

Next, when the heat resistance was tested in the same manner as in Example 25, the resistance value was 0.2Ω or less, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 38 4. N, N- Add 500 parts by weight of dimethylformamide to dissolve the polyamideimide, then add 600 parts by weight of nickel fine particles with an average particle size of 3 μm, and uniformly disperse using a ball mill.
A paste-like composition was obtained.

The composition thus obtained was screen printed in the same manner as in Example 25 and heat treated at 100° C. for 30 minutes.

The resistance value was 0.3Ω or less, and the adhesiveness was also good.

Next, when the heat resistance was tested in the same manner as in Example 25, the resistance value was 0.4Ω or less, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 39 400 parts by weight of hexamethylphosphoramide was added to 100 parts by weight of polyamideimide (reduced viscosity 1.0) synthesized from bisimido dicarboxylic acid obtained from metaphenylene diamine and trimellitic anhydride, and 2,4-toluylene diisocyanate. Parts by weight were added to dissolve the polyamideimide, and then 500 parts by weight of tin fine particles having an average particle size of 5 μm were added and uniformly dispersed using a ball mill to obtain a paste composition.

The composition thus obtained was screen printed in the same manner as in Example 25, and heat treated at 150° C. for 30 minutes.

The resistance value was 0.3Ω or less, and the adhesiveness was also good.

Next, when the heat resistance was tested in the same manner as in Example 47, the resistance value was 0.3Ω or less, and there was no peeling from the substrate and the adhesiveness was excellent.

Example 40 100 parts by weight of polyamideimide (reduced viscosity 0.4) obtained from bisimidocarboxylic acid synthesized from metaphenylene diamine and trimellitic anhydride and 3,3'-diisocyanatodiphenyl ether (reduced viscosity 0.4), N, N - 400 parts by weight of dimethylacetamide was added to dissolve the polyamideimide, and then 400 parts by weight of 5N02 fine particles having an average particle size of 10 μm were added and uniformly dispersed using a ball mill to obtain a paste-like composition.

The composition thus obtained was screen printed in the same manner as in Example 25, and heat treated at 100° C. for 30 minutes.

It had a resistance value of 15Ω, sufficiently withstood a heat resistance test at 400° C. for 30 minutes, and had good adhesion.

Examples 41-44 Bisimidodicarboxylic acid and diphenyl-3,3'- synthesized from metaphenylenediamine and trimellitic anhydride
100 parts by weight of polyamideimide having various reduced viscosities obtained from diisocyanates and 400 parts by weight of N-methyl-2-pyrrolidone were added to dissolve the above polyamideimide, and then the polyamideimide having an average particle size of 5 μm was added to Table 5 below. 500 parts by weight of the indicated fine particles were added and uniformly dispersed using a ball mill to obtain a paste-like composition.

Each of the compositions thus obtained was screen printed in the same manner as in Example 25, and heat treated at 150°C for 30 minutes.

The results of resistance value, heat resistance test at 400° C. for 30 minutes, and adhesiveness are as shown in Table 5.

, Examples 45-48 Bisimidodicarboxylic acid and diphenyl-3,3'- synthesized from metaphenylenediamine and trimellitic anhydride
400 parts by weight of N,N-dimethylacetamide was added to 100 parts by weight of a polyamideimide obtained from a diisocyanate and having a reduced viscosity of Enoki to dissolve the polyamideimide, and then the average particle size shown in Table 6 was 10μ. 500 parts by weight of fine particles were added thereto and uniformly dispersed using a ball mill to obtain a paste-like composition.

Each of the compositions thus obtained was treated in the same manner as in Example 36.

The results of the heat resistance test at 400° C. for 30 minutes and the dimensional accuracy are shown in Table 6.

Example 49 Aromatic polyamideimide 100 of the formula (reduced viscosity: 1.0) was placed on a circuit board having a first layer wiring obtained by etching a 35 μ thick copper-clad laminate.
A composition consisting of 600 parts by weight of N-methyl-2-pyrrolidone and 400 parts by weight of N,N-dimethylacetamide was screen printed so that the thickness of the composition after drying was 50μ, and then heated at 150°C. A heat treatment was performed for 1 hour to form a crossover insulating layer.

On this crossover insulating layer, a formula (reduced viscosity: 0.
5) 100 parts by weight of the aromatic polyamideimide, 300 parts by weight of N-methyl-2-pyrrolidone, 200 parts by weight of N,N-dimethylacetamide, and an average particle size of 1.8.
A composition consisting of 900 parts by weight of fine silver particles of 150 μm was screen printed so that the thickness after drying was 30 μm.
A second layer of conductive wiring was formed by heat treatment at .degree. C. for 30 minutes.

The specific resistance of this conductor is 1.0 x 10-4 Ωcm,
The measurement was performed by applying a voltage of 100 V to the first layer wiring and the second layer wiring.

The interlayer insulation resistance of the insulating layer was 3×10 6 MΩ.

Thereafter, 100 parts by weight of an aromatic polyamideimide of the formula (reduced viscosity: 1.0), 600 parts by weight of N-methyl-2-pyrrolidone and N,
A composition consisting of 400 parts by weight of N-dimethylacetamide was screen printed to a dry thickness of 100 μm, and then heat treated at 150° C. for 1 hour to form a protective layer.

The obtained multilayer circuit board was heated to 100°C at 70°C and 90%RH.
Even after the treatment for 0 hours, no change was observed in the specific resistance of the conductor and the interlayer insulation resistance of the insulating layer, indicating excellent stability.

Example 50 Aromatic polyamideimide 100 of the formula (reduced particle size: 0.6) was deposited on a glass epoxy laminate.
parts by weight, 300 parts by weight of N-methyl-2-pyrrolidone, 200 parts by weight of N,N-dimethylacetamide, and 900 parts by weight of fine silver particles with an average particle size of 1.8 μm. After screen printing so that the diameter of the conductor was 40 μm, a conductor portion was formed by heat treatment at 150° C. for 30 minutes.

The specific resistance of this conductor was 1.0×10 −4 Ω·cm.

Next, 100 parts by weight of aromatic polyamideimide of the formula (reduced particle size: 0.8) and 40 parts by weight of N-methyl-2-pyrrolidone were added.
0 parts by weight, and 400 carbon fine particles with an average particle size of 5μ
A composition consisting of parts by weight was prepared with a width Lrnrrt and a length of 2 cm.
After screen printing, the thickness after drying was 40 μm, and heat treatment was performed at 150° C. for 2 hours to form a resistance line.

This resistance value was 400Ω.

Thereafter, 100 parts by weight of aromatic polyamideimide of the formula (reduced viscosity: 1.0) and 60 parts by weight of N-methyl-2-pyrrolidone were added.
A protective layer was formed by heat-treating a screen-printed edge of a composition consisting of 0 parts by weight and 400 parts by weight of N,N-dimethylacetamide at 150° C. for 1 hour so that the thickness after drying was 100 μm.

The obtained hybrid circuit board was heated at 70°C and 90% RH.
Even after being treated for 1000 hours, there was no change in the specific resistance of the conductor or the resistance value of the resistor, and it had excellent stability.

Example 51 A lead wire consisting of a GAPAS light emitting diode and a metal frame was made of aromatic polyamideimide 100 of the formula (reduced viscosity: 0.4).
Using a composition consisting of 5 parts by weight of epoxy resin AER-33125 parts by weight manufactured by Mukasei Co., Ltd., 400 parts by weight of N-methyl-2-pyrrolidone, and 500 parts by weight of fine silver particles with an average particle size of 1.8 μm, The adhesive was bonded by heat treatment for 30 minutes.

Thereafter, wire bonding was performed at 350° C. for 2 minutes, and the results were satisfactory.

Example 52 A silicon tantalum resistor was made of aromatic polyamideimide 100 of the formula (reduced viscosity: 1.O).
parts by weight, 600 parts by weight of N-methyl-2-pyrrolidone, and 400 parts by weight of N,N-dimethylacetamide, and heat-treated at 150°C for 30 minutes.

The resistance change rate of the obtained resistor after treatment at 70° C. and 90% RH for 11,000 hours was 0.1% or less, and had excellent stability.

Example 53 Aromatic polyamideimide 100 (reduced viscosity: 1.0)
A composition consisting of 1200 parts by weight of N-methyl-2-pyrrolidone and 800 parts by weight of N,N-dimethylacetamide was heated at 150°C for 1 hour and then at 200°C for 1 hour.
On both sides of the 10μ thick film obtained by time treatment
An electrode was formed by sputtering G to a thickness of 1 μm in a size of 1 cm×1 square.

The capacitance of the capacitor thus obtained is 6×10
-4 μF, which sufficiently withstood a heat resistance test at 400° C. for 30 minutes.

Example 54 Aromatic polyamideimide 100 (reduced viscosity: 0.5)
parts by weight, and 300 parts by weight of N-methyl-2-pyrrolidone.
A composition consisting of 200 parts by weight of N,N-dimethylacetamide and 500 parts by weight of fine silver particles with an average particle size of 1.8 μm was adhered to a silicon chip, and then adhered to an alumina ceramic substrate and heat-treated at 150° C. for 1 hour. did.

This was placed on a hot plate at 400° C. and bounced off using Pu11 gauge with a force of 50 g, but did not come off and had excellent heat-resistant adhesion.

Example 55 Aromatic polyamideimide 100 (reduced viscosity: 0.6)
parts by weight, and 300 parts by weight of N-methyl-2-pyrrolidone.
An alumina ceramic circuit obtained by firing an Ag-Pd-based high-temperature firing thick film paste using a composition consisting of 200 parts by weight of N,N-dimethylacetamide and 500 parts by weight of fine silver particles with an average particle size of 1.8 μm. The circuit on the board and the light emitting diode were combined and heat treated at 150° C. for 1 hour.

Thereafter, wire bonding was performed at 350° C. for 2 minutes, and the wire bonding was sufficiently resistant.

Claims (1)

[Scope of Claims] 1 General formula % Formula % (wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a carbonyl group) oxy group, methylene group, ethylene group or dimethylmethylene group, which may be the same or different, n is an integer of 2 or more] 100 parts by weight of an aromatic polyamideimide having a reduced viscosity of 0.3 to 1.5 and soluble in a polar organic solvent;
, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide. Characteristic polyamide-imide composition. (However, R is a hydrogen atom or a methyl group, and X is an oxygen atom, a yellow atom, a sulfonyl group, a carbonyl group, a methylene group, or an ethylene group.) The polyamide-imide composition described in . The polyamide-imide composition according to item 1. 4. The polyamide-imide composition according to claim 1, wherein the solvent contains at least 5% by weight of N-methyl-2-pyrrolidone or hexamethylphosphoramide. 5. The polyamide-imide composition according to claim 1 or 4, wherein the solvent is blended in an amount of 20 to 200 parts by weight based on 100 parts by weight of the polyamide-imide. 6 Claim 1, in which 2 to 100 parts by weight of an epoxy resin and/or 2 to 60 parts by weight of a silane coupling agent are added to 100 parts by weight of aromatic polyamideimide.
The polyamide-imide composition described in . 7 The epoxy resin is represented by the following formula (wherein m has an average value of 0 to several tens) or (wherein m2 has an average value of 0 to about 5) The polyamide-imide composition according to item 6. 8 General formula (wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group, or (dimethylmethylene group, which may be the same or different), n is an integer of 2 or more, with a reduced viscosity of 0.3 to 1. 100 parts by weight of aromatic polyamideimide soluble in a polar organic solvent of No. 5, 100 to 4000 parts by weight of electrical property-imparting granules imparting electrical properties such as conductivity, electrical resistance, electrical insulation, or dielectricity. , a polyamide-imide composition containing uniformly dispersed particles. (However, 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.) Claim 8 is a divalent residue represented by The granulate-containing polynamide-imide composition as described. A granular material-containing polyamide-imide composition according to claim 8. 11 For 100 parts by weight of aromatic polyamideimide,
The polyamide-imide composition containing granules according to claim 8, wherein 2' to 100 parts by weight of an epoxy resin and/or 2 to 60 parts by weight of a silane coupling agent are added. 12. Claim 11, wherein the epoxy resin is represented by the following formula (wherein m1 has an average value of 0 to several tens) or (wherein m2 has an average value of 0 to about 5) The granular material-containing polyamide-imide composition described in 1. 13 The electrical property-imparting granules are selected from metals, metal oxides, metal nitrides, metal carbides, metal silicides, silicon silicon oxides, silicon nitrides, silicon carbides, boron, boron nitrides, carbon, and mixtures thereof. 9. The granular-containing polyamide-imide composition according to claim 8, which is at least one type of granular material. 14 The electrical property-imparting particles are Au, Ag, Pd, pt
. The granular-containing polyamide-imide composition according to claim 8 or 13, which is at least one selected from Cu, Ni, Al, Sn, alloys thereof, and mixtures thereof. 15 The electrical property imparting particles are 5nO2-Ta2O5゜Mo03-B, ZnO, Cd0-ZnO, Ag-Pd0
゜Ag-Pd0-Pd, Ni02-Ag, C-B-Ag
. AAg-Pd0-8b20', C-B, Cu20zC
uO. ■n203. ■n203-8b203. Tt203,5
n02゜SnO25b203 p RuO2y, TaN
pTINyTiN-TipTaN Ta'y”WCy
WCWpCyCo51pZrSi, Taxi, M
The polyamide-imide composition containing granules according to claim 8, which is at least one selected from nSi, MoSi, NiSi, TiSi, and mixtures thereof. 16 Electrolytic granules are CoO, PbO, B203p
BL+03. Bad, Sin, 5i02. Si3N...
SiC. Ta2O3, At203. TiO2, BaTi03yB
N. The granular-containing polyamide-imide composition according to claim 8 or 13, which is at least one selected from BeO and mixtures thereof! . 17 General formula (wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group, or (dimethylmethylene group, which may be the same or different), n is an integer of 2 or more, with a reduced viscosity of 0.3 to 1. 100 parts by weight of an aromatic polyamideimide soluble in a polar organic solvent of .5 and N
, N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and 10 to 10,000 parts by weight of at least one solvent selected from hexamethylphosphoramide, and Electric property imparting granules 100 to impart electrical properties such as conductivity, electrical resistance, electrical insulation or dielectricity
A polyamide composition containing granules, characterized in that 4000 parts by weight are uniformly dispersed therein. and A″r is a divalent residue represented by the formula (R is a hydrogen atom or a methyl group, and The polyamide-imide composition containing granules according to claim 17, wherein the polyamide-imide composition contains granules according to claim 17. 20 The solvent is N-methyl-2-pyrrolidone or hahexamethyl The granular-containing polyamide-imide composition according to claim 17, which contains at least 5% by weight of phosphoramide. 21. A patent in which the solvent is 20 to 200 parts by weight based on 100 parts by weight of the polyamide-imide. The granular material-containing polyamide-imide composition according to claim 17 or 20.22-2 to 100 parts by weight of an epoxy resin and/or 2 to 60 parts by weight of a silane coupling agent per 100 parts by weight of aromatic polyamide-imide. Added Claim No. 1
The granular material-containing polyamide-imide composition according to item 7. 23. Claim 17, wherein the epoxy resin is represented by the following formula (wherein m1 has an average value of 0 to several io) or (wherein m2 has an average value of 0 to about 5) The granular material-containing polyamide-imide composition described in 1. 24 The electrical property-imparting granules are made of metal, metal oxide, metal nitride, metal carbide, metal silicide, silicon silicon oxide, silicon nitride, silicon carbide, boron, boron nitride, carbon, and mixtures thereof. The granular-containing polyamide-imide composition according to claim 17, which is at least one selected one. 25 Electric property imparting particles are Au, Ag, Pd, Pt
. Cu, Ni, A7. The polyamide-imide composition containing granules according to claim 17 or 24, which is at least one selected from Sn, alloys thereof, and mixtures thereof. 26 The electrical property imparting particles are 5HO2-Ta2O5゜Mo03-B, ZnO, Cd0-ZnO, Ag-Pd0
゜Ag-Pd0-Pd, Ni02-Ag, C-B-A
g. Ag-Pd0-8b2O3, C-B, Cu2O-CuO
. In2O3, In2O3-8b203. Tl2O3,5
n02゜5n02-8b203. RuO2, TaN, T
iN, TiN-Ti. TaN-Ta, WC, WC-W, C, CoSi, ZrS
i. The polyamide-imide composition containing granules according to claim 17, which is at least one selected from TaSi, MnSi, MoSi, NiSi, TiSi, and mixtures thereof. 27 Electric property imparting granules are Co0yPbO, B20s
tBi203. BaO, SiO, 5i02. Si3N4
．． sic. Ta205. At20s, TiO2, BaTiO3, B
N. The granular-containing polyamide-imide composition according to claim 17 or 24, which is at least one selected from BeO and mixtures thereof.