JPS6157865B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a heat-resistant resin paste having long-term stability. In ordinary resin pastes, simply blending a mixture of two or more types of electrical property-imparting particles does not produce the sintering effect that provides long-term stability with excellent electrical properties, and only shows the properties as a mixture. . In addition, conventional resin pastes have poor heat resistance and lack reliability, so they are only used for simple applications that do not particularly require reliability.
It was pointless to add a sintering effect that would give long-term stability with excellent electrical properties. However, on the other hand, there is a need for a highly reliable paste that can be processed at low temperatures and has a sintering effect that provides long-term stability with excellent electrical properties, and although much research has been conducted, this has not been realized. is the current situation. In view of the above, the present inventors conducted extensive research and found that aromatic polyimides soluble in organic polar solvents,
In producing a heat-resistant resin paste consisting of at least one type of heat-resistant polymer selected from aromatic polyamide-imide and aromatic polyamide acid and two or more types of particles imparting electrical properties, first, two or more types of particles imparting electrical properties are added. By heat-treating a homogeneous mixture of particles at a temperature of 500 to 2000°C and then dispersing it in the above-mentioned heat-resistant polymer and solvent, sintering can be performed at low temperatures and provides long-term stability with excellent electrical properties. The inventors have discovered that a highly reliable heat-resistant resin paste that is effective can be obtained, and have completed the present invention. That is, the present invention includes 100 parts by weight of at least one heat-resistant polymer selected from organic polar solvent-soluble aromatic polyimide, aromatic polyamideimide, and aromatic polyamic acid, and the above-mentioned heat-resistant polymer is substantially dissolved. Produce a heat-resistant resin paste consisting of 100 to 5,000 parts by weight of a solvent and 5 to 2,000 parts by weight of particles imparting electrical properties of at least two or more types selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron. In the method, first,
A homogeneous mixture of one or more types of particles imparting electrical properties to 500
The present invention provides a method for producing a heat-resistant resin paste, which is characterized in that the paste is heat-treated at a temperature of ~2000°C and then dispersed in the heat-resistant polymer and solvent. A method for heat-treating a homogeneous mixture of two or more types of particles imparting electrical properties according to the present invention at a temperature of 500 to 2000°C is to use a conventional device such as an electric furnace in air, nitrogen, hydrogen, etc. Under the atmosphere of
Heat treated at a temperature of 500-2000℃ for 10 minutes to 10 hours. Further, if necessary, the electrical property-imparting particles are pulverized after the heat treatment. If the heat treatment temperature is below 500°C, a long time is required to produce the sintering effect, and if it is above 2000°C, the heat treatment equipment becomes expensive and both are impractical. The heat treatment temperature varies depending on the type of particles imparting electrical properties to be mixed, but
The preferred range is 700 to 1200°C, particularly 700 to 1200°C. The organic polar solvent-soluble heat-resistant polymer used in the present invention includes aromatic polyimide, aromatic polyamide-imide, and aromatic polyamide acid, and in particular aromatic polyimide and aromatic polyamide-imide that do not generate water when drying the paste. is optimal. The organic solvent soluble polyimide used in the present invention has the formula:

[Formula] (R ₁ is −CH(CH ₃ ) ₂ , −SO ₂ NH ₂ , CH ₃ ),

[Formula] (R ₂ is

[Formula] -O-, -S -, _-CH2- , [-C( _CF3 ) ₂ ] _-3 ,

[Formula] −SO ₂ −,

【formula】

[Formula] (R' is -S-,

【formula】

【formula】 【formula】

【formula】),

【formula】

[Formula] -C(CF ₃ ) ₂ -,

【formula】),

[Formula] (R ₃ is -O -, -CH ₂ -, -SO ₂ -,

[Formula] −CH ₂ −, R ₄ is

[Formula] −CH ₃ , −OCH ₃ )

【formula】

[Formula] (R ₅ is

[Formula] -O-, (x+y=3),

[Formula] (R ⁶ is -O-, -CH ₂ -, -SO ₂ -,

[Formula] -C ₆ H ₄ -O-C ₆ H ₄ -, -O-C ₆ H ₄ -O-, R ₇ is

【formula】

[Formula]-OH),

【formula】

【formula】

( _R8 is -O-, _-SO2- , _-CH2- ,

[Formula] − CO ₂ −,

[Formula] -S-) diamine and formula,

【formula】

【formula】

[Formula] (R ₉ is -O -,

【formula】

【formula】

[Formula] −SO ₂ −,

[Formula] -C(F ₂ ) ₃ -, -C(CF ₃ ) ₂ -, -(CF ₂ ) ₆ -, -O(CF ₂ ) ₅ -O-),

[Formula] (R ₁₀ is P −C ₆ H ₄ −, C ₆ H ₄ −O−C ₆ H ₄ −, −C ₆ H ₄ −O−
_{C6H4 -} O _{- C6H4-} ), (R ₁₁ is -O-, -O(-CH ₂ ) ₂ -, -O-(CH ₂ ) ₄ -
O, -O-( _CH2 ) ₆ -O-,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

A polyimide obtained from a tetracarboxylic dianhydride represented by the following is suitable. The organic polar solvent-soluble aromatic polyamideimide used in the present invention has the general formula Or Or [Here, Ar is

【formula】

【formula】 【formula】

Ar′ is

【formula】

【formula】

[Formula] (R represents hydrogen, an alkyl group (e.g. methyl, ethyl, propyl, isopropyl, etc.), halogen, and X represents O, SO ₂ , CH ₂ , CO, COO, C
(CH ₃ ) ₂ and S, which may be the same or different. ), and n represents a positive integer. ] An aromatic polyamideimide represented by the following is suitable. This manufacturing method uses the general formula

【formula】

【formula】

【formula】

(Here, R represents hydrogen, an alkyl group, or a halogen, and X represents O, SO ₂ , CH ₂ , CO, COO, C
(CH ₃ ) ₂ and S, which may be the same or different. ) A method for reacting an aromatic diamine represented by the formula with trimellitic acid chloride, general formula (Here, R represents hydrogen, an alkyl group, or a halogen, and X represents O, SO ₂ , CH ₂ , CO, COO, C
(CH ₃ ) ₂ and S, which may be the same or different. A method of reacting bisimidocarboxylic acid represented by ) with 3,3'-diisocyanatodiphenyl. General formula O=C=N-Ar (or Ar')-N=C=O (where Ar is

【formula】

【formula】

【formula】

Ar′ is

【formula】

【formula】

[Formula] (R represents hydrogen, alkyl group, halogen, X represents O, SO ₂ , CH ₂ ,
It represents CO, COO, C(CH ₃ ) ₂ and S, and these may be the same or different. ) and the formula There is a method of reacting with bisimide carboxylic acid. Aromatic polyamic acids used in the present invention include 4,4'-diaminodiphenyl ether, 4,
4'-diaminophenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, metaphenylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylpropane, 4. 4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,6-diaminopyridine,
4,4'-di(p-aminobenzoin) diphenyl ether, 4,4'-di(p-aminophenoxy)
Aromatic diamines such as diphenylsulfone, 1,4-di(p-aminophenoxy)benzene, 1,3-di(p-aminophenoxy)benzene, 4,4'-di(o-aminophenoxy)diphenylsulfone, or・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'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-
Diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone -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-4-sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 11.
4-diaminobenzene-2-sulfonamide,
4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-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-carbonamide,
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'-
Aromatic diaminoamide compounds such as diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-carbonamide, 1,4-diaminobenzene-2-carbonamide, and 3. 3', 4, 4'-benzophenonetetracarboxylic 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-perylenetetracarboxylic acid, 4,4'-sulfonyl diphthalic acid, 3,3',4'-diphenyl ether tetracarboxylic acid, trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl enyl ether 3,3',4-tricarboxylic acid,
Diphenylsulfide-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-tricarboxylic acid, diphenylpropane-3,3',4-
Aromatic polyamic acids obtained from aromatic tetracarboxylic acids or tricarboxylic acids such as tricarboxylic acid and diphenyl-3,3',4-tricarboxylic acid, or their anhydrides, lower alkyl esters, acid halides, etc. are suitable. Next, the at least two or more kinds of electrical property imparting particles used in the present invention are at least two or more kinds of particles selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron, and after heat treatment, The shape may be spherical, angular, needle-like, flake-like, etc., and the particle size may generally be fine, usually between 20 Å and 500 μm.
selected within the range. Specific examples include Au, Ag,
Pd, Ru, Pt, Rh, Ir, Tl, Mo, Zn, Mn, Mg,
Cd, Cr, Nb, Ge, Zr, Cu, Ni, Al, Sn, Pb,
Two or more materials selected from Bi, In, Fe, Co, Ti, and their oxides, nitrides, carbides, carbon, boron, etc. are used. Among these, particularly preferred are Au, Ag, Pd,
Pt, Mn, Cu, Ni, Al, Sn, Fe, Co, Cr, Ta,
Ti, W, _RuO2 , _CrO2 , ZnO, _SnO2 , _{Fe2O3 ,}
In ₂ O ₃ , PdO, Tl ₂ O ₃ , IrO ₂ , RhO, Sb ₂ O ₃ ,
They are at least two or more selected from Bi ₂ O ₃ , CdO, TaN, TiN, WC, C, B, and the like. The blending amount of these fine particles is 5 to 5 parts by weight per 100 parts by weight of the heat-resistant polymer soluble in organic polar solvent.
selected within the range of 2000 parts by weight, particularly preferably
It is 50 to 1000 parts by weight. If the amount is less than 5 parts by weight, the electrical properties will be insufficient, and if the amount is more than 2000 parts by weight, cracking or peeling will occur, making it impossible to use it practically. The solvent for the organic solvent-soluble heat-resistant polymer used in the present invention may be any solvent as long as it substantially dissolves the polymer, but preferred ones include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, Examples include hexamethylphosphoramide, cresol, and mixtures of these and ordinary solvents. The blending amount of these solvents is selected in the range of 100 to 5000 parts by weight, particularly preferably 140 to 5000 parts by weight, based on 100 parts by weight of the organic polar solvent-soluble heat-resistant polymer.
2000 parts by weight. The blending amount is 100 parts by weight or less, or
If the amount is 5000 parts by weight or more, the solution viscosity will be too high or too low, resulting in poor dispersibility and handling properties, which is not preferred in practice. In order to improve adhesiveness, reliability, etc. of the heat-resistant resin paste according to the present invention, a silane coupling agent, an epoxy resin, etc. may be added.
The amount added is a heat-resistant polymer soluble in organic polar solvents.
The preferable range is 2 to 100 parts by weight, particularly 5 to 60 parts by weight, based on 100 parts by weight. If the amount is less than 2 parts by weight, no effect will be observed, and if it is more than 100 parts by weight, the heat resistance will deteriorate. As the dispersion method used in the present invention, a ball mill, a pebble mill, a sand grinder, a Szeg variant attritor, a three-roll mill, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, etc. are used. The heat-resistant polymer solution and at least two or more types of particles imparting electrical properties are first mixed in such a manner that the amount of the solution added is minimized until reaching the point, and after uniformly dispersing, the mixture is adjusted to a desired blending ratio. Particularly preferred is a method in which the heat-resistant polymer solution is added and further dispersed. Next, Examples will be described to explain the present invention more specifically, but the present invention is not limited to the Examples. Example 1 600 parts by weight of a mixture of silver particles with an average particle size of 700 Å and palladium particles with an average particle size of 0.5 μ in a 1:1 weight ratio was heat treated at 800°C for 2 hours, and then mixed with metaphenylene diamine and anhydrous. A heat-resistant resin paste was obtained by dispersing it in 100 parts by weight of polyamideimide synthesized from trimellitic acid chloride and 400 parts by weight of dimethylacetamide. The thus obtained heat-resistant resin paste was screen printed on an alumina substrate with 20 lines of 1 mm width and 2 cm length (approximately 50 μ thick) and heated at 100°C.
Treated for 30 minutes. The specific resistance of this pattern is 5×
10 ^-4 Ω-cm, there was no variation in specific resistance, and no change in specific resistance over time was observed. Example 2 Polyimide synthesized from 4,4'-di(m-aminophenoxy)diphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic dianhydride
100 parts by weight of N-methylpyrrolidone, 430 parts by weight of N-methylpyrrolidone, and 70 parts by weight of toluene were mixed with 250 parts by weight of tantalum titanide with an average particle size of 20 μm and tantalum with an average particle size of 50 μm in a 1:1 weight ratio at 1200°C. After heat treatment for 2 hours, the mixture was dispersed to obtain a heat-resistant resin paste. The thus obtained heat-resistant resin paste was screen printed with 20 lines (approximately 50 μm thick) with a width of 1 mm and a length of 2 cm on an alumina substrate, and treated at 100° C. for 1 hour. The resistance value of this single pattern is
It was 35KΩ, and there was no variation in resistance value, and no change in resistance value over time was observed. Example 3 500 parts by weight of fine particles made by mixing carbon with an average particle size of 10 μm and boron with an average particle size of 20 μm in a 1:1 weight ratio,
After heat treatment at 1000°C for 2 hours, 4,4'-diaminodiphenyl ether-3-carboxylic acid amide, 4,4'-diaminodiphenyl ether and 3.
A heat-resistant resin paste was obtained by dispersing the mixture in 100 parts by weight of polyamic acid obtained from 3', 4, 4'-benzophenone tetracarboxylic dianhydride and 500 parts by weight of dimethylacetamide. The thus obtained heat-resistant resin paste was screen printed with 20 lines (approximately 50 μm thick) with a width of 1 mm and a length of 2 cm on an alumina substrate, and treated at 300° C. for 1 hour. The specific resistance of this pattern is 0.3Ω
-cm, there was no variation in specific resistance, and no change in specific resistance over time was observed.

Claims (1)

[Claims] 1 At least one heat-resistant polymer selected from organic polar solvent-soluble aromatic polyimide, aromatic polyamideimide, and aromatic polyamide acid
100 parts by weight, 100 to 5,000 parts by weight of a solvent that substantially dissolves the heat-resistant polymer, and at least two or more elements selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron to impart electrical properties. In a method for producing a heat-resistant resin paste consisting of 5 to 2000 parts by weight of particles, first, a homogeneous mixture of two or more types of particles imparting electrical properties is heat-treated at a temperature of 500 to 2000°C, and then the above-mentioned heat-resistant polymer and A method for producing a heat-resistant resin paste characterized by dispersing it in a solvent.