JP5300232B2 - Heat dissipation resin composition - Google Patents

Description

  The present invention relates to a heat-dissipating resin composition, and more particularly relates to a heat-dissipating resin composition having excellent heat dissipation and having both flexibility and metal adhesion, and a heat-dissipating sheet or molded product using the same.

  Conventionally, a heat-dissipating resin material based on a thermoplastic resin or rubber and a heat-conductive filler added thereto is known as a heat-dissipating resin material. Further, heat radiating material parts mainly for electronic parts have been made using such heat radiating resin materials. Examples of such heat-dissipating resin materials include high-density polyethylene, polyolefin-based thermoplastic elastomer or resin material in which aluminum nitride is blended with polypropylene (Patent Document 1), and resin in which metal hydroxide is blended with (meth) acrylate-based polymer. Material (Patent Document 2), Resin material in which an inorganic thermal conductive filler is blended with a thermoplastic elastomer (Patent Document 3), Resin material for a storage battery battery case in which a thermal conductive filler is blended in a thermoplastic resin (Patent Document 4) ) Etc. are known. However, in the case of a conventional heat-dissipating resin material based on a polyolefin resin, the adhesion and adhesion to metal are not sufficient. For example, in order to improve the adhesion and adhesion to metal, an adhesive sheet or Adhesives and the like have been used.

  However, it has been pointed out that they have a problem that heat dissipation efficiency is lowered due to insufficient thermal conductivity, or adhesiveness / tackiness is lowered due to deterioration due to long-term use. In addition, general-purpose resins such as polyethylene and polypropylene are inferior in flexibility, and if a large amount of thermally conductive filler is added to increase heat dissipation, the moldability and material strength are remarkably lowered. There have also been pointed out problems such as contamination due to the blades and contact failure due to low molecular weight siloxane in the case of silicon rubber.

JP-A-10-132493 JP 2002-285121 A JP 2004-35721 A JP 2003-187757 A

  This invention is made | formed in view of the said situation, and is providing the heat dissipation resin composition which was excellent in heat dissipation, and also had a softness | flexibility and metal adhesiveness. Moreover, this invention is providing the sheet | seat for thermal radiation or molded article using such a heat-radiating resin composition.

  As a result of diligent efforts to solve the above problems, the inventors of the present invention do not impair flexibility even when a large amount of a thermally conductive filler is blended by using an ethylene copolymer resin as the olefin resin, and further By using an ethylene copolymer, it has been found that a heat dissipation material with high heat dissipation, metal adhesion, and good moldability can be obtained, and heat dissipation of any shape using such a heat dissipation resin composition The present invention was completed by finding that a sheet or molded product can be obtained.

  That is, the present invention belongs to 2 to 5 periods of the periodic table of elements with respect to 100 parts by weight of the ethylene copolymer resin (A), and is of 2A group, 4A group, 7A group, 8 group, 2B group, 3B group. It contains 150 to 1,500 parts by weight of a thermally conductive filler (B) made of a compound having at least one kind selected from any of the elements belonging to any of the elements, and has a thermal conductivity of at least 0.5 W / K · M. Provided is a heat-dissipating resin composition characterized by (ISO / CD22007-2 method).

As the ethylene copolymer resin (A) , a copolymer resin (A-1) of ethylene and a polar monomer and / or an ethylene / α-olefin copolymer resin (polyethylene or ethylene / α-olefin copolymer resin) polar monomer modified product of (a-2) can be mentioned.

As a copolymer resin (A-1) of ethylene and a polar monomer,
(A-1-a) an ethylene-vinyl ester copolymer resin and / or an acid-modified product thereof,
(A-1-b) an ethylene- (meth) acrylate copolymer resin and / or an acid-modified product thereof,
One selected from (A-1-c) ethylene- (meth) acrylic acid copolymer resin and / or acid-modified product thereof, and (A-1-d) ethylene- (meth) acrylic acid copolymer resin ionomer Or 2 or more types of resin is mentioned .

Ethylene copolymer resin (A) of the present invention, (A-1-d) ethylene - an ionomer over a (meth) acrylic acid copolymer resin.

  The thermally conductive filler (B) is one or more fillers selected from (B-1) metal nitride compounds, (B-2) metal oxides, and (B-3) metal hydroxides. The heat-dissipating resin composition is a preferred embodiment of the present invention.

  The heat-radiating resin composition in which the heat conductive filler (B) has an average particle diameter of 5 μm or less is a preferred embodiment of the present invention.

  A heat dissipating resin composition in which the heat conductivity of the heat dissipating resin composition is at least 1.5 W / K / M (ISO / CD22007-2 method) is a preferred embodiment of the present invention.

  The heat-dissipating resin composition in which the heat-dissipating resin composition can be adhered or thermally bonded to the metal plate is a preferred embodiment of the present invention.

  The present invention further provides a heat radiating sheet or molded product using the heat radiating resin composition.

  The heat-dissipating resin composition of the present invention is a polyolefin-based heat-dissipating resin composition, and is a heat-dissipating material that has high heat-dissipating properties, has its own adhesiveness or adhesiveness to a metal substrate, is flexible, strong, and has good moldability. is there. Moreover, the heat-radiation sheet or molded article of arbitrary shapes is obtained using such a heat-radiating resin composition.

  The heat-dissipating resin composition of the present invention is a thermally conductive filling comprising a compound having at least one element selected from 2 to 4 periods of the periodic table of elements with respect to 100 parts by weight of the ethylene copolymer resin (A). It contains 150 to 1,500 parts by weight of the agent (B) and has a thermal conductivity of at least 0.5 W / K · M (ISO / CD22007-2 method).

  The content of the thermally conductive filler (B) with respect to 100 parts by weight of the ethylene copolymer resin (A) is in the range of 150 to 1,500 parts by weight, and in such a range, depending on the necessity of thermal conductivity. What is necessary is just to set content. The heat-dissipating resin composition of the present invention also has a thermal conductivity of at least 0.5 W / K · M (ISO / CD22007-2 method). However, a preferable thermal conductivity is 1.0 W / K / M or more, and a more preferable thermal conductivity is 1.5 W / K / M or more.

As the ethylene copolymer resin (A) in the heat dissipating resin composition of the present invention,
It is a copolymer resin (A-1) of ethylene and a polar monomer or a polar monomer modified product (A-2) of an ethylene / α-olefin copolymer resin, and melt flow rate (JISK7210: 1999 method, 190 ° C. × 2.16 kg load) is in the range of 0.01 to 500 g / 10 min, preferably 0.05 to 100 g / 10 min, and more preferably 0.1 to 100 g / 10 min.

  In the copolymer resin (A-1) of ethylene and a polar monomer, examples of the polar monomer include unsaturated carboxylic acids, salts thereof, esters thereof, amides, vinyl esters, and carbon monoxide. . More specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium, sodium of these unsaturated carboxylic acids, Monovalent metal salts such as potassium, polyvalent metal salts such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate , Unsaturated carboxylic acid esters such as ethyl methacrylate, isobutyl methacrylate, dimethyl maleate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl salicylate, vinyl stearate, vinyl benzoate, carbon monoxide, sulfur dioxide, etc. A kind of It can be exemplified a two or more.

  More specifically, as ethylene / polar monomer copolymer resin (A-1), ethylene / acrylic acid copolymer resin, ethylene / methacrylic acid copolymer resin (in the present invention, ethylene- (meta ) Ethylene / unsaturated carboxylic acid copolymer resin, which may be referred to as an acrylic acid copolymer resin), a part or all of the carboxyl groups of the ethylene / unsaturated carboxylic acid copolymer resin are lithium, sodium, Ionomer neutralized with monovalent metals (ions) such as potassium, and polyvalent metals (ions) such as magnesium, calcium and zinc, ethylene / methyl acrylate copolymer resins, ethylene / ethyl acrylate copolymer resins, ethylene / Methyl methacrylate copolymer resin, ethylene / isobutyl acrylate copolymer resin, ethylene / butyl acrylate Ethylene / unsaturated carboxylic acid ester copolymer resin such as copolymer resin, ethylene / unsaturated carboxylic acid copolymer resin such as ethylene / isobutyl acrylate / methacrylic acid copolymer resin, ethylene / n-butyl acrylate / methacrylic acid copolymer resin Typical examples include ester / unsaturated carboxylic acid copolymer resins, ionomers in which some or all of the carboxyl groups have been neutralized with the above metals, and ethylene / vinyl ester copolymer resins such as ethylene / vinyl acetate copolymer resins. It can be illustrated.

  Among these, a copolymer resin of ethylene and an unsaturated carboxylic acid, a metal salt thereof, an ester thereof, and a polar monomer selected from vinyl acetate is preferable. Among them, an ethylene-vinyl ester copolymer resin, ethylene- (meth) is preferable. An ionomer of an acrylate copolymer resin, an ethylene- (meth) acrylic acid copolymer resin, or an ethylene- (meth) acrylic acid copolymer resin is preferable, and an ionomer of an ethylene / (meth) acrylic acid copolymer resin is most preferable.

  The ethylene / polar monomer copolymer (A-1) varies depending on the kind of the polar monomer, but the polar monomer content is preferably 1 to 70% by weight, particularly preferably 5 to 50% by weight. However, in consideration of heat resistance, adhesiveness, flexibility, moldability, durability, etc., for example, in the case of ethylene / vinyl acetate copolymer or ethylene / unsaturated carboxylic acid ester copolymer, polar monomer content Is 10 to 50% by weight, preferably 30 to 50% by weight. In the ethylene / unsaturated carboxylic acid copolymer or its ionomer, the unsaturated carboxylic acid content is 1 to 30% by weight, preferably 5 to 20% by weight. Therefore, the neutralization degree is 90% or less, preferably 80% or less. Such a copolymer resin is not only a binary copolymer resin of ethylene and the above polar monomer, but also a multi-component copolymer resin in which two or more kinds of the above polar monomers are combined or any other monomer is copolymerized. Also good.

  Preferred examples of any other such monomer include unsaturated epoxy monomers. Examples of such unsaturated epoxy monomers include unsaturated epoxy monomers such as unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, and unsaturated glycidyl ethers such as vinyl glycidyl ester and allyl glycidyl ester.

As such an ethylene / polar monomer copolymer resin, in consideration of molding processability, mechanical strength and the like, the melt flow rate (MFR, hereinafter the same) at JIS K7210-1999, 190 ° C. and 2160 g load is 0.01 to 300 g / 10 min, preferably 0.1-100 g / 10 min, in particular 1-70 g / 10 min are preferably used.
A copolymer of ethylene and unsaturated carboxylic acid, unsaturated carboxylic acid ester, vinyl ester or the like can be obtained by radical copolymerization at high temperature and high pressure. A copolymer (ionomer) of a metal salt of ethylene and an unsaturated carboxylic acid can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a corresponding metal compound.

  The ethylene / polar monomer copolymer resin (A-1) in the present invention also includes acid-modified products thereof. An acid-modified product of an ethylene / polar monomer copolymer resin is also a preferred embodiment of the ethylene copolymer resin (A) in the present invention.

  Among them, preferred acid-modified products of ethylene / polar monomer copolymer resins include acid-modified products of ethylene / unsaturated carboxylic acid copolymer resins, acid-modified products of ethylene / unsaturated carboxylic acid ester copolymer resins, and ethylene-vinyl. This is an acid-modified product of an ester copolymer resin.

  The acid used for acid modification of such an ethylene / polar monomer copolymer resin is not particularly limited as long as it is an acid that can be grafted with the copolymer resin. However, it is preferable to use an acid selected from an unsaturated carboxylic acid anhydride, an unsaturated dicarboxylic acid or its anhydride, and an unsaturated dicarboxylic acid half ester, and it is particularly preferable to use an unsaturated dicarboxylic acid anhydride. Such an acid-modified product of an ethylene / polar monomer copolymer resin is obtained from an unsaturated carboxylic acid anhydride, an unsaturated dicarboxylic acid or an anhydride thereof, or an unsaturated dicarboxylic acid half ester to an ethylene / polar monomer copolymer resin as a base polymer. It can be obtained by a known method such as a method of graft polymerization of a selected acid or a method of half-esterification after grafting an unsaturated dicarboxylic acid or its anhydride to a base polymer.

  Further, unsaturated carboxylic anhydrides, unsaturated dicarboxylic acids or anhydrides thereof or half esters of unsaturated dicarboxylic acids that can be used as a grafting agent for the acid-modified products include maleic anhydride, itaconic anhydride, tetrahydro Examples include phthalic anhydride, norbornene dicarboxylic acid anhydride, fumaric acid, tetrahydrophthalic acid, monomethyl maleate, monoethyl maleate and the like, but it is most preferable to use maleic anhydride which is inexpensive and excellent in modification effect. The acid-modified product is obtained by grafting an acid using a radical initiator such as an organic peroxide under the melting condition of the base copolymer or by dissolving or suspending the copolymer in a suitable solvent. It can be easily obtained by adding.

  For example, as the organic peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, t-butyl cumylper Examples thereof include oxide and 1,3-bis (2-t-butylperoxyisopropyl) benzene. These organic peroxides are used at a ratio of about 0.1 to 2% by weight with respect to the ethylene / polar monomer copolymer resin.

The amount of acid grafted as these modifiers in the acid-modified product varies depending on the type of acid, but is 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly 0.5 to 3% by weight. Something good. The acid-modified product also preferably has a melt flow rate at 190 ° C. under a load of 2160 g of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes, particularly about 1 to 50 g / 10 minutes. Acid-modified product of the above-mentioned ethylene / polar monomer copolymer resin, preferably an acid-modified product of ethylene-vinyl ester copolymer resin, an acid-modified product of ethylene- (meth) acrylate copolymer resin, or ethylene- (meth) The acid-modified products of acrylic acid copolymer resins can be used alone, but other resins, preferably the unmodified ethylene / polar monomer copolymer resin or ethylene / α-olefin copolymer resin in the present invention. Or the polar monomer modification | denaturation thing and these can also be used together.

  In the case of the combined use, it can be added and mixed when a metal compound-based thermally conductive filler is blended with the resin to form a heat-dissipating resin composition, or can be blended in advance by dry blending. However, it is preferable that the acid-modified product used in combination is melt blended with another resin such as an unmodified resin before blending. In this melt blending, an organic peroxide can be coexisted to perform melt blending with dynamic crosslinking. As such an organic peroxide, those exemplified above can be used. The amount used is preferably 0.1 to 2% by weight based on the resin. By using it by melt blending, it can be more uniformly mixed and dispersed.

  As the ethylene copolymer resin (A) in the heat-dissipating resin composition of the present invention, another preferred resin is a polar monomer modified product (A-2) of an ethylene / (α-olefin) copolymer resin. The polar monomer-modified product (A-2) of ethylene / α-olefin copolymer resin is an ethylene / α-olefin copolymer resin obtained by copolymerizing polyethylene or ethylene with an α-olefin having 3 to 20 carbon atoms. A resin grafted with a polar monomer, preferably an unsaturated carboxylic acid or derivative thereof, an unsaturated dicarboxylic acid or anhydride thereof, or an unsaturated glycidyl ester, preferably having a tensile modulus (YM; ASTM D-658) It is a modified ethylene / α-olefin copolymer resin showing 1600 MPa or less, usually 1 to 1600 MPa, preferably 1 to 150 MPa.

  Specific examples of the α-olefin having 3 to 20 carbon atoms to be copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -Decene, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene and the like can be mentioned. Preferred α-olefins are propylene, 1-butene and 4-methyl-1-pentene. These α-olefins are used alone or in combination of two or more.

  The ethylene / α-olefin copolymer resin contains 50 to 96 mol% of structural units derived from ethylene and 4 to 50 mol% of structural units derived from α-olefins having 3 to 20 carbon atoms. It is desirable to contain.

The density of the ethylene / α-olefin copolymer resin (ASTM D 1505) is 0.855 to 0.915 g / cm ³ , preferably 0.865 to 0.885 g / cm ³ , and the melt flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) is in the range of 0.01 to 200 g / 10 min, preferably 0.5 to 40 g / 10 min.

Specific examples of the ethylene / α-olefin copolymer resin include an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, an ethylene / propylene / 1-butene random copolymer, an ethylene / 1- Examples include hexene random copolymers, ethylene / 1-butene / 1-hexene random copolymers, ethylene / 1-octene random copolymers, and the like. Preferred copolymer resins are ethylene / propylene random copolymers, ethylene / 1-butene random copolymers, and ethylene / propylene / 1-butene random copolymers. These copolymer resins may be used in combination of two or more. The ethylene / α-olefin copolymer resin as described above is produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst. be able to.

  The polar monomer-modified product (A-2) of the ethylene / α-olefin copolymer resin used in the present invention is a polar monomer, preferably an unsaturated carboxylic acid or a derivative thereof, to the ethylene / α-olefin copolymer resin. Alternatively, it is a soft resin grafted with an unsaturated epoxy monomer.

  The graft amount of the polar monomer in the ethylene / α-olefin copolymer resin is 0.01 to 30% by weight, preferably 0.01 to 10% with respect to 100% by weight of the ethylene / α-olefin copolymer resin before graft modification. % By weight, more preferably 0.1 to 3% by weight.

Specific examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^TM (endocis-bicyclo [2,2, 1] hept-5-ene-2,3-dicarboxylic acid and the like.

  Examples of the derivative of unsaturated carboxylic acid include acid halide compounds, amide compounds, imide compounds, acid anhydrides and ester compounds of unsaturated carboxylic acids as described above. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like. Examples of the unsaturated epoxy monomer include unsaturated epoxy monomers such as unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, and unsaturated glycidyl ethers such as vinyl glycidyl ester and allyl glycidyl ester.

Among these, unsaturated dicarboxylic acid anhydrides are preferable, and maleic anhydride and nadic anhydride ^TM are particularly preferable.

  Therefore, as a preferable polar monomer modified body of ethylene / α-olefin copolymer resin, an unsaturated dicarboxylic acid anhydride modified body of ethylene / α-olefin copolymer resin can be cited.

  The graft position of the polar monomer grafted on the ethylene / α-olefin copolymer resin is not particularly limited, and the polar monomer may be bonded to any carbon atom of the ethylene / α-olefin copolymer resin. That's fine.

  Graft modification of the ethylene / α-olefin copolymer resin with a polar monomer can be performed using a conventionally known graft polymerization method. For example, a method in which the ethylene / α-olefin copolymer resin is melted and an unsaturated dicarboxylic acid anhydride is added to perform graft polymerization, and the ethylene / α-olefin copolymer resin is dissolved in a solvent to dissolve the unsaturated dicarboxylic acid anhydride. There is a method of performing graft polymerization by adding a product.

  In these methods, when graft polymerization is performed in the presence of a radical initiator, the graft monomer of the unsaturated dicarboxylic acid anhydride can be efficiently grafted. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the ethylene / α-olefin copolymer resin.

  As such a radical initiator, an organic peroxide, an azo compound, or the like is used. Specific examples of such radical initiators include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5- Dialkyl peroxides such as dimethyl-2,5-di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

  The reaction temperature of the graft polymerization reaction using the radical initiator as described above or the graft polymerization reaction performed without using the radical initiator is usually set in the range of 60 to 350 ° C, preferably 150 to 300 ° C. The

  In the present invention, the ethylene copolymer resin (A) may be used alone, or may be used as a mixture by arbitrarily combining two or more, and further, the heat-dissipating resin composition of the present invention. As long as the characteristics are not impaired, a synthetic or natural resin other than the ethylene copolymer resin (A) may be mixed as an auxiliary component, for example, in an amount of 20 wt% or less.

  Next, in the heat-dissipating resin composition of the present invention, the thermally conductive filler belongs to 2 to 5 periods of the periodic table of elements, and is 2A group, 4A group, 7A group, 8 group, 2B group, 3B. Although the heat conductive filler (B) made of a compound having at least one kind selected from elements belonging to any one of the groups can be used without limitation, the heat conductivity and heat conduction as the heat-dissipating resin composition can be used. Specifically, from the viewpoint of the filling property of the resin filler into the resin, flexibility, mechanical properties, etc., it was selected from beryllium, boron, magnesium, aluminum, calcium, titanium, manganese, iron, nickel, zinc, zirconium A metal compound-based thermally conductive filler (B) having thermal conductivity containing an element is preferable. Examples of the thermally conductive metal compound include metal oxide, metal nitride, metal carbide, and metal hydroxide. At least one member selected from the group consisting of metal carbonates and the like. Specifically, for example, the metal oxide includes aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, manganese oxide, zinc oxide, iron oxide, nickel oxide, and the like, and the metal nitride includes boron nitride. Aluminum nitride, titanium nitride, etc., as the metal carbide, boron carbide, aluminum carbide, etc., as the metal hydroxide, aluminum hydroxide, magnesium hydroxide, etc., as the metal carbonate, magnesium carbonate, calcium carbonate, etc. Is exemplified.

  Among these, metal nitride compounds, metal oxides, and metal hydroxides are preferable, and metal nitride compounds such as aluminum nitride and boron nitride are particularly preferable in view of thermal conductivity and reactivity with polymer materials.

  The average particle size of the thermally conductive filler is preferably 5 μm or less, more preferably 0.1 to 3 μm, and still more preferably 0.1 to 1.5 μm.

Such a heat conductive filler may be used alone, or different kinds of heat conductive fillers may be arbitrarily mixed depending on the purpose.
The blending amount of the heat conductive filler is preferably in the range of 150 parts by weight to 1,500 parts by weight with respect to 100 parts by weight of the ethylene copolymer resin (A). , 500 parts by weight or more is not preferable because it is inferior in adhesion or adhesion to metal, softness, strength and the like.

  With such a content, the heat-dissipating resin composition of the present invention exhibits a thermal conductivity of at least 0.5 W / K · M (ISO / CD22007-2 method). However, for the heat-dissipating resin composition of the present invention, the preferred thermal conductivity is at least 1.0 W / K / M, and the more preferred thermal conductivity is at least 1.5 W / K / M.

  In the present invention, in order to improve the heat resistance of the heat-dissipating resin composition, in order to improve the heat resistance of the ethylene copolymer resin as the base polymer, a single or one or more ethylene copolymer resins ( The organic peroxide as exemplified above in A) is generally present in a proportion of 0.1 to 2% by weight with respect to the resin, and dynamic partial cross-linking is performed under a melt blend by a known method. You can also. Alternatively, after preparing a compound in which the ethylene copolymer resin (A) and the heat conductive filler (B) are blended, cross-linking such as chemical cross-linking or electron beam cross-linking is performed using a known cross-linking method of polyolefin resin. It doesn't matter.

  In addition to the ethylene copolymer resin (A) and the metal compound-based thermally conductive filler (B), the heat-dissipating resin composition of the present invention can contain, for example, an antioxidant, an ultraviolet absorber, A range that does not impair the object of the present invention, such as a flame retardant, a crosslinking aid, a colorant, a lubricant, an adhesiveness imparting agent, a release agent, an antistatic agent, a silane or titanium coupling agent, and other fillers such as carbon. Can be blended.

  The heat-dissipating resin composition of the present invention can be adhered or thermally bonded to a metal plate, and the adhesiveness to such a metal is not only at the level at which both are completely adhered, but also at the degree of adhesion that does not peel off. Even levels are included.

  When such a heat-dissipating resin composition of the present invention is used, a heat-dissipating sheet or molded product that can be adhered or thermally bonded to the metal plate as described above can be produced.

  The sheet or molded product using the heat-dissipating resin composition of the present invention contains an ethylene copolymer resin (A), a metal compound-based thermally conductive filler (B) and other compounding agents blended as necessary. After mixing uniformly by a known method such as a blender, mill, Banbury mixer, kneader, Henschel mixer, super floater, etc., a single-screw extruder, a twin-screw extruder, It can be easily molded by a known molding method such as a pressure kneader, calendar, compression molding machine, injection molding machine or hollow molding machine. Moreover, what is necessary is just to melt-knead at the temperature below the melting | fusing point, when mix | blending an organic peroxide. Such blending may be performed all at once or in stages. As molding temperature, it is about 50-300 degreeC normally.

  Specific examples of sheets and molded articles molded from the heat-dissipating resin composition of the present invention include, for example, electronic devices such as automobiles, LED products, notebook-type personal computers, mobile phones, projectors, etc. Those used in the field of parts are listed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the raw material used in the Example and the comparative example is as follows.

<Description of raw materials>
(1) EVA: ethylene-vinyl acetate copolymer [vinyl acetate content 46 wt%, melt flow rate (MFR) 2.5 g / 10 min (190 ° C., 2160 g load JIS K7210-1999)]
(2) EMAA: ethylene-methacrylic acid copolymer [methacrylic acid content 15% by weight, MFR 60 g / 10 min (190 ° C., 2160 g load JIS K7210-1999)
(3) Ionomer: Zinc ionomer of an ethylene-methacrylic acid copolymer (EMAA) having a methacrylic acid content of 15% by weight (degree of neutralization 59%, MFR 0.9 g / 10 min (190 ° C., 2160 g load JIS K7210) -1999)
(4) LDPE: Low density polyethylene resin (trade name: Mirason 50) manufactured by Prime Polymer Co., Ltd.
(5) Magnesium hydroxide: Magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd. (trade name: Kisuma 5 L, average particle size 0.6 μn).
(6) Aluminum hydroxide: Aluminum hydroxide manufactured by Showa Denko Co., Ltd. (trade name: Heidilite H-42STV, average particle size 1 μn)
(7) Boron nitride: Boron nitride manufactured by Mitsui Chemicals (trade name: MBN-010T, average particle size 1 μn)
(8) Antioxidant: Irganox 1010 manufactured by Ciba Specialty Chemicals

<Sample preparation method>
The mixture was kneaded at 160 ° C. × nitrogen atmosphere × 10 minutes using a small pressure kneader. Thereafter, press molding (160 ° C. × 5 minutes (preheating) × 5 minutes (pressurization) × 5 minutes (cooling)) was performed using a press molding machine.

<Measurement of thermal conductivity>
It measured by the hot disk method (ISO / CD22007-2) using the 00000 company thermal conductivity meter. Measurement conditions: room temperature.

<Metal adhesion test>
Leave the metal plate (SUS304-SB, 1 mm thickness) and the sample (3 mm × 3 mm × 2 mm thickness) separately for 15 minutes in an oven at a temperature (setting 50 to 120 ° C.) at which the sample can keep its shape, Next, the sample was placed on the metal plate, and further allowed to stand for 10 minutes under a load of 1 kg. After taking out from the oven, it was left in an atmosphere at 23 ° C. for 3 hours, and then a sensory test was conducted to see if it could be removed by hand. Based on the following determination, Δ or more was determined to be acceptable.
○: Level that cannot be peeled △: Level that is not easy but can be peeled with force (adhesion level)
X: Level at which peeling can be easily performed <Measurement of flexibility>
A 1 mm-thick press sheet was punched into a JIS K7106 test piece (W: 20 × L: 100 mm), and both ends of the test piece were lightly bent by hand to check the occurrence of cracks, and used as an index of flexibility. Judgment criteria were as follows.
(Judgment)
○: No cracking or whitening was confirmed.
Δ: A level where no small cracks are confirmed but no problem.
X: A level at which a large crack occurs and the specimen is broken.

Example 1
After 100 parts by mass of the ethylene-vinyl acetate copolymer (EVA), magnesium hydroxide and an antioxidant were uniformly blended with a Henschel mixer at the blending ratio shown in Table 1, the small size was obtained according to the method for preparing the sample. 160 ° C x nitrogen atmosphere x 10 minutes using a pressure kneader, melt-kneaded for 10 minutes, pelletize, and then press sheet (160 ° C x preheating 5 minutes x pressure 5 minutes x cooling 5 minutes) did. Table 1 shows various physical properties of the obtained heat-dissipating resin composition.

(Example 2-7, comparative example)
In Example 1, the heat dissipation resin composition was obtained like Example 1 except having mix | blended the compounding ratio shown in Table 1 with the compounding ratio shown to each Example 2-7 of Table 1, and a comparative example. . Table 1 shows various physical properties of the obtained heat-dissipating resin composition.

Claims (6)

For 100 parts by weight of the ethylene copolymer resin (A), it belongs to 2 to 5 periods of the periodic table, and belongs to any of 2A group, 4A group, 7A group, 8 group, 2B group, 3B group. A resin composition containing 150 to 1,500 parts by weight of a heat conductive filler (B) made of a compound having at least one selected from elements, wherein the ethylene copolymer resin (A) is (A-1 -d) ethylene - (meth) ionomer over acrylic acid copolymer resin, heat dissipation resin characterized in that its thermal conductivity is at least 0.5W / K · M (ISO / CD22007-2 method) Composition.   The thermally conductive filler (B) is one or more fillers selected from (B-1) metal nitride compounds, (B-2) metal oxides, and (B-3) metal hydroxides. The heat-dissipating resin composition according to claim 1, wherein   The heat conductive resin composition according to claim 1 or 2, wherein the heat conductive filler (B) has an average particle diameter of 5 µm or less.   The heat dissipation resin composition according to any one of claims 1 to 3, wherein the heat dissipation resin composition has a thermal conductivity of at least 1.5 W / K / M (ISO / CD22007-2 method).   The heat-dissipating resin composition according to any one of claims 1 to 4, wherein the heat-dissipating resin composition can be adhered or thermally bonded to the metal plate.   A heat-dissipating sheet or molded product using the heat-dissipating resin composition according to claim 1.