KR920009540B1 - Electroconductive composition - Google Patents

Abstract

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Description

Electrically conductive composition

The present invention relates to a plastisol composition having good thermal conductivity. The prior art is as follows.

Various conventional polymer materials include electric component substrates (eg, printed wiring boards, power transformer substrates, and thyristor module substrates), element casings, encapsulants for electrical components, insulating adhesives for electrical components, and machines. It is used as a part (eg bearing, bearing). Typically, composite materials are used in the field of low thermal conductivity and thermal insulation. However, in some fields of use, they are used despite poor thermal conductivity due to their excellent moldability and light weight. When used as electrical and mechanical parts, polymer materials with poor thermal conductivity accumulate heat and deform without proper heat dissipation. Sometimes these flaws can fatally damage electronic components.

Special fillers with high thermal conductivity, such as magnesia, alumina, and beryllium oxide, have been incorporated into the resin to attempt to eliminate this drawback. However, such attempts have not been successful until the inclusion of a large amount of filler results in a composition of low strength, and the inclusion of a small amount of filler results in a composition with poor thermal conductivity.

On the other hand, high heat resistant polymer materials such as phenol resins, epoxy resins, and other thermosetting resins have been used. However, they are low in formability and productivity and improvements are desired. Attempts have been made to use thermoplastic resins in place of thermosetting resins with low formability and low productivity. However, they also have disadvantages of poor heat resistance and dimensional stability. Incorporating a large amount of filler therein to improve thermal conductivity provides a molded product having a poor melt viscosity and poor mechanical properties and surface appearance.

The inventors of the present invention have found a new material to solve the above problems, and have therefore focused on using a thermotropic liquid crystal polymer exhibiting anisotropy in a molten state. In addition, the inventors have found that a close mixture composed of such a polymer and a filler having a thermal conductivity of at least 10 w / m.K at 300 ° K has very good performance.

The electrically conductive composition of the present invention may form an anisotropic phase in a molten state, and is composed of a polymer which is a thermotropic liquid crystal and a filler having a thermal conductivity of 10 W / m.K or more at 300 ° K. The mechanical properties and heat resistance are improved. Preferred fillers are those metals, metal oxides, metal nitrides or metal carbides belonging to columns 1 to 7 of groups II, III and IV of the periodic table. They can be usefully formed as commutator part insulator parts of electrical appliances, shaft bearings or commutator motors.

The filler is one or more compounds selected from metal oxides, metal nitrides and metal carbides. For example, there are oxides, nitrides and carbides among the elements belonging to columns 1 to 7 of the respective periodic tables II, III and IV. Examples of such fillers include one or more compounds selected from the group consisting of beryllium oxide, magnesium oxide, aluminum oxide, thorium oxide, zinc oxide, silicon nitride, boron nitride, aluminum nitride and silicon carbide.

The amount of filler used in the present invention varies with particle size, specific surface area, and surface activity. Typically the amount of filler is 5 to 90% by volume, preferably 20 to 70% by volume, based on the total composition weight. The shape of the filler is not particularly limited.

The thermotropic liquid crystal polymer exhibiting anisotropy in the molten state is a newly developed resin including the following polymer. The polymer forming the anisotropic molten phase has the property of being regularly oriented alongside the other when the polymer chain is in the molten state. The state in which the molecules are aligned as described above is called a liquid crystal state or a nematic phase of the liquid crystal. Such polymers are made from monomers having a thin, long, flat arrangement, high rigidity along the long axis of the molecule, and having a plurality of chain extension bonds in another axial or side by side.

The properties of the anisotropic molten phase can be determined by conventional polarization tests using crossed nicols. In more detail, the sample placed in the Leitz hot stage in a nitrogen atmosphere can be observed to measure its properties with a 40-fold Leitz polarizing microscope. This polymer is optically anisotropic. In other words, when the polymer is placed between orthogonal polarizers, light is transmitted. If the sample is optically anisotropic, it transmits polarized light even in a stationary state.

The component of the polymer which forms said anisotropic molten phase is as follows.

(1) one or more aromatic and cycloaliphatic dicarboxylic acids, (2) one or more aromatic, cycloaliphatic, and aliphatic diols, (3) one or more aromatic hydroxy carboxylic acids, (4) one Or more aromatic thiol carboxylic acids, (5) one or more aromatic dithiols and aromatic thiolphenols, and (6) one or more aromatic hydroxyamines and aromatic diamines.

The polymer forming the anisotropic molten phase consists of the following combinations.

I) Polyester consisting of (1) and (2), II) Polyester consisting solely of (3), III) Polyester consisting of (1), (2) and (3), IV) (4) Polythiol ester composed of only V, polythiol ester composed of (1) and (5), polythiol ester composed of (VI) (1), (4) and (5) (1), ( Polyesteramide consisting of 3) and (6), and iii) polyesteramide consisting of (1), (2), (3) and (6).

In addition to the combination of the above components, as a polymer forming an anisotropic molten phase, poly (nitrilo-2-methyl-1,4-phenylenenitroethylidine-1,4-phenyleneethylidine) , Poly (nitrilo-2-methyl-1,4-phenylene nitrilomethylidine-1,4-phenylenemethylidine) and poly (nitrilo-2-chloro-1,4-phenylenenitrilomethylidine Aromatic polyazomethines, such as -1,4-phenylenemethylidine).

Furthermore, in addition to the combination of the above components, the polymer forming the anisotropic molten phase is essentially a polycarbonate composed of 4-hydroxybenzoyl, dihydroxyphenyl, dihydroxycarbonyl, and terephthaloyl units. Esters;

Examples of the compound composed of the above polymers I) to iii) include terephthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, and 2,6-naphthalenedicarboxyl Acid, diphenyl ether-4,4'-dicarboxylic acid, dipenoxyethane-4,4'-dicarboxylic acid, dipenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4 ' -Dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid And aromatic dicarboxylic acids such as naphthalene-1, 6-dicarboxylic acid; Chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, etherterephthalic acid, methoxyterephthalic acid, and alkyl substituted ethoxyterephthalic acid and alkoxy groups and acids substituted with halogen atoms.

Examples of alicyclic dicarboxylic acids include alkyl and alkoxy groups such as trans-1,4- (1-methyl) cyclohexane dicarboxylic acid and trans-1,4- (1-chloro) cyclohexanedicarboxylic acid. And trans 1,4-cyclohexane dicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid, as well as acids substituted with halogen atoms.

Examples of aromatic diols include chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4- Hydroquinones, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, 2,6 as well as substituted with alkyl and alkoxy groups and halogen atoms such as methylresorcinol Naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis- (4-hydroxyphenoxy) ethane, 3,3'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl ether , 1, 6-naphthalenediol, 2, 2-bis (4-hydroxyphenyl) propane, and 2, 2-bis (4-hydroxyphenyl) methane.

Examples of alicyclic diols include those substituted with alkyl, alkoxy groups and halogen atoms such as trans-1,4- (1-methyl) -cyclohexanediol and trans-1,4- (1-chloro) cyclohexanediol As well as trans 1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol, trans-1,3-cyclo Hexanediol, cis-1, 2-cyclohexanediol, and trans-1,3-cyclohexanedimethanol.

Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and straight or branched aliphatic diols such as neopentylglycol.

Examples of aromatic hydroxycarboxylic acids include 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4 -Hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 3-chloro-4 -Hydroxybenzoic acid, 2-chloro-4-hydroxy-benzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxy Benzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, and 6-hydroxy-5,7 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxy-2-naphthoic acid, and 6-hydroxy- as well as substituted alkyl and alkoxy groups and halogen atoms such as dichloro-2-naphthoic acid 1-naphthoic acid.

Examples of aromatic mercaptocarboxylic acid include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

Examples of aromatic dithiols include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalenedithiol, and 2,7-naphthalenedithiol.

Examples of aromatic mercaptophenols include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol, 7-mercaptophenol and the like.

Examples of aromatic hydroxyamines and aromatic diamines are 4-aminophenol, N-methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N'- Dimethyl-1,4-phenylenediamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxy Cidiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxyphenylmethane, sulfided 4-amino-4'-hydroxydiphenyl, sulfided 4,4'-diaminophenyl (Thiodianiline), 4,4'-diaminodiphenylsulfone, 2,5-diaminotoluene, 4, 4-ethylenedianiline, 4, 4-diaminodiphenoxyethane, 4,4'-diamino Diphenylmethane (methylenedianiline), and 4,4'-diaminodiphenylether (oxydianiline).

The polymers I) to iii) composed of the above components may be divided into groups capable of forming an anisotropic molten phase and those which cannot be formed depending on the components, the polymer composition, and the continuous distribution. Polymers used in the present invention are limited to the polymers of the preceding group.

Among the polymers capable of forming an anisotropic molten phase suitably used in the present invention, polyesters I), II), III) and polyesteramides i) each have an organic group each having a functional group capable of condensation to form the necessary repeating unit. It can be prepared by various ester formation methods in which monomers are reacted with each other.

Functional groups of such organic monomers include a carboxyl group, a hydroxyl group, an ester group, an acryloxy group, a halogen acyl group, and an amine group. Such organic monomers can be reacted by molten asidolisis even without a heat exchange fluid.

In such a manufacturing method, a monomer is heated and a melt is formed. As the reaction proceeds, the solid polymer particles are suspended in the melt. In the final stage of the condensation reaction, the reaction system is vacuumed to conveniently remove volatile byproducts such as acetic acid and water.

Slurry polymerization can also be used in the preparation of fully aromatic polyesters suitable for use in the present invention. In such a process, the solid product is obtained in its suspended form in a heat exchange medium.

In the molten asidolisis and the slurry polymerization method, the organic monomer reactant from which the aromatic aromatic polyester can be induced is reacted in a modified form (ie, in the form of lower acyl ester) obtained by esterifying the hydroxyl group of the monomer at room temperature. Can be used in Lower acyl groups preferably have about 2 to 4 carbon atoms. Preferably, acetate of the organic monomeric reactant is used in the reaction.

Representative examples of catalysts that can be used in the molten acytolysis and slurry processes include dialkyltin oxides (e.g. dibutyltin oxide), dilauryl tin oxide, titanium dioxide, antimony trioxide, alkoxytitanium silicate, alkoxytitanium, and carboxylic acid. Alkali metal and alkaline earth metal salts (eg, zinc acetate), Lewis acids (eg, BF ₃ ), and gaseous acid catalysts such as hydrogen halide (ie, HCl). The catalyst is typically used in amounts of about 0.001 to 1% by weight, preferably about 0.01 to 0.2% by weight, based on the monomers.

Fully aromatic polymers suitable for use in the present invention are substantially insoluble in conventional solvents and are therefore not suitable for use in solution processing. However, as described above, such a polymer can be easily processed by conventional melt processing. More preferred fully aromatic polymers are to some extent soluble in pentafluorophenols.

Fully aromatic polyesters preferably used in the present invention typically have a weight average molecular weight of about 2,000 to 200,000, preferably about 10,000 to 50,000, and more preferably about 20,000 to 25,000. Fully aromatic polyesteramides preferably used typically have a molecular weight of about 5,000 to 50,000, preferably about 10,000 to 30,000, for example 15,000 to 17,000.

The molecular weight is determined by other standard methods in which no polymer solution is formed, such as gel permeation chromatography or a method in which the end groups of the compression molded membrane are determined by an infrared spectrometer. Alternatively, the molecular weight of the polymer can be measured according to the light-scattering method after dissolving in pentafluorophenol.

When a wholly aromatic polyester or polyesteramide is dissolved in pentafluorophenol at 60 ° C. to obtain a 0.1 wt% solution, the solution is typically at least about 2.0 dl / g, for example from about 2.0 to 10.0 dl / g of algebraic viscosity. Has

Anisotropic melt phase forming polyesters particularly preferably used in the present invention include at least about 10 molar such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene, and 2,6-dicarboxynaphthalene. Polyesters containing% naphthalene moiety containing repeat units. Preferred polyesteramides include those having a repeating unit composed of the above naphthalene moiety and 4-aminophenol or 1,4-phenylenediamine moiety. An example of them is as follows.

(1) Polyesters consisting essentially of the following repeating units I and II:

Such polyesters comprise about 10 to 90 mole% of unit I and about 10 to 90 mole% of unit II. In one example, unit I is included in an amount of about 65 to 85 molar%, preferably about 70 to 80 molar% (eg about 75 molar%). As another example, Unit II is included in small amounts, such as about 15 to 35 molar%, preferably about 20 to 30 molar%. The hydrogen atom moiety bonded at least directly to the ring is from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and combinations thereof It may be substituted with a selected substituent.

(2) Polyesters consisting essentially of the following repeating units I, II and III:

Such polyesters contain about 30 to 70 molar% of Unit I. They are preferably composed of about 40 to 60 molar% of unit I, about 20 to 30 molar% of unit II, and about 20 to 30 molar% of unit III. At least the hydrogen atom moiety bonded directly to the ring is a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof Can be substituted.

(3) Polyesters consisting essentially of the following repeating units I, II, III and IV:

Wherein R represents a substituent of a hydrogen atom bonded to an aromatic ring which is methyl, chlorine, bromine or a combination thereof

Such polyesters comprise from about 20 to 60 molar% of unit I, from about 5 to 18 molar% of unit II, from about 5 to 35 molar% of unit III and from about 20 to 40 molar% of unit IV.

Preferably they are about 35 to 45 molar% of unit I, about 10 to 15 molar% of unit II, about 15 to 25 molar%, if the total molar concentration of units II and III is substantially equal to that of unit IV. And unit IV of about 25 to 35 molar percent.

At least the hydrogen atom moiety bonded directly to the ring is a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof Can be substituted. When the wholly aromatic polyester is dissolved in pentafluorophenol at 60 ° C. to obtain a 0.3 w / v% solution, the solution typically has an algebraic viscosity of at least 2.0 dl / g, for example 2.0 to 10.0 dl / g.

(4) Polyesters consisting essentially of the following repeating units I, II, III and IV:

III dioxyaryl of the general formula: [-O-Ar-O-]

Wherein Ar represents a divalent group having at least one aromatic ring.

IV dicarboxyaryl units of the general formula:

Wherein Ar 'represents a divalent group having at least one aromatic ring.

The amount of unit I is about 20-40 molar%. The amount of unit II is greater than 10 molar% and less than or equal to about 50 molar%. The amount of unit III is greater than 5 mol% and less than about 30 mol% and the amount of unit IV is greater than 5 mol% and less than 30 mol%.

Such polyesters may comprise about 20 to 30 molar% (eg about 25 molar%) of Unit I, about 25 to 40 molar% (eg about 35 molar%) of Unit II, about 15 to 25 molar% (eg about 20 molar%) of unit III and about 15 to 25 molar% (eg about 20 molar%) of unit IV.

If necessary, at least the hydrogen atom portion directly bonded to the ring is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups and combinations thereof It may be substituted with a substituent.

Units III and IV are preferably symmetrical.

More specifically, the divalent bonds connecting adjacent units of unit III or IV are arranged symmetrically in one or more aromatic rings. (For example, if they are placed in the naphthalene ring, they are arranged in mutual para positions or in diagonal rings.) However, asymmetric units derived from resorcinol and isophthalic acid can also be used.

Preferred dioxyaryl units III are as follows:

Preferred dicarboxyaryl units IV are as follows:

(5) Polyesters consisting essentially of the following repeating units I, II and III:

II. Dioxyaryl of the formula: [-O-Ar-O-]

In the formula, Ar represents a divalent group having at least one aromatic ring.

III. Dicarboxy aryl units of the general formula

Wherein Ar 'represents a divalent group having at least one aromatic ring. The amounts of units I, II and III are about 10 to 90 molar%, 5 to 45 molar%, 5 to 45 molar% and 5 to 45 molar%, respectively.

Such polyesters are preferably composed of about 20 to 80 molar% of unit I, about 10 to 40 molar% of unit II and about 10 to 40 molar% of unit III.

More preferably, they consist of about 60 to 80 molar% of Unit I, about 10 to 20 molar% of Unit II, and about 10 to 20 molar% of Unit III. If necessary, at least the hydrogen atom portion directly bonded to the ring is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. It may be substituted with a selected substituent.

Preferred dioxyaryl units II are as follows:

Preferred dicarboxyaryl units III are as follows:

(6) Polyester amides consisting essentially of the following repeating units I, II, III and IV:

II. Unit of the following general formula:

Wherein A represents a divalent group having at least one aromatic ring or a divalent transcyclohexane group.

III. Unit of the following general formula:-[-Y-Ar-Z-]-

Wherein Ar represents a divalent group having at least one aromatic ring, Y represents O, NH, or Nr, Z represents NH or NR, R, which is an alkyl group having 1 to 6 carbon atoms or an aryl group.

Ⅳ. Unit of the following general formula:-[-O-Ar´-O-]-

Wherein Ar 'represents a divalent group having at least one aromatic ring. The amounts of units I, II, III and IV are about 10 to 90 molar%, about 5 to 45 molar%, about 5 to 45 molar%, and about 0 to 40 molar%, respectively. If necessary, at least the hydrogen atom portion directly bonded to the ring is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. It may be substituted with a selected substituent.

Preferred dicarboxyaryl units II are as follows:

Preferred unit III is as follows:

Preferred dioxyaryl units IV are as follows:

The anisotropic molten phase forming polymer of the present invention may be a polymer in which a part of the polymer chain is composed of a portion of the anisotropic molten phase forming polymer and the remaining portion is a portion of a thermoplastic resin which does not form an anisotropic molten phase.

Filled thermoplastic resins are generally known to have a lower thermal conductivity than filled thermoset resins. It is also known that thermoplastic resins vary greatly in thermal conductivity (see, for example, Zenkoko Zaireyo Volume 31, No. 2, p. 109).

The inventors have found that the thermotropic liquid crystal polymer exhibiting anisotropy in the molten state has unique properties even if it is thermoplastic. Originally, liquid crystal polymers have high strength and low melt viscosity, but incorporation of a filler results in very high thermal conductivity. For example, molded articles made from a thermotropic liquid crystalline polymer and terephthalic acid polyethylene having anisotropy in a molten state containing 55% by volume and 35% by volume of magnesium oxide, respectively, have the thermal conductivity shown in Table 1.

TABLE 1

The thermally conductive composition of the present invention is prepared by mixing a heat-sensitive polymer exhibiting anisotropy in a molten state with a filler in powder form. The mixture is then assembled using an extruder and the pellets are formed into the required shapes by compression molding, transfer molding, injection molding, extrusion molding and the like. If desired, the composition may be incorporated into asbestos, ground glass, kaolin, and other fillers such as clay, fiberglass, mica, talc and inorganic pigments.

The filler used in the present invention is surface treated to improve the wettability of the filler surface. Examples of surface treatments include surfactants and low viscosity oily materials (ie, silicone oils, mineral oils, and other oils). Preferred fillers are binders which react with the filler surface and carry a surface modification effect.

The surface active agent used in the present invention serves as a humectant. Surface active agents that can be used in the present invention can be composed of cationic, anionic, nonionic and amphoteric forms. Anionic surfactants include:

Phosphate ester type

M = K, Na or (C ₂ H ₄ O) _n H

M = K, Na, or (C ₂ H ₄ O) _n H

Sulfonic acid type

RSO ₃ M or ROSO ₃ MM = K or Na

Sulfate ester type

RO (C ₂ H ₄ O) _n SO ₃ M

Cationic surfactants include:

Quaternary ammonium salt type

Imidazoline type

Amide Amine Type

Nonionic surfactants include:

Alkyl ether, ester type

RO (C ₂ H ₄ O) _n H and RCOO (C ₂ H ₄ O) _n H

Polyoxyethylene sorbitan ester type

Alkylamine type

Alkylamide type

Amphoteric surfactants include:

Beta Doll

Alanine type

RNHCH ₂ COONa

The above surfactant may be used in the same manner as used in the usual thermoplastic resin. Anionic, nonionic, and both molding surfactants are preferred, and nonionic surfactants are particularly preferred for thermal stability. The surfactant is used in an amount of 0.1 to 5% by weight based on the total weight containing the resin.

The binder that can be used in the present invention is composed of silane type and titanate type. They should have a decomposition point higher than 270 ° C., because the resin is processed above 280 ° C. and the compositions of the present invention are processed above 300 ° C. At decomposition points below 270 ° C., the binder thermally decomposes during melt processing, reducing the miscibility of the resin with the filler. This compromises the processability and mechanical properties of the present invention. In addition, cracking gases are generated due to thermal decomposition, causing bubbles on the surface of the molded article. Examples of silane binders include the following.

Amino type: N, N-dimethyl-P-aminophenyltrimethoxysilane, P- (N-β- (aminoethyl) -aminoethyl) phenethyltrimethoxysilane, P- (aminomethyl) phenethyltrimeth Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilanes, and polyaminosilanes.

Vinyl type: vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris- (2-methoxyethoxy) silane.

Chloroform: 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane.

Methacryloxy type: 3-methacryloxypropyltrimethoxysilane.

Preferred binders are those having a decomposition point of 300 ° C or higher. Examples thereof include the following epoxy type and mercapto type binders.

Epoxy type: 3-glycidoxy oxytrimethoxysilane, 3-glycidoxy propylmethyldimethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

Mercapto type: 3-mercaptopropyltrimethoxysilane.

The following is an example of a titanic acid type binder having a decomposition point of 270 ° C or higher.

Isopropyl triisostearoyl titanate, Isopropyl trioctanoyl titanate, Isopropyl diisostearoyl cumyl phenyl titanate, Isopropyl distearoyl methacrylate titanate, Isopropyl dimethacrylic acid isopropyl dimethacrylic isostearoyl titanate Isopropyl dodecylbenzenesulfonyl, isopropyl diisostearoyl titanate, acrylic, isopropyl isostearoyl diacrylic acid, isopropyl polysulfate titanate (dioctylphosphate), isopropyl tri-n-stearoyl titanate , Isopropyl-4-aminobenzenesulfonyldi (dodecylbenzenesulfonyl) titanate, isopropyltrimethacryl titanate, isopropyltricumylphenyl titanate, isopropyldi (4-aminobenzoyl) -isostearoyl, Isopropyl tricarbonate (dioctylpyrophosphate), isopropyl triacyl titanate, isopropyl tricarbonate (N, N-dimethyl-ethylamino), iso titanate Sopropyl tri (N-ethylamino-ethylamino), isopropyl trianthranyl titanate, isopropyl octylbutyl pyrophosphate titanate, isopropyl di titanate (butyl-methylpyrophosphate), tetraisopropyl di titanate (dilauryl phosphite) ), Tetraisopropyldi titanate (dioctylphosphite), tetraoctyldi titanate (ditridecylphosphite), tetra titanate tetra (2,2-diaryloxymethyl-1-butoxy) di (di-tridecyl) Phosphite, diisostearoyloxyacetate titanate, isostearoyl methacryloxyacetate titanate, isostearoylacryloxyacetate titanate, di (dioctylphosphate) titanate titanate, 4-aminobenzenesulfonide dodetan titanate Silbenzenesulfonyloxyacetate, dimethacryloxyacetate titanate, dicumylphenolate oxyacetate titanate, 4-aminobenzoyl isotate titanate Aroyloxyacetate, di (dioctylpyrophosphate) oxyacetate, diacrylonitrile titanate, di (octylbutylpyrophosphate) titanate, oxyacetate, diisostearoylethylene titanate, isostaroyl methacrylate titanate, Di (dioctylphosphate) ethylene titanate, 4-aminobenzene sulfonide dodecyl benzenesulfonyl ethylene titanate, dimethacrylethylene titanate, 4-aminobenzene isostaroyl ethylene titanate, di (dioctyl pyrophosphate) ethylene titanate Diacrylethylene titanate, dianthranylethylene titanate, and di (butylmethyl-pyrophosphate) ethylene titanate.

The amount of such binder varies with the particle size, specific surface area and surface activity of the filler used. Typically they are used in amounts of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the filler.

The composition of the present invention is formed into the required shape by conventional plastic molding techniques such as extrusion and injection molding. Molded products include substrates for electrical components (e.g. printed wiring boards, power transformer and die Lister module substrates), element casings, encapsulants for electrical components, insulating adhesives for electrical components, and mechanical components (e.g. shaft bearings). Used. Molded articles in plate form are used as substrates. Device casings and mechanical parts can be manufactured by injection molding. Where the composition is used as an encapsulant or binder, the composition is ejected by placing the part to be encapsulated or bonded in a mold. The effect of the invention is as follows.

The thermally conductive composition of the present invention can be produced as a molded article having excellent thermal conductivity as well as excellent electrical insulation having a conductivity of 10 ⁻⁸ Scm ⁻¹ or less. Therefore, it is suitable for electrical appliances. The heat-sensitive liquid crystal polymer exhibiting anisotropy in the molten state is easier to mold than the conventional thermoplastic resin and has excellent heat resistance.

The composition of the present invention will find use in the field of thermosetting resins are widely used. In other words, the composition of the present invention is an electronic component substrate (e.g., a printed wiring board, a power transformer device board, and a diester module substrate), an element casing, an encapsulant for an electrical component, an insulating adhesive for an electrical component, and a mechanical component (e.g., , Bearing). All of them have excellent electrical insulation and thermal conductivity that conventional plastics never reach. Thus, the present invention provides significant economic and industrial advantages.

EXAMPLE

An embodiment of the present invention will be described as follows, which does not limit the scope of the present invention.

[Examples 1 to 4]

The thermotropic liquid crystal polymer forming the anisotropic molten phase (to be described later) is mixed with 35% by volume of α-alumina having an average particle diameter of 80 μm and a thermal conductivity of 36 W / m · K. The mixture is extruded at 300 ° C. and pelletized to form a 1 mm thick substrate. Polymers A, B, C and D used in the examples each consist of the following structural units.

= 60/20/20

= 70/30

= 70/15/15

Said resins A, B, C and D are prepared by the following method.

[Resin A]

1081 parts of 4-acetoxybenzoic acid (the same by weight), 460 parts of 6-acetoxy-2-naphthoic acid, 166 parts of isophthalic acid, and 194 parts of 1,4-diacetoxybenzene were mixed with a stirrer, a nitrogen introduction tube, And a reactor equipped with a distillation tube. The mixture was heated to 260 ° C. under a nitrogen stream and stirred vigorously at 260 ° C. for 2.5 hours and then at 280 ° C. for 3 hours, while acetic acid was distilled off from the reactor. The temperature was raised to 320 ° C. and nitrogen introduction was stopped. The pressure in the reactor was slowly depressurized to 0.1 mm Hg after 15 minutes. The mixture was stirred at that temperature and pressure for 1 hour. The obtained polymer has an intrinsic viscosity of 5.0 measured in pentafluorophenol at a concentration of 0.1 wt.

[Resin B]

1081 parts 4-acetoxybenzoic acid, 489 parts 2,6-diacetoxynaphthalene, and 332 parts terephthalic acid are fed to a reactor equipped with a stirrer, a nitrogen introduction tube, and a distillation tube. The mixture was heated to 250 ° C. under a stream of nitrogen and vigorously stirred at 250 ° C. for 2 hours and then at 280 ° C. for 2.5 hours, while acetic acid was distilled off from the reactor. The temperature was raised to 320 ° C. and nitrogen introduction was stopped. The reactor pressure was gradually reduced to 0.2 mmHg after 30 minutes. The mixture was stirred at that temperature, pressure for 1.5 h. The polymer obtained had an intrinsic viscosity of 5.4 measured in pentafluorophenol at a concentration of 0.1% by weight and 60 ° C.

[Resin C]

1261 parts 4-acetoxybenzoic acid and 691 parts 6-acetoxy-2-naphthoic acid were placed in a reactor equipped with a stirrer, a nitrogen introduction tube, and a distillation tube. The mixture was heated to 250 ° C. under a nitrogen stream and vigorously stirred at 250 ° C. for 3 hours and then at 280 ° C. for 2 hours, while acetic acid was distilled off from the reactor. The temperature was raised to 320 ° C. and nitrogen introduction was stopped. The pressure in the reactor was slowly depressurized to 0.1 mmHg after 20 minutes. The mixture was stirred at that temperature, pressure for 1 hour. The polymer obtained had an intrinsic viscosity of 5.4 measured in pentafluorophenol at a concentration of 0.1% by weight and 60 ° C.

[Resin D]

1612 parts 6-acetoxy-2-naphthoic acid, 290 parts 4-acetoxy-acetanilide, 249 parts terephthalic acid, and 0.4 parts sodium acetate were placed in a reactor equipped with a stirrer, a nitrogen introduction tube, and a distillation tube. The mixture was heated to 250 ° C. under a nitrogen stream and stirred vigorously at 250 ° C. for 1 hour, then at 300 ° C. for 3 hours, while acetic acid was distilled off from the reactor. The temperature was raised to 340 ° C. and nitrogen introduction was stopped. After 30 minutes, the pressure of the reactor was gradually reduced to 0.2 mmHg. The mixture was stirred at that temperature, pressure for 30 minutes. The polymer thus obtained had an intrinsic viscosity of 3.9 measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C. Substrates made from polymers A, B, C and D have thermal conductivity of 1.7, 1.7, 1.5 and 1.6 W / m.K, respectively. Such a substrate remains unchanged in appearance when heated to 200 ° C.

[Comparative Examples 1 to 2]

The same procedure as in Example was repeated except that the thermotropic liquid crystal resin was replaced with low density polyethylene (thermal conductivity 0.3W / m.K) or polyamide (thermal conductivity 0.29W / m.K). Therefore, the substrate has a thermal conductivity of 0.9 W / mK. By heating to 200 ° C., the polyethylene base plate melts and the polyamide base plate is severely deformed.

Claims (2)

Polyester comprising a naphthalene moiety containing repeating unit selected from 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene or the above-mentioned naphthalene moiety and 4-aminophenol or 1, 10 to 95% by volume of a polymer which is a molten phase anisotropic thermotropic liquid crystal containing about 10 mol% or more of polyesteramide containing a 4-phenylenediamine partial containing repeating unit, and beryllium oxide, magnesium oxide, aluminum oxide, and thorium oxide An electroconductive composition comprising from 5 to 90 volume percent of a filler selected from zinc oxide, silicon nitride, boron nitride, aluminum nitride and silicon carbide. The composition of claim 1 wherein the filler has a thermal conductivity of at least 10 W / m.K at 300 ° K.