JPS6157866B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a heat-resistant resin paste having excellent dispersibility. The present inventors have previously proposed a heat-resistant resin paste using as a binder at least one heat-resistant polymer soluble in an organic polar solvent selected from aromatic polyimide, aromatic polyamide-imide, and aromatic polyamide acid. If the heat-resistant polymer, solvent, and electrical property-imparting particles are mixed in a desired blending ratio from the beginning and then dispersed using a ball mill, etc., the electrical property-imparting particles will not be uniformly dispersed, and the electrical properties will change. Adversely affects uniformity, printability, etc. As a result of research on dispersibility, the present inventors found that the above-mentioned solvent solution of the above-mentioned heat-resistant polymer has a concentration that minimizes the amount of solution added until the Daniel pour point is reached for the electrical property-imparting particles used initially. After adding and dispersing uniformly, if necessary, further add and disperse the above heat-resistant polymer and/or the above-mentioned solvent to obtain a desired blending ratio, thereby creating a heat-resistant polymer with excellent dispersibility. It was discovered that a resin paste could be obtained, and the present invention was completed. That is, the present invention provides 100 parts by weight of a heat-resistant polymer soluble in an organic polar solvent of at least one kind selected from aromatic polyimide, aromatic polyamide-imide, and aromatic polyamide acid, and the above-mentioned heat-resistant polymer is substantially dissolved. A method for producing a heat-resistant resin paste comprising 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 one kind selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron. In, first,
The above solvent solution of the above heat resistant polymer having a concentration that minimizes the amount of added solution until reaching the Daniel pour point is added to the electrical property-imparting particles to be used, and after uniformly dispersing, the mixture is adjusted to the desired blending ratio. The present invention provides a method for producing a heat-resistant resin paste, which further comprises adding and dispersing the above-mentioned heat-resistant polymer and/or the above-mentioned solvent, if necessary. The Daniel pour point referred to in the present invention can be determined as follows. Take the electrical property-imparting particles in a beaker, stir them with a glass rod, and continue adding the solvent and the above-mentioned heat-resistant polymer mixed solution while kneading the particles until they form a thick, sticky paste. Then gradually add the mixture until the paste becomes less resistant to stirring. At this time, the glass rod is quickly pulled up onto the beaker and a droplet is observed to adhere to the rod (keeping the rod vertical). The end point of the pour point is characterized by a thin film-like substance remaining on the rod, the last few drops falling at intervals of 1 to 2 seconds, and a sticky, rubber-like feel when touched with the hand. This pour point end point corresponds to approximately 80 KU as measured by a Stormer viscometer. Such measurements are performed for each concentration of the heat-resistant polymer solution, and the concentration and amount of the heat-resistant polymer solution that minimizes the amount of solution added until reaching the Daniel pour point is determined. For example, when polyamideimide synthesized from metaphenylene diamine and trimellitic anhydride chloride is used as the heat-resistant polymer and dimethylacetamide is used as the solvent, the following formula holds true.

[Table] Minimum polyamide solution Concentration of polyamide-imide solution (wt%) Reduced viscosity of the solution After uniformly dispersing the electrical property-imparting particles, the heat-resistant polymer and solvent added should be a solution of the heat-resistant polymer. This produces particularly good results. 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-), (R ₁₀ is P−C ₆ H ₄ −, C ₆ H ₄ −O−C ₆ H ₄ −, −C ₆ H ₄
-O-C ₆ H ₄ -O-C ₆ H ₄ -), (R ₁₁ is -O-, -O(-CH ₂ ) ₂ -, -O-(CH ₂ ) ₄ -
O
-, -O-(CH ₂ ) ₆ -O-,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

) Polyimides obtained from tetracarboxylic dianhydrides and the like are 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 (Here, 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 bisimide carboxylic acid. Aromatic polyamic acids used in the present invention include 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 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-sulfamide, 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, 1,4-
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'-diaminodiphenyl sulfide-3-
Carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-
Aromatic diaminoamide compounds such as 3'-carbonamide and 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',4,4'-diphenyl ether tetracarboxylic acid, trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylmethane-3,3',4-tricarboxylic acid, enyl ether-3,3',4-tricarboxylic acid, diphenylsulfide-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-
Tricarboxylic acid, diphenylpropane-3・3′・
4-tricarboxylic acid, diphenyl-3, 3', 4-
Aromatic polyamic acids obtained from aromatic tetracarboxylic acids such as tricarboxylic acid or tricarboxylic acids or their anhydrides, lower alkyl esters, acid halides, etc. are suitable. Next, the electrical property-imparting particles used in the present invention may be particles selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron, and are generally fine particles, and the shape thereof may be spherical or angular. , needle-like, flake-like, etc. are acceptable. The particle size is usually selected in the range of 20 Å to 500 μ. Examples of metals include Au, Ag, Pd, Ru,
Pt, Rh, Ir, Tl, Mo, Zn, Mn, Mg, Cd, Cr,
Nb, Ge, Zr, Cu, Ni, Al, Sn, Pb, Bi, In,
Examples include Fe, Co, Ti, Ta, W and alloys thereof. In addition, these oxides, nitrides,
Carbide, carbon, or boron may be used, and further,
A mixture of these may be used. Among these, particularly preferred are Au, Ag, Pd, Pt,
Mn, Cu, Ni, Al, Sn, Fe, Co, Cr, Ta, Ti,
W and alloys or mixtures thereof, or RuO ₂ ,
_CrO2 , ZnO, _SnO2 , _Fe2O3 , _{In2O3 , PdO} ,
Tl ₂ O ₃ , IrO ₂ , RhO, Sb ₂ O ₃ , Bi ₂ O ₃ , CdO,
Examples include TaN, TiN, WC, C, B, and mixtures thereof. 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 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.
2 to 100 parts by weight, especially 5 to 60 parts by weight per 100 parts by weight
The preferred range is 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. Preferred dispersion methods used in the present invention include a ball mill, a pebble mill, a sand grinder, a szegvariator, a three-roll mill, a high-speed impeller disperser, a high-speed stone mill, and a high-speed impact mill. Next, Examples will be described to explain the present invention more specifically, but the present invention is not limited to the Examples. Example 1 A dimethylacetamide solution of polyamideimide with a reduced viscosity of 0.4 synthesized from metaphenylene diamine and trimellitic anhydride and silver fine particles 5 with an average particle size of 1.8μ as particles imparting electrical properties.
When the Daniel pour point was determined using g, the minimum amount was found when the concentration of the dimethylacetamide solution of polyamideimide was 7.5% by weight, and the amount added at that time was 2.2 g. 10.7 g of the above 7.5% by weight solution of polyamideimide in dimethylacetamide and 25 g of the above silver fine particles
was dispersed for 12 hours using a ball mill, 18.2 g of a 30% by weight dimethylacetamide solution of the above polyamideimide was added, and ball milling was further carried out for 6 hours to obtain a heat-resistant resin paste with excellent dispersibility. Ta. The heat-resistant resin paste obtained in this way was screen printed on an alumina substrate, and 100%
Heat treatment was performed at ℃ for 30 minutes. The surface quality and end face precision of the obtained conductor line were good, and the resistivity was 2×10 ⁻⁴ Ω·cm with no variation. Example 2 Reduced viscosity obtained from 4,4'-di(m-aminophenoxy)diphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic dianhydride
When the Daniel pour point was determined using an N-methylpyrrolidone solution of polyimide with a concentration of 0.5% and 5g of ruthenium oxide fine particles with an average particle size of 0.8μ as particles imparting electrical properties, it was found that the concentration of the N-methylpyrrolidone solution of polyimide was 5% by weight. is the minimum amount when
The amount added at that time was 3 g. 15 g of the above 5% by weight polyimide N-methylpyrrolidone solution and 25 g of the above ruthenium oxide fine particles
g was dispersed for 12 hours using a ball mill, and then 25
9 g of a solution of the above polyimide in N-methylpyrrolidone (% by weight) was added, and ball milling was further carried out for 6 hours to obtain a heat-resistant resin paste having excellent dispersibility. The heat-resistant resin paste obtained in this way was screen printed on an alumina substrate.
Heat treatment was performed at ℃ for 30 minutes. The surface quality and end face accuracy of the obtained resistance line were good, and the specific resistance was
It was 40Ω・cm and there was no variation. Example 3 Obtained from 4,4'-diaminodiphenyl ether-3-carboxylic acid amide, 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic dianhydride reduced viscosity
0.6 dimethylacetamide solution of polyamic acid and an average particle size of 10μ as particles imparting electrical properties.
When the Daniel pour point was determined using 5 g of fine particles mixed with carbon and boron with an average particle size of 20 μ at a weight ratio of 1:1, the minimum amount was found when the concentration of the dimethylacetamide solution of polyamic acid was 4% by weight. The amount added at that time was 2.5 g. After dispersing 12.5 g of the above 4% by weight solution of the polyamic acid in dimethylacetamide and 25g of the above fine particles for 12 hours using a ball mill, 13g of the 20% by weight solution of the above polyamic acid in dimethylacetamide
was added and ball milled for further 6 hours to obtain a heat-resistant resin paste with excellent dispersibility. The heat-resistant resin paste obtained in this way was screen printed on an alumina substrate and
Heat treatment was performed at ℃ for 1 hour. The surface quality and end face accuracy of the obtained resistance line were good, and the specific resistance was
It was 0.5Ω-cm and there was no variation.

Claims (1)

[Claims] 1 At least one organic polar solvent-soluble heat-resistant polymer selected from 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 one kind of electrical property imparting particles selected from metals, metal oxides, metal nitrides, metal carbides, carbon, and boron. In a method for producing a heat-resistant resin paste consisting of 5 to 2000 parts by weight, first, the above-mentioned heat-resistant polymer having a concentration that minimizes the amount of solution added until reaching the Daniel pour point is added to the electrical property imparting particles to be used. After adding the solvent solution and dispersing it uniformly, as necessary, to obtain the desired blending ratio.
A method for producing a heat-resistant resin paste, which further comprises adding and dispersing the above-mentioned heat-resistant polymer and/or the above-mentioned solvent.