JPS6351183B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heat-resistant resin composition that has excellent water resistance and electrical properties, particularly low water absorption and low dielectric loss. In recent years, electronic components are particularly required to be highly integrated and highly reliable. Along with this, there has been a desire to develop polymeric electronic materials with excellent heat resistance, water resistance, and electrical properties, but this has not yet been achieved. Most of the synthetic resins known so far are
At temperatures above 250°C, it exceeds its softening point or approaches its decomposition point, making it thermally unstable.
Therefore, polymers with excellent heat resistance are used as materials for electronic components that are exposed to high temperatures during use. However, no polymer material is known that satisfies many electrical properties in addition to heat resistance.
Polyamide-imide has excellent heat resistance, alkali resistance, abrasion resistance, etc., and is attracting attention as a polymeric electronic material, but it also has slightly high water absorption and dielectric loss. As a result of research aimed at lowering the water absorption rate and dielectric loss of polyamide-imide materials, the present inventors found that a composition made by blending a specific amount of fluorine-containing polymer with polyamide-imide has excellent heat resistance. Furthermore, they have discovered that both water absorption and dielectric loss are small, leading to the completion of the present invention. Surprisingly, a composition formed by blending a specific amount of fluorine-containing polymer with polyamide-imide has extremely low water absorption and dielectric loss compared to polyamide-imide alone. This is thought to be due to an interaction between the polyamide-imide and the fluorine-containing polymer, rather than a simple mixture, and this is due to the water absorption rate calculated from the blending ratio of the polyamide-imide and the fluorine-containing polymer. This is clear from the fact that the water absorption rate and dielectric loss of the actual composition are much smaller than the dielectric loss. An object of the present invention is to provide a polymer composition with excellent heat resistance, water resistance, and electrical properties. moreover,
Another object of the present invention is to provide a resin 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 has a repeating unit represented by the following general formula: or (In the above general formula, A ₁ represents an aliphatic, aromatic or alicyclic tetravalent residue, and A ₅ and A ₇ represent an aliphatic, aromatic or alicyclic trivalent residue. , A ₂ , A ₃ , A ₄ , A ₆ , A ₈ represent aliphatic, aromatic or alicyclic divalent residues, m ₁ , m ₄ , m ₅ ,
m ₆ , m ₇ , m ₈ represent positive integers, m ₂ and m ₃ are 0
Or represents a positive integer. ) 40 to 66% by weight of a polyamideimide containing at least 50% by mole of Fluorine-containing polymer 1 selected from the combination
A heat-resistant resin composition comprising ˜60% by weight is provided. In another aspect of the present invention, a metal, a metal oxide, a metal nitride, a metal carbide, a metal silicide,
At least one granule selected from the group consisting of silicon, silicon oxide, silicon nitride, silicon carbide, boron, boron nitride, and carbon 5 to 4000
Provided is a heat-resistant resin composition in which parts by weight are blended. The polyamide-imide used in the present invention may be a polymer containing at least 50 mol% of repeating units consisting of an amide group and an imide group as defined above, but among these polyamide-imides, In the above general formula, A ₁ is

【formula】

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[expression] or

[Formula] A ₂ , A ₃ , A ₄ , A ₆ , A ₈ are

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

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or A ₅ , A ₇ are

[Formula] (In the formula, R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom,
A sulfur atom, a sulfonyl group, a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group, a dimethylmethylene group, etc., and multiple R's and multiple X's in the same molecule may be the same or different. An aromatic polyamideimide represented by the following is preferable from the viewpoint of heat resistance. Furthermore, the aromatic polyamideimide, which is soluble in organic polar solvents and contains 50 mol% or more of the following repeating units, is easy to create compositions with fluorine-containing polymers and can be applied to various uses. It is particularly preferable in terms of properties. or Ar in the formula is

【formula】

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[Formula] or Ar′ is the formula

【formula】

【formula】

【formula】

[Formula] or Ar″ is the expression

【formula】

【formula】

[Formula] or Ar is the formula

【formula】

[Formula] or (wherein R and X are as defined above). Polyamideimide 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 consisting of ester bonds, It may be a polymer having repeating units based on ether bonds, sulfonyl bonds, carbonyl bonds, etc. The ring base viscosity of the above polyamideimide is 0.1 to 2.0.
In particular, it is preferably 0.3 to 1.5. 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 0.1, it is difficult to obtain practical properties, and when the reduced viscosity exceeds 2.0, workability decreases. The fluorine-containing polymer used in the present invention is selected from polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and copolymers containing 10 mol% or more of units derived from vinylidene fluoride. Copolymers containing 10 mol% or more of units derived from vinylidene fluoride include 10 mol% or more of vinylidene fluoride and other fluorine-containing monoethylenically unsaturated monomers (e.g., tetrafluoroethylene, chlorotrifluoride). fluoroethylene, pentafluoropropylene, hexafluoropropylene, vinyl fluoride) and/or other monoethylenically unsaturated monomers (e.g. ethylene, propylene, other fluorine-free vinyl monomers and vinylidene monomers) A copolymer derived from 90 mol% or less of Preferred fluorine-containing polymers are polyvinylidene fluoride and copolymers containing 10 mol% of units derived from vinylidene fluoride (e.g., copolymers of vinylidene fluoride and pentafluoropropylene or hexafluoropropylene). . The preferred molecular weight of the above fluorine-containing polymer is:
10 ³ to 10 ⁷ , especially 10 ⁴ to 10 ⁶ . The blending ratio of polyamide-imide and fluorine-containing polymer is 40-99% by weight of the former and 1-60% by weight of the latter, preferably 5-95% by weight of the former and 5-95% by weight of the latter.
40% by weight, especially the former 70-90% by weight and the latter 10-90% by weight
It is 30% by weight. The amount of fluorine-containing polymer is 1
When the amount is less than 60% by weight, almost no effect is obtained, and when it exceeds 60% by weight, the heat resistance deteriorates. It should be noted that other polymers, such as
For example, polyamide, polyester, polyether, polyimide, polysulfone, and epoxy resin may be blended. The resin composition containing polyamide-imide and a fluorine-containing polymer may contain metal, metal oxide, metal nitride, metal carbide, metal silicide, silicon, silicon oxide, silicon nitride, silicon carbide, boron,
By blending at least one type of granular material selected from boron nitride and carbon, conductivity and
It is possible to freely impart electrical properties such as resistance, insulation, and dielectricity. In general, metals impart electrical conductivity or resistance (i.e., limited electrical conductivity); metal oxides impart resistance, insulation, or dielectric properties; metal nitrides impart resistance; metal carbides impart resistance; metals Silicide imparts resistance, silicon imparts resistance, silicon oxide imparts insulation or dielectricity, silicon nitride imparts insulation or dielectricity, silicon carbide imparts insulation or dielectricity, boron imparts resistance. , boron nitride can be blended for the purpose of imparting insulation or dielectric properties, and carbon can be blended for the purpose of imparting resistance. 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 spherical, angular, needle-like, flake-like, 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,
It may also be an alloy thereof, or an oxide, nitride, carbide, or silicide thereof, or a mixture thereof. Among these, conductivity-imparting granules include:
Au, 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,
More preferably, it is selected from Sn, alloys thereof and mixtures thereof. The resistance-imparting granules include SnO ₂ --Ta ₂ O ₅ ,
MoO ₃ -B, ZnO, CdO-ZnO, Ag-PdO, Ag
―PdO―Pd, NiO ₂ ―Ag, C―B―Ag, Ag―
PdO―Sb ₂ O ₃ , C―B, Cu ₂ O―CuO, In ₂ O ₃ ,
In ₂ O ₃ ―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,
Preferably, it is selected from TaSi, MnSi, MoSi, NiSi, TiSi, Si, B 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 ,
TiO ₂ , HfO ₂ , ZrO ₂ , Y ₂ O ₃ , BaTiO ₃ , BN,
BeO, CoO, PbO, B ₂ O ₃ , Bi ₂ O ₃ , BaO and mixtures thereof are preferred, and SiO, SiO ₂ , Si ₃ N ₄ ,
SiC, Ta ₂ O ₃ , Al ₂ O ₃ , TiO 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 blending amount of these granules is as follows:
5 to 4000 parts by weight, preferably 100 to 4000 parts by weight
Selected in the range of 2000 parts by weight. If the amount is less than 5 parts by weight, almost no effect will be observed, and if it exceeds 4,000 parts by weight, it will be difficult to form a film. As a method for producing the composition of the present invention, when polyamide-imide is soluble in a solvent, it is dissolved in the solvent in the form of polyamide-imide, and when polyamide-imide is not dissolved in the solvent, it is dissolved in the solvent in the form of polyamide-imide. Then, the fluorine-containing polymer is directly dissolved or dispersed in the polyamide-imide solution or polyamide acid solution, or the fluorine-containing polymer is dissolved in another solvent and blended into the polyamide-imide solution or polyamide acid solution. Then,
The solvent may then be removed. When dissolved in the form of polyamide acid, it is necessary to subsequently convert it to polyamideimide, and it is preferable that the fluorine-containing polymer is dissolved in the same solvent as the polyamideimide. In order to form an interaction between the polyamide-imide and the fluorine-containing polymer, it is preferable to heat the mixture to about 100°C after blending the polyamide-imide or polyamide acid with the fluorine-containing polymer, and when removing the solvent. It is also preferable to remove it by heating it to about 100°C. When polyamide-imide melts,
It is also possible to obtain a composition of polyamide-imide and a fluorine-containing polymer by melt compounding, or by polymerizing polyamide-imide or polyamide acid in the presence of a fluorine-containing polymer, and then in the case of polyamide acid. It is also possible to obtain a composition of polyamide-imide and a fluorine-containing polymer by converting it into polyamide-imide. As a solvent for dissolving polyamideimide or polyamide acid, N,N-dimethylformamide,
N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, phenol, etc., and solvents for dissolving fluorine-containing polymers include methyl ethyl ketone, cyclohexanone, methyl acetate,
Diethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, 1,
1,3-trifluoropentachloropropane,
2,5-dichlorobenzotrifluoride, O-
Examples include chlorobenzotrifluoride. When producing a composition containing granules, when producing a composition of the above-mentioned polyamide-imide and a fluorine-containing polymer, the granules are blended at all times and uniformly dispersed. and a fluorine-containing polymer. The composition of the present invention has excellent heat resistance, water resistance, and electrical properties, and is used as a conductor for circuit wiring, a resistor, an insulator, a dielectric, a protective material, an adhesive, and a conductive adhesive for bonding. It is suitable as an encapsulation agent for electrical elements such as dielectrics for capacitors, integrated circuits, active devices, passive devices, and conversion devices. By using the composition of the present invention, highly accurate and highly reliable conductor circuit boards, resistance circuit boards, insulating boards, circuit boards, multilayer circuit boards,
Electrical elements such as high-grid circuit boards, mounted circuit boards, capacitors and other integrated circuits, active devices, passive devices, conversion devices, etc. 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 is heat resistant,
The moisture resistance was insufficient, and therefore the stability of the resistance value of the product obtained was poor. The composition comprising polyamide-imide and a fluorine-containing polymer of the present invention has excellent heat resistance and moisture resistance, and the stability of the resistance value of the paste obtained from the above composition is very good. The composition of the present invention comprises:
It 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 10 Polyamideimide or polyamic acid, a fluorine-containing polymer, and a solvent shown in Table 1 were heat-treated on a Teflon sheet at 100°C for 4 hours and then at 250°C for 2 hours to form a 200μ thick sheet. created a film. The water absorption rate of the obtained film was determined according to JIS-K6911-
The dielectric loss at 1MHz was measured by immersion at 20℃ for 24 hours in accordance with the 1962 standard, and the dielectric loss at 1MHz was measured by depositing silver electrodes in accordance with ASTM-D150-70.
The thermal decomposition initiation temperature was measured using a thermobalance at a heating rate of 10°C/min. The results are shown in Table 1, showing excellent heat resistance,
It had water resistance and electrical properties. Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out using polyamide-imide and fluorine-containing polymer, respectively.
The results were as shown in Table 1.

【table】

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[Table] Examples 11 to 23 The granules shown in Table 2 were prepared using the same amounts of polyamideimide or polyamic acid, fluorine-containing polymer, and solvent as in Examples 1 to 10, respectively. In addition, the mixture was uniformly dispersed using a ball mill, and then treated in the same manner as in Examples 1 to 10 to obtain a granule-containing film (thickness: 200 μm). Example 1 of water absorption rate
Table 2 shows the results of measurements made in the same manner as in samples 1 to 10, and it was found that the samples 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 and then at 250°C for 1 hour. The resistance value of one of the obtained lines is shown in Table 2, and it can be seen that it is possible to provide desired conductivity, resistance, insulation, and excellent electrical properties.

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Claims (1)

[Claims] 1. Repeating unit represented by the following general formula or (In the above general formula, A ₁ represents an aliphatic, aromatic or alicyclic tetravalent residue, and A ₅ and A ₇ represent an aliphatic, aromatic or alicyclic trivalent residue. , A ₂ , A ₃ , A ₄ , A ₆ , A ₈ represent aliphatic, aromatic or alicyclic divalent residues, m ₁ , m ₄ , m ₅ ,
m ₆ , m ₇ , m ₈ represent positive integers, m ₂ and m ₃ are 0
Or represents a positive integer. ) and a copolymer containing 40 to 99% by weight of polyamideimide containing 50% or more of Fluorine-containing polymer 1 selected from among
A heat-resistant resin composition comprising ~60% by weight. 2 In the general formula, A ₁ is [formula] [formula] [formula] [formula] [formula] or [formula] A ₂ , A ₃ , A ₄ , A ₆ , A ₈ is [formula] [formula] [formula] ] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] or A ₅ , A ₇ are [formula] (wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom,
A sulfur atom, a sulfonyl group, a carbonyl group, a carbonyloxy group, a methylene group, an ethylene group, a dimethylmethylene group, etc., and multiple R's and multiple X's in the same molecule may be the same or different. The resin composition according to claim 1, which is 3. The resin composition according to claim 1 or 2, wherein the polyamide-imide is an organic polar solvent-soluble aromatic polyamide-imide containing 50 mol% or more of repeating units represented by the following general formula. or [In each of the above general formulas, Ar is [Formula] [Formula] [Formula] [Formula] or Ar′ is [formula] [formula] [formula] [formula] or Ar″ is [formula] [formula] [formula] or Ar is [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, X is an oxygen atom,
A sulfur atom, sulfonyl group, carbonyl group, carbonyloxy group, methylene group, ethylene group or dimethylmethylene group, and multiple R in the same molecule
and the plurality of Xs may be the same or different. ] 4 Repeating unit represented by the following general formula (In the above general formula, A ₁ represents an aliphatic, aromatic or alicyclic tetravalent residue, and A ₅ and A ₇ represent an aliphatic, aromatic or alicyclic trivalent residue. , A ₂ , A ₃ , A ₄ , A ₆ , A ₈ represent aliphatic, aromatic or alicyclic divalent residues, m ₁ , m ₄ , m ₅ ,
m ₆ , m ₇ , m ₈ represent positive integers, m ₂ and m ₃ are 0
Or represents a positive integer. ) 40 to 99% by weight of polyamideimide containing at least 50% by mole of Fluorine-containing polymer 1 selected from the combination
Metal, metal oxide, metal nitride, metal carbide, metal silicide, silicon, silicon oxide, silicon nitride, silicon carbide, boron, boron per 100 parts by weight of the resin composition comprising ~60% by weight. At least one selected from the group consisting of nitride and carbon
A heat-resistant resin composition containing 5 to 4,000 parts by weight of granular seeds. 5. The resin composition according to claim 4, wherein the granules are at least one selected from the group consisting of Au, Ag, Pd, Pt, Cu, Ni, Al, Sn, and alloys thereof. 6 The granules are SnO ₂ - Ta ₂ O ₅ (means 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-Sb ₂ O ₃ ,
C-B, _Cu2O -CuO, _{In2O3 , In2O3 - Sb2O3 ,}
Tl ₂ O ₃ , SnO ₂ , SnO ₂ -Sb ₂ O ₃ , RuO ₂ , TaN,
TiN, TiN-Ti, TaN-Ta, WC, WC-W,
C, CoSi, ZrSi, TaSi, MnSi, MoSi, NiSi,
The resin composition according to claim 4, which is at least one member selected from the group consisting of TiSi, B, and Si. 7 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 resin composition according to claim 4, which is at least one selected from the group consisting of Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , BN and BeO.