JPS6038011B2 - Heat-resistant resistance material composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat-resistant resistance material composition, and more particularly to an electrical resistance material composition that can be processed at low temperatures and has excellent heat resistance and temperature characteristics.

Up until now, ceramics have been mainly used as electrical resistance materials;
Heat treatment at a high temperature of 0 to 1000 q○ was required.

Incidentally, in recent years, in the field of electronic components, there has been a strong demand for electrically resistive materials with good heat resistance and electrical properties that can be manufactured by low-temperature processing, and various attempts have been made. Among these, an electric resistance material based on synthetic resin has been proposed, but this material has the fatal drawbacks of poor heat resistance and lack of reliability, so it can never be put to practical use. Ta. The present inventors have overcome the drawbacks of conventional synthetic resin-based electrical resistance materials and have developed a highly reliable synthetic resin-based resistance material composition that is fully comparable to ceramic materials in terms of heat resistance and temperature characteristics. As a result of extensive research in order to develop the product, we discovered that the goal could be achieved by dispersing specific electrically resistive particles into a heat-resistant polymer base that is soluble in organic polar solvents. Based on this finding, the present invention has been made. That is, in the present invention, a metal silicide is added to parts by weight of at least one heat-resistant polymer 10 selected from aromatic polyimide, aromatic polyamideimide, and aromatic polyamide acid that are soluble in organic polar solvents. A heat-resistant resistive material composition comprising 5 to 200 parts by weight of resistive granules as a main component uniformly dispersed therein, and 100 to 50 parts by weight of the above composition in a solvent that can substantially dissolve the above polymer.
The present invention provides a heat-resistant resistance material composition in which resistive granules are uniformly dispersed by adding 0 parts by weight.

Heat-resistant polymers soluble in organic polar solvents used in the present invention include aromatic polyimide, aromatic polyamideimide, aromatic polyamide acid, and mixtures thereof.
In particular, aromatic polyimide and aromatic polyamideimide, which do not generate water during heat treatment, are optimal.

Aromatic polyamideimide is particularly good. The polyimide soluble in the organic polar solvent used in the present invention has the structural formula (
In the formula, RI is -CH(CH3)2, -S02N is or -
C), [R2 in the formula is "0-, 1S-, 1C-, fC(CF3)2na3,,-S02-' (However, RI is 1S-, >N- C6&, >N-CH3 or >NH), -C(CF3)21 or >CH-C6day.,], (R3 in the formula is -○-, 1C uniform, 1S02, or 1 (R6 in the formula is -01,1CH2) -,1S021,-C
6 days 101 C6 days 4- or 10-C6 days 4-0-, R7
or 10H), and (in the formula, R8 is -○-, -S02-, -CH2-, -C
02-,>C(CH3)2 or -S-), and the structural formula (R9 in the formula is -01, "S02 -(CF2)3-, -C(CF3) 2 - -(CF2)6- or 1○-(CF2)51○-), (RI〇 in the formula is 1C6 days 40 - C6 days 4 - or 1C6 ratio - 01C6 days 41) ○-C6day41) or (RII in the formula is -○-, 1○-(CH2)2-
○、−.

・(C&)4-. ·'one. -(CH2)6-. A compound obtained from an aromatic tetracarboxylic dianhydride represented by the following formula is suitable.

In addition, as polyamideimide soluble in organic polar solvents, the general formula or (or Ar) [in the formula - is the formula or (where R is a hydrogen atom, a halogen atom or an alkyl group (e.g. methyl group, ethyl group] group, propyl group, etc.); a divalent residue represented by the formula, ~' is a divalent residue represented by the formula or (where R and × have the same meanings as above), and n is an integer of 2 or more]. suitable.

These poamides can be produced, for example, by reacting an aromatic diamine represented by or (in which R and has the same meaning as above) and diphenyl-3,3'-diisocyanate, or the general formula OCN-
It can be produced by reacting a diisocyanate represented by ~(or ~')-NC○ (in the formula, ~ and ~' have the same meanings as above) and a bisimidecarboxylic acid represented by the formula. can.

The aromatic polyamic acid used in the present invention includes 4,
4'-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, metaphenylenediamine, /graffenylenediamine, 4 ,4-
Diaminodiphenylpro/dine, 4,4-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,
6-diaminonaphthalene, 2,6-diaminopyridine,
4,4'-di(P-aminobenzoin) diphenyl ether
ter, 4,4'-di(P-aminophenoxy) diphenyl sulfone, 1,4-di(P-aminophenoxy)benzene, 1,3-di(P-aminophenoxy)benzene,
Aromatic diamines such as 4,4-di(0-aminophenoxy)diphenyl sulfone, or 4,4-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'
-Diaminodiphenyl ether-3'-sulfonamide, 3,3-diaminodiphenyl ether-4-sulfonamide, 4,4-diaminophenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-
Sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3-diaminodiphenylmethane-4-sulfonamide, 4,4-diaminodiphenyl sulfone-3-sulfonamide, 3,4-diaminodiphenyl sulfone -4-sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3
, 3-diaminodiphenylsulfone-4-sulfonamide, 4,4-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-4-sulfonamide, 3,3-diaminodiphenylsulfide Do-4-sulfonamide, 3,4'-diaminodiphenyl sulfide-3-sulfonamide, 1,4-diami/benzene-2-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4
'-Diamino diphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl blue 3'-carbonamide, 3,3'-diaminodiphenyl ether-
4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane-3'-carbonamide, 3,3 ′−
Diaminodiphenylmethane-4-triponamide, 4,
4'-diaminodiphenylsulfone-3-carbonamide, 3,4-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3
'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3
, 3'-diaminodiphenyl sulfide-4-carbonamide, 3,4-diaminodiphenyl sulfide-3'
- aromatic diaminoamide compound such as carbonamide, 1,4-diaminobenzene-2-carbonamide, and 3
, 3,4,4'-penzophenonetetracarboxylic acid, pyromellitic acid, 3,3',4,4'-diphenyltetracarboxylic acid, 2,3,6,7 naphthalenetetracarboxylic acid, 1,4 ,5,8-naphthalenetetracarboxylic acid,
3,4,9,10-berylenetetracarboxylic acid, 4,4
'-Sulfonyl diphthalic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ether-3,3', 4-tricarboxylic acid, diphenylsulfide-3,3,4-tricarboxylic acid, diphenylsulfone-3,34-tricarboxylic acid, diphenylp.

Pan-3,34-tricarboxylic acid, diphenyl-3,3
, 4-tricarboxylic acid, or their anhydrides, lower alkyl esters, acid halides, etc. are suitable. The ring base viscosity of the above polymer is 0.
2 to 1.9 and 0.4 to 1.3 are preferred.

Ring element viscosity is 0. Under sand conditions, the strength of the film is weak and its practical properties are insufficient, and when the ring base viscosity is 1.5 or more, workability is reduced. Next, in the present invention, the aromatic polyimide,
The granules containing a metal silicide as a main component and used dispersed in one or more heat-resistant polymers selected from aromatic polyamideimides and aromatic polyamide acids may be fine particles, and their shape may be , spherical, angular, needle-like, flake-like, etc.

The grains are usually selected in the range of 20△ to 500 mountains. Furthermore, the granules may be manufactured by any method. Any type of metal silicide can be used, including molybdenum silicide, tantalum silicide,
Manganese silicide, nickel silicide, titanium silicide and mixtures thereof are preferred.

Further, aluminum, boron, or ordinary resistors and conductors may be added to these materials. The blending amount of these granules is 10% of a heat-resistant polymer soluble in an organic polar solvent.
5 to 2000 parts by weight, preferably 50 to 2 parts by weight
000 parts by weight.

If the amount is less than 5 parts by weight, the desired characteristics as a resistor such as conductivity and resistance cannot be obtained, and if it exceeds 200 parts by weight, undesirable phenomena such as cracking and peeling occur, making practical use impossible. It is. Furthermore, especially 200 to 200
The range of cloud cover is good. Another composition of the invention is
100 parts by weight of at least one polymer selected from aromatic polyimide, aromatic polyamideimide, and aromatic polyamic acid that are soluble in organic solvents, and 100 to 100 parts by weight of a solvent that can substantially dissolve this polymer. 5000 parts by weight of 5 to 200 parts by weight per 10 parts by weight of polymer to the mixture.
parts by weight of resistive granules containing metal silicide as a main component are uniformly dispersed. The solvent used in this case is not particularly limited as long as it can substantially dissolve the polymer, but examples include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide. , cresol and mixtures thereof with other customary solvents are preferred. The amount of these solvents used is as follows:
The amount is selected in the range of 100 to 500 parts by weight relative to 0 parts by weight, and the range of 140 to 200 parts by weight is particularly preferred.

If this amount is less than 10 parts by weight or more than 5000 parts by weight, the solution viscosity will be inappropriate and difficult to handle. The composition of the present invention exhibits sufficient properties without the addition of any other components other than those listed above, but if desired, in order to further improve adhesion and reliability, silane coupling agents and epoxy agents may be added. Resins and the like can also be added. The amount added at this time is selected within the range of 2 to 10 parts by weight, with a range of 5 to 6 parts by weight being particularly preferred, based on 100 parts by weight of the polymer.

If this amount is less than 2 parts by weight, no effect will be observed;
If it exceeds 0 parts by weight, heat resistance will deteriorate. In order to produce the composition of the present invention, granules containing metal silicide as a main component,
It is mixed with the above polymer and its solvent, and stirred and dispersed until the polymer is completely dissolved.

In this way, a composition is prepared in which a solvent is added to fine particles containing the above-mentioned polymer and metal silicide as main components.

Furthermore, by completely removing the solvent of the polymer, a composition in which fine particles containing metal silicide as a main component are dispersed in the polymer can be obtained. When aromatic polyamic acid is used, heat treatment at around 300° C. is required, but when organic sacrificial solvent-soluble polyimide or polyamideimide is used, heat treatment at 200 qo or less is sufficient. The composition of the present invention in which fine particles mainly composed of metal silicide are dispersed can be used as molded products such as films and sheets. It is used as a coating agent, adhesive, etc.

The composition of the present invention in which fine particles containing metal silicide as a main component are dispersed has extremely high heat resistance and excellent temperature characteristics, so it has a wide range of applications such as thick film resistors and resistance heating elements. .

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

Example 1 Polyimide (reduced viscosity: 0
．． 4) Dissolve 10 parts by weight of N-methylpyrrolidone in 430 parts by weight and 70 parts by weight of toluene, and then add nickel silicide with an average particle size of 10 µm and titanium silicide with an average particle size of 20 µm in a weight ratio of 1:1. 20 parts by weight of the mixture of fine particles mixed in step 1 was added and dispersed using a pole mill to prepare a paste-like heat-resistant resistance material composition.

This composition was screen printed on an alumina substrate to form 20 conductor lines with a width of 1 line and a length of 2 lines (approximately 20 meters thick).
Heat treatment was performed at qC for 1 hour. The resistance value of this single pattern is 5/0, and the resistance temperature coefficient is 50//. It was 0.

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 2 Polyamideimide (reduced viscosity 0.7) produced from metaphenylene diamine and trimellitic anhydride chloride 1
00 parts by weight, 24 parts by weight of N-methylpyrrolidone and 16 parts by weight of dimethylacetamide were added to melt the polyamideimide, and then 27 parts by weight of tantalum silicide and 3 parts by weight of aluminum were added in a nitrogen atmosphere. 120
300 parts by weight of fine particles having an average particle size of 20 mm, which had been heat-treated at a temperature of 0.0 mm for 1 hour, were added and 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 1, the resistance value was 1 plate ○, and the temperature coefficient of resistance was 30 pm/°C. Next, 3 at 40000 to test heat resistance.
Heat treatment was performed for 0 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 3 Polyamic acid produced from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride (reduced viscosity 1.1
) 30 parts by weight of dimethylacetamide were added to 10 parts by weight of dimethylacetamide to dissolve the above polyamic acid, and then 200 parts by weight of molybdenum silicide with an average particle size of 20 μm and 30 parts by weight of dimethylacetamide were added to 10 parts by weight of
After adding 20 parts by weight of tantalum silicide with an average particle size of 20 and 15 parts by weight of manganese silicide having an average particle size of 20, the mixture was dispersed using a ball mill, and then the dimethylacetamide was removed by drying at 80°C for 30 minutes. A film was prepared and then heat treated at 300° C. for 1 hour to obtain a film-like heat-resistant resistance material composition.

The resistance value is arc 0, and the resistance temperature coefficient is -50 pm/℃
Met. Next, when the heat resistance was tested in the same manner as in Example 1, no change in resistance was observed, and the adhesiveness to the substrate was excellent.

Claims (1)

[Claims] 1. 100 parts by weight of at least one heat-resistant polymer selected from aromatic polyimide, aromatic polyamideimide, and aromatic polyamide acid that are soluble in organic polar solvents,
Resistant granules mainly composed of metal silicides 5 to 2000
A heat-resistant resistance material composition in which parts by weight are uniformly dispersed. 2 100 parts by weight of at least one heat-resistant polymer selected from aromatic polyimide, aromatic polyamideimide, and aromatic polyamide acid that are soluble in organic polar solvents,
Solvent that can substantially dissolve this polymer 100-500
1. A heat-resistant resistance material composition comprising adding 0 parts by weight to the mixture and uniformly dispersing 5 to 2000 parts by weight of resistive granules containing metal silicide as a main component per 100 parts by weight of polymer.