JPS6226347B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyamide resin composition that has excellent water resistance and electrical properties, particularly low water absorption and low dielectric loss. Polyamide is used in many applications,
Because of their high water absorption and dielectric loss, they are rarely used as electronic materials, and although improvement in water absorption and dielectric loss is desired, this has not yet been achieved. As a result of research to solve the above problems, the present inventors found that a composition formed by blending a specific amount of fluorine-containing polymer with a specific aromatic polyamide has a small water absorption rate and dielectric loss. The present invention has now been completed. Surprisingly, a composition made by blending a specific amount of fluorine-containing polymer with a specific aromatic polyamide has the following properties:
Both water absorption and dielectric loss are extremely small compared to specific aromatic polyamides alone. This is thought to be due to an interaction between the specific aromatic polyamide and the fluorine-containing polymer, rather than a mere mixture; This is clear from the fact that the water absorption coefficient and dielectric loss of the actual composition are much smaller than the water absorption coefficient and dielectric loss calculated from the ratio. An object of the present invention is to provide a polyamide resin composition with excellent water resistance and electrical properties. Furthermore, another object is to provide a composition useful as an electronic component material that has desired conductivity, resistance, or insulation properties and exhibits high precision and reliability. In one aspect, the present invention provides polyamide 40-99
% by weight and 1 to 60% by weight of a polymer containing 10 mol% or more of units derived from a fluorine-containing monoethylenically unsaturated monomer, the total amount of the polyamide and the fluorine-containing polymer. Provided is a polyamide resin composition in which the amount of polyamide resin is 50% by weight or more. In one aspect, the present invention comprises an aromatic polyamide containing 50 mol % or more of repeating units represented by the following general formula and having a reduced viscosity of 0.3 to 2.0 and 40 to 99 weight % of an aromatic polyamide containing fluorine-containing monoethylenically unsaturated monomers. Polymer 1 containing 10 mol% or more of units derived from
-60% by weight, and the total amount of the aromatic polyamide and the fluorine-containing polymer accounts for 50% by weight or more.

[expression] or

[Formula] [In the formula, A ₁ , A ₂ , A ₃ are

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or (However, R in the formula 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 a dimethylmethylene group. etc., and multiple R's and multiple X's in the same molecule may be the same or different.) It is a divalent residue represented by: ] The aromatic polyamide used in the present invention contains at least 50 mol% of the following repeating units.

【formula】

[Formula] (In the formula, A ₁ , A ₂ , A ₃ are

【formula】 【formula】

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or (However, R in the formula 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 a dimethylmethylene group. etc., and multiple R's and multiple X's in the same molecule may be the same or different). Polyamide may be a polymer consisting only of the above-mentioned repeating units, or it may contain 50 mol% or more of the above-mentioned repeating units in the molecule, with the remaining 50 mol% or less being ester bonds or ether bonds. The polymer may be a repeating unit based on bonds, sulfonyl bonds, carbonyl bonds, etc. The polyamide has a reduced viscosity of 0 to 3 to 2.0. Here, the reduced viscosity refers to a value measured at 30°C for a dimethylacetamide solution with a polymer concentration of 0.5% by weight. When the reduced viscosity is less than 0.3, it is difficult to obtain practical properties, and when the reduced viscosity exceeds 2.0, workability decreases. Examples of the fluorine-containing polymer used in the present invention include fluorine-containing monoethylenically unsaturated monomers, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, etc. Homopolymers of these monomers, copolymers of these monomers, and copolymers of 10 mol% or more of these monomers with 90 mol% or less of other monoethylenically unsaturated monomers are mentioned. As other monoethylenically unsaturated monomers, ethylene, propylene, other vinyl monomers not containing fluorine, vinylidene monomers, etc. are used. Among these fluorine-containing polymers, polychlorotrifluoroethylene,
Polyvinylidene fluoride, 10 mol% of units derived from polyvinylidene fluoride and vinylidene fluoride
Copolymers containing the above (for example, copolymers of vinylidene fluoride and pentafluoropropylene or hexafluoropropylene) are preferable, and especially copolymers containing polyvinylidene fluoride and 10 mol% or more of units derived from vinylidene fluoride are preferable. Coalescence is particularly preferred. The preferred molecular weight of the above-mentioned fluorine-containing polymer is from 10 ³ to 10 ⁷ , especially from 10 ⁴ to 10 ⁶ . The blending ratio of polyamide and fluorine-containing polymer is 40-99% by weight of the former and 1-60% by weight of the latter, preferably 60-95% by weight of the former and 5-40% by weight of the latter, particularly 70-90% by weight of the former. %, the latter is 10-30% by weight. The amount of fluorine-containing polymer is 1% by weight.
If it is less than 60, there will be almost no effect of the combination.
If it exceeds % by weight, mechanical strength and adhesion will decrease. In addition, other polymers such as polyamideimide, polyester, polyether, polyimide, polysulfone may be added to the composition consisting of polyamide and fluorine-containing polymer within the limits that do not impair its water resistance and desired electrical properties. , an epoxy resin may be blended. The blending amount of these polymers may be appropriately selected within a range of 50% by weight or less based on the total weight of the composition containing these polymers. The resin composition containing polyamide and a fluorine-containing polymer may contain metal, metal oxide, metal nitride, metal carbide, metal silicide, silicon, silicon oxide, silicon nitride, silicon carbide, boron, or boron nitride. By blending at least one type of granular material selected from carbon and carbon, it is possible to freely impart electrical properties such as conductivity, resistance, insulation, and dielectricity. The metal, metal oxide, metal nitride, metal carbide, metal silicide, silicon, silicon oxide, silicon nitride, silicon carbide, boron, boron nitride, and carbon used in the present invention are generally fine particles. The shape may be any shape such as radial shape, square shape, needle shape, flake shape, etc. The particle size is usually
Selected in the range of 20 Å to 500 μ. 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, Bi, In, Fe, Co, Ti,
W, Ta, Hf, Zr, Y, Ba, Be, Si, C, B and their alloys or their oxides, nitrides,
It may be a carbide, a silicide, or a mixture thereof. Among these, conductivity-imparting granules include:
Ai, Ag, Pd, Pt, Cu, Ni, Al, Sn, Mo, Mn,
Co, W, alloys thereof and mixtures thereof are preferred; Au, Ag, Pd, Pt, Cu, Ni, Al, Sn,
More preferably, it is selected from these alloys and mixtures thereof. As the resistance-imparting granules, SnO ₂ −Ta ₂ O ₅ ,
MoO ₃ −B, ZnO, CdO−ZnO, Ag−PdO, Ag−
PdO-Pd, _NiO2 -Ag, C-B-Ag, Ag-PdO
_{-Sb2O3 ,} C _- B, _Cu2O -CuO, _{In2O3 , In2O3}
−Sb ₂ O ₃ , Tl ₂ O ₃ , SnO ₂ , SnO ₂ −Sb ₂ O ₃ , IrO ₂ ,
RhO, RuO ₂ , TaN, TiN, TiN−Ti, TaN−
Ta, WC, WC-W, C, CoSi, ZrSi, TaSi,
Preferably it is selected from MnSi, MoSi, NiSi, TiSi and mixtures thereof. As the insulating or dielectric property imparting granules,
SiO, SiO ₂ , Si ₃ N ₄ , SiC, Ta ₂ O ₃ , Al ₂ O ₃ ,
_TiO2 , _HfO2 , _ZrO2 , _{Y2O3 , BaTiO3} , BN,
BeO, CoO, _PdO , _B2O3 , _Bi2O3 , _BaO and mixtures thereof are preferred; SiO, _SiO2 , _{Si3N4 ,}
SiC, Ta ₂ O ₃ , Al ₂ O ₃ , iO ₂ , BaTiO ₃ , BN,
More preferably it is selected from BeO, CoO, PbO, B ₂ O ₃ , Bi ₂ O ₃ , BaO and mixtures thereof. The amount of these granules to be blended is selected within the range of 5 to 4,000 parts by weight, preferably 100 to 2,000 parts by weight, per 100 parts by weight of the composition containing the aforementioned polyamidenofluorine-containing polymer. If the amount is less than 5 parts by weight,
Almost no blending effect is observed, and on the contrary, if it exceeds 4000 parts by weight, it becomes difficult to form a film. The composition of the present invention can be produced by dissolving the polyamide in a solvent and dissolving or dispersing the fluorine-containing polymer directly in the polyamide solution, or by dissolving the fluorine-containing polymer in another solvent. The solvent may be added to the polyamide solution, and then the solvent may be removed. In this case, it is preferable to dissolve the fluorine-containing polymer in the same solvent as the polyamide. In order to form an interaction between the polyamide and the fluorine-containing polymer, it is preferable to heat the polyamide and the fluorine-containing polymer to about 100°C after blending them. It is preferable to remove it by heating to a certain temperature. A composition of a polyamide and a fluorine-containing polymer can be obtained by melt compounding, or a composition of a polyamide and a fluorine-containing polymer can be obtained by polymerizing the polyamide in the presence of a fluorine-containing polymer. It is also possible to obtain compositions with coalescence. As a solvent for dissolving polyamide, N・N-
Dimethylformamide, N・N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2
- Pyrrolidone, hexamethylphosphoramide, formic acid, phenol, toluene, methanol, isopropanol, etc., and solvents for dissolving fluorine-containing polymers include methyl ethyl ketone, cyclohexanone, methyl acetate, diethyl carbonate, γ-butyrolactone, and tetrahydrofuran. , dioxane, N/N-dimethylformamide, N/N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, dimethyl sulfoxide, 1,1,3-trifluoropentachloropropane, 2,5-dichloro Examples include benzotrifluoride and O-chlorobenzotrifluoride. When producing a composition containing granules, when producing a composition of the above-mentioned polyamide and a fluorine-containing polymer, the granules are blended at any time and dispersed uniformly, so that the above-mentioned polyamide and fluorine-containing polymer are mixed together. It can be prepared in the same manner as in the method for producing a composition with a polymer containing element. The composition of the present invention has excellent water resistance and electrical properties, and is used for conductors, resistors, insulators, dielectrics, protective materials, adhesives, conductive adhesives for bonding, and capacitors for circuit wiring. dielectrics, integrated circuits,
It is suitable as an encapsulation agent for electrical elements such as active elements, passive elements, and conversion elements. By using the composition of the present invention, highly accurate and highly reliable conductive circuit boards, resistive circuit boards,
Electrical elements such as insulating substrates, circuit boards, multilayer circuit boards, hybrid circuit boards, mounted circuit boards, capacitors and other integrated circuits, active elements, passive elements, and conversion elements can be obtained. The composition of the present invention can also be used in the form of a paste. The base polymer of conventional pastes has insufficient moisture resistance, and therefore the stability of the resistance value of the paste obtained is poor. The composition comprising the polyamide and fluorine-containing polymer of the present invention has excellent moisture resistance, and the stability of the resistance value of the paste obtained from the composition is good. The composition of the present invention has a wide range of applications other than those mentioned above. Next, in order to explain the present invention more specifically,
Although examples will be described, the present invention is not limited to these examples. Examples 1 to 5 Polyamides, fluorine-containing polymers, and solvents shown in Table 1 were heat-treated on a Teflon sheet at 100°C for 4 hours and then at 200°C for 2 hours to form a 200μ
A thick film was created. The water absorption of the obtained film was measured according to JIS-K6911-1962 by immersing it at 20℃ for 24 hours, and the dielectric loss at 1MHz was measured according to ASTM-D150-70 by depositing a silver electrode. It was formed and measured using the Bridge method at 20°C and 60%RH. The results are shown in Table 1, and it was found that it had excellent water resistance and electrical properties. Examples 6 to 10 Using the same polyamide, fluorine-containing polymer, and solvent as in Examples 1 to 5 in the same amounts as in Examples 1 to 5, the granules shown in Table 2 were added and uniformly dispersed with a ball mill. After that, it was treated in the same manner as in Examples 1 to 5 to obtain a granule-containing film (thickness: 200μ).The water absorption rate was measured in the same manner as in Examples 1 to 5, and the results are shown in Table 2. It had excellent water resistance. In addition, 20 lines of 1 mm width and 2 cm length were drawn on the ceramic substrate using the paste obtained by adding the granules.
After main screen printing (approximately 50μ thick), heat treatment was performed at 100°C for 1 hour. The resistance value of one of the obtained lines is shown in Table 2, and it is possible to provide desired conductivity, resistance, insulation, and excellent electrical properties.

【table】

【table】

Claims (1)

[Scope of Claims] 1 40-99% by weight of an aromatic polyamide containing 50 mol% or more of repeating units represented by the following general formula and having a reduced viscosity of 0.3 to 2.0 and a fluorine-containing monoethylenically unsaturated monomer. 10 mol% of units derived from the body
1-60% by weight of a polymer containing
A polyamide resin composition in which the total amount of the aromatic polyamide and the fluorine-containing polymer is 50% by weight or more. [Formula] or [Formula] [In the formula, A ₁ , A ₂ , A ₃ are [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] 【formula】 or (However, R in the formula 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 a dimethylmethylene group. etc., and multiple R's and multiple X's in the same molecule may be the same or different.) It is a divalent residue represented by: 2. The polyamide resin composition according to claim 1, wherein the fluorine-containing monoethylenically unsaturated monomer is vinylidene fluoride. 3 A unit derived from 40-99% by weight of an aromatic polyamide containing 50 mol% or more of repeating units represented by the following general formula and having a reduced viscosity of 0.3 to 2.0 and a fluorine-containing monoethylenically unsaturated monomer. 10 mole%
1-60% by weight of a polymer containing
Resin composition 100 in which the total amount of the aromatic polyamide and the fluorine-containing polymer is 50% by weight or more
Based on parts by weight, metals, metal oxides, metal nitrides,
Contains 5 to 4000 parts by weight of at least one granular material selected from the group consisting of metal carbide, metal silicide, silicon, silicon oxide, silicon nitride, silicon carbide, boron, boron nitride, and carbon. Polyamide resin composition. [Formula] or [Formula] [In the formula, A ₁ , A ₂ , A ₃ are [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] 【formula】 or (However, R in the formula 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 a dimethylmethylene group. etc., and multiple R's and multiple X's in the same molecule may be the same or different.) It is a divalent residue represented by: ] 4 Claim 3, wherein the granules are at least one selected from the group consisting of Au, Ag, Pb, Pt, Cu, Ni, Al, Sn, and alloys thereof.
The polyamide resin composition described in . 5 The granules are SnO ₂ −Ta ₂ O ₅ (meaning a mixture of SnO ₂ and Ta ₂ O _5. The same applies hereinafter), MoO ₃ −
B, ZnO, CdO−ZnO, Ag−PdO, Ag−PdO−
Pd, NiO ₂ -Ag, C-B-Ag, Ag-PdO-
_{Sb2O3 ,} C _- B, _Cu2O -CuO, _{In2O3 , In2O3-
Sb2O3} , _Tl2O3 , _SnO2 , _{SnO2 - Sb2O3 , RuO2 ,}
TaN, TiN, TiN−Ti, TaN−Ta, WC, WC−
W, C, CoSi, ZrSi, TaSi, MnSi, MoSi,
The polyamide resin composition according to claim 3, which is at least one member selected from the group consisting of NiSi and TiSi. 6 The granules are CoO, PbO, B ₂ O ₃ , Bi ₂ O ₃ ,
BaO, SiO, SiO ₂ , Si ₃ N ₄ , SiC, Ta ₂ O ₃ ,
The polyamide resin composition according to claim 3, which is at least one selected from the group consisting of Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , BN and BeO.