JP2007009084A - Resin composition excellent in heat dissipation and heat-dissipating resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in heat conductivity, having slight volatile component by heating and remarkably suppressed in occurrence of cut powder in an extrusion process, and a heat-dissipating resin sheet using the resin composition. <P>SOLUTION: The resin composition comprises (I) ≥1 wt.% and ≤20 wt.% one or more kinds of thermoplastic resins selected from polyamide-based resins, polyacetal-based resins, polyphenylene ether-based resins, polycarbonate-based resins, ABS-based resins, polyolefin-based resins, polystyrene-based resins, methacrylate-based resins and thermoplastic elastomers and (II) >80 wt.% and ≤99 wt.% zinc oxide composed of a needle crystal having a nuclear part and extending to different four axial directions from the nuclear part. The heat-dissipating resin sheet is obtained by molding the resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has excellent thermal conductivity and heat resistance to dissipate the heat generated from parts such as electronic devices, further suppresses the generation of chips during processing, and greatly suppresses volatile components caused by heating. The present invention relates to a resin composition and a heat dissipation resin sheet using the resin composition.

  Conventionally, with the spread of digital home appliances, there is an increasing demand for higher speed and higher functionality of electrical components and electronic devices. However, in these electronic components and electronic devices, electronic elements such as LSIs and CPUs that perform electronic control have increased power consumption due to an increase in the degree of integration of computers and an increase in operation speed. Therefore, heat dissipation measures are indispensable. For heat dissipation in general electronic equipment, a heat sink or the like is attached, and the heat sink is forcibly cooled by a cooling fan or the like. Small devices such as notebook personal computers and electronic parts mounted with high density have limitations such as a small installation space such as a cooling fan, and measures against heat radiation have been taken by applying silicone grease. In addition, in order to meet the demand for higher performance of electronic components, the number of cases using heat dissipation sheets is increasing. The heat-dissipating sheet is used for the purpose of effectively transferring heat to the cooling component by attaching a close contact between the two when the cooling component such as a heat sink is attached to the heating element.

In recent years, in each application, a resin sheet excellent in heat dissipation property that diffuses heat has been demanded.
So far, heat dissipation sheets have been used in which a material based on silicone rubber or silicone gel sheet is filled with a filler having relatively high thermal conductivity.
However, since silicone grease is a highly viscous liquid, it is difficult to control the amount applied when it is applied to a heat-generating component, and in some cases, there is a risk of adhesion to other heat-generating components or contamination. In addition, the silicone rubber sheet is complicated in process management because the silicone resin itself is expensive and a vulcanization process is required. Furthermore, since a low molecular weight siloxane is contained in the silicone resin, a low molecular weight siloxane gas is generated when used attached to a heating element, and the gas adheres to electrode contacts and the like to generate silicon dioxide. This can cause contact failure.

On the other hand, although a resin composition in which zinc oxide is blended with a thermoplastic resin has been proposed, zinc oxide is mainly used in the resin composition for the purpose of improving the mechanical properties and electrical properties of the resin. .
Patent Document 1 proposes a method for obtaining a resin composition in which a thermoplastic resin is filled with zinc oxide whiskers. This is a composition for the purpose of imparting electrical conductivity and improving mechanical strength, and there is no description regarding heat dissipation. Patent Document 2 proposes a method for obtaining a resin composition in which a polyarylene sulfide resin is filled with zinc oxide whiskers. This is for the purpose of dimensional stability of the molded product in the obtained resin composition, and there is no description regarding heat dissipation.
Patent Document 3 proposes a method of obtaining a heat radiating member in which a thermoplastic polyester is filled with a heat conductive filler, and particulate zinc oxide is used as the heat conductive filler. Although there is an effect of the property, the generation of chips during the extrusion process when producing this resin composition is not sufficient, and in the obtained member, there are not a few volatile components due to heating, and it is further as a heat radiating member Improvement was desired.

JP-A-1-225663 Japanese Patent Laid-Open No. 5-140452 Japanese Patent Laid-Open No. 2004-175812

  The present invention has been made in order to solve the problems of the heat conductive material as described above, and the object of the present invention is excellent in heat conductivity and less volatile components due to heating. It is in providing the resin composition which suppressed generation | occurrence | production of the cutting powder of this, and the thermal radiation resin sheet using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the thermoplastic resin contains zinc oxide that is 80% by weight and 99% by weight of zinc oxide, which is a needle-like crystal extending in different four-axis directions from the core. By adding the following, it is possible to obtain a resin composition excellent in thermal conductivity, less volatile components due to heating, and further suppressing the generation of chips during extrusion processing, and a heat dissipation resin sheet using the resin composition The headline, the present invention has been reached.

That is, the present invention
[1] (I) One selected from polyamide resin, polyacetal resin, polyphenylene ether resin, polycarbonate resin, ABS resin, polyolefin resin, polystyrene resin, methacrylic resin, and thermoplastic elastomer The above thermoplastic resin is 1% by weight or more and less than 20% by weight, and (II) the core part and zinc oxide which is acicular crystals extending from the core part in different four-axis directions are more than 80% by weight and 99% by weight or less. A resin composition comprising:
[2] (I) The thermoplastic resin is 5 wt% or more and 18 wt% or less, and (II) zinc oxide which is a needle-like crystal extending in a different four-axis direction from the core and the core is 82 wt% or more and 95 [1] the resin composition comprising not more than% by weight,
[3] [1] or [2], wherein the thermoplastic resin is at least one selected from polyamide resins, polyacetal resins, polyphenylene ether resins, polyolefin resins, and thermoplastic elastomers. Resin composition,
[4] The resin composition according to any one of [1] to [3], wherein the thermoplastic resin is at least one selected from polyolefin resins and thermoplastic elastomers,
[5] The resin composition according to any one of [1] to [4], wherein the thermoplastic resin is a thermoplastic elastomer,
[6] (II) A thermal conductive filler having a thermal conductivity of 10 W / m · k or more is further added to the core and zinc oxide, which is a needle-like crystal extending in different four-axis directions from the core. [1] to the resin composition according to any one of [5],
[7] A heat dissipating resin sheet obtained by molding the resin composition according to any one of [1] to [6] into a sheet shape,
[8] The heat-dissipating resin sheet according to [7], which is formed into a sheet by injection molding,
[9] The heat-radiating resin sheet according to [7] or [8], wherein the surface gloss value on the surface is 10 or more,
[10] A thermoplastic resin in which the water absorption rate of the thermoplastic resin of (I) is 800 ppm or less, and (II) a core part and zinc oxide that is a needle-like crystal extending from the core part in different four axial directions. The method for producing a resin composition according to any one of [1] to [5], wherein the resin composition is melt-kneaded,
Is to provide.

  Based on the present invention, it is possible to provide a resin composition excellent in thermal conductivity, having less volatile components due to heating, and greatly suppressing the generation of chips during extrusion, and a heat dissipation resin sheet using the resin composition. is there.

  The thermoplastic resin used in the present invention is selected from polyamide resins, polyacetal resins, polyphenylene ether resins, polycarbonate resins, ABS resins, polyolefin resins, polystyrene resins, methacrylic resins and thermoplastic elastomers. One or more thermoplastic resins selected, preferably one or more thermoplastic resins selected from polyamide resins, polyacetal resins, polyphenylene ether resins, polyolefin resins, and thermoplastic elastomers; One or more thermoplastic resins selected from polyolefin resins and thermoplastic elastomers are preferred, and thermoplastic elastomers are more preferred. In the present invention, other thermoplastic resins can be further added as necessary in addition to the above combinations.

  The polyamide-based resin in the present invention is a polyamide-based resin mainly composed of amino acids, lactams, or diamines and dicarboxylic acids. Specific examples of the constituent components include ε-caprolactam, enantolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other amino acids, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylene. Diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethyl Diamines such as cyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, metaxylylenediamine, adipic acid, suberic acid, and azelai There are dicarboxylic acids such as acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid. These constituent components are used for polymerization alone or in the form of a mixture of two or more, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention. For example, there are polyamide 66, polyamide 610, polyamide 612, polyamide 46, polyamide 1212, polyamide MXD (metaxylylenediamine) 6 obtained by polycondensation of diamine and dicarboxylic acid, and also obtained by ring-opening polymerization of lactam. Examples thereof include polyamide 6 and polyamide 12. As polyamide copolymers, polyamide 66/6, polyamide 66/610, polyamide 66/612, polyamide 66 / 6T (T is terephthalic acid component), polyamide 66 / 6I (I is isophthalic acid component), polyamide 6T / 6I Etc. Moreover, the blended material of these polyamide resins is also mentioned. Preferred are polyamide 66 and polyamide 6. Two or more polyamide resins may be used in combination. These polyamide resins can be produced by a generally known method. In the case of polyamide, a melt polymerization method is generally carried out, but it may be batch polymerization or continuous polymerization.

  The polyphenylene ether resin used in the present invention is a homopolymer having a repeating unit represented by the following general formula (1) or (2), or a repeating represented by the general formula (1) and / or (2). It is a copolymer having units.

(Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or hydrogen, provided that R ₅ and R ₆ are simultaneously hydrogen. is not.)

  Representative examples of the homopolymer of polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2 , 6-Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxy) And homopolymers such as ethyl-1,4-phenylene) ether.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferred. Further, 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene described in JP-A-63-301222 and the like Polyphenylene ether containing an ether unit or the like as a partial structure is also preferably used.
Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer of o-cresol, a copolymer of 2,6-dimethylphenol and bisphenol represented by the following general formula (3), and the like.

(Here, R ₉ and R ₁₀ each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. In the formula, X represents —C (CH ₃ ) ₂ —, —SO ₂ —, — Represents S- or -O-.)

In the present invention, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydrous dicarboxyl group is grafted or copolymerized on part or all of the polyphenylene ether resin. A modified polyphenylene ether resin introduced by any method can be used as long as the object of the present invention is not impaired. These may be used alone or in combination of two or more.
Modified polyphenylene ether resins obtained by modifying part or all of polyphenylene ether resins with unsaturated carboxylic acids or functional derivatives thereof are disclosed in JP-A-2-276823, JP-A-63-108059, JP-A-59. For example, it is produced by melt-kneading and reacting an unsaturated carboxylic acid or a functional derivative thereof with a polyphenylene ether resin in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving polyphenylene ether, an unsaturated carboxylic acid, or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.

  Examples of unsaturated carboxylic acids or functional derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, and endo-cis-bicyclo (2,2,1). ) -5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. Can be mentioned. In addition, a compound which is a saturated carboxylic acid but can be thermally decomposed itself at the reaction temperature when producing the modified polyphenylene ether to become a functional derivative used in the present invention can be used. An acid etc. are mentioned. These may be used alone or in combination of two or more.

It is also possible to use the polyphenylene ether resin in combination with a different resin. For example, a resin composition comprising a polyphenylene sulfide resin, a polyphenylene ether resin and a compatibilizer described in JP-A-2003-226809, a polypropylene resin and polyphenylene ether described in JP-A-11-80453 And a resin composition made of a polyamide resin and a polyphenylene ether resin described in JP-A-2004-315552.
The polyacetal resin in the present invention includes a homopolymer obtained by polymerizing cyclic oligomers such as formaldehyde or its trimer, trioxane or tetramer, tetraoxane, and both ends of the polymer are blocked with ether and ester groups. , Carbon number obtained by copolymerizing formaldehyde or its trimer trioxane or tetramer tetraoxane with ethylene oxide, propylene oxide, 1,3-dioxolane, glycol formal, diglycol formal, etc. Oxymethylene copolymers containing 0.1 to 40 mol% of oxyalkylene units of 2 to 8 with respect to oxymethylene, those having branched molecular chains, and different from 50% by weight or more of segments comprising oxymethylene units 50% by weight of segment A oxymethylene block polymers containing a lower.

Examples of the oxymethylene block polymer include block polymers of polyalkylene glycol and polyoxymethylene homopolymer disclosed in JP-A-57-31918, and hydrogenated polybutadiene and oxymethylene copolymers disclosed in JP-A-2001-064479. The block polymer is preferred. Moreover, these polyoxymethylene resins can be properly used depending on the purpose. From the viewpoint of slidability and rigidity, it is preferable to use a homopolymer or a copolymer having a small amount of comonomer. From the viewpoint of thermal stability or impact resistance, a copolymer having a large amount of comonomer or a block polymer of hydrogenated polybutadiene and oxymethylene copolymer is preferred. Use is preferred.
For the use of the present invention, a copolymer is preferable from the viewpoint of thermal stability, and a copolymer having a small amount of comonomer is most preferable from the balance of thermal stability and rigidity. Moreover, the melt flow rate (measured under the conditions of ASTM-D1238-57T) of the polyoxymethylene resin used in the present invention is 0.5 to 100 g / 10 minutes, preferably 1.0 to 80 g / 10 minutes, and more preferably 5 -60 g / min, most preferably in the range of 7-50 g / 10 min. If it is less than 0.5 g / 10 minutes, molding is difficult, and if it exceeds 100 g / 10 minutes, the durability is insufficient.

  For the polyacetal resin of the present invention, stabilizers used in conventional polyacetal resins, such as heat stabilizers and light stabilizers, can be used alone or in combination. As heat stabilizers, antioxidants, formaldehyde and formic acid scavengers, and combinations thereof are effective. The antioxidant is preferably a hindered phenol antioxidant, such as n-octadecyl-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3. -(3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3'5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate), 1,4-butanediol-bis- (3- (3,5-di -T-butyl-4-hydroxyphenyl) -propionate), triethyleneglycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl)- Lopionate), tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane, 3,9-bis (2- (3- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- ( 3'5'-di-t-butyl-4-hydroxyphenol) priionyl hexamethylenediamine, N, N'-tetramethylenebis-3- (3'-methyl-5'-t-butyl-4-hydroxy) Phenol) propionyldiamine, N, N′-bis- (3- (3,5-di-tert-butyl-4-hydroxyphenol) propionyl) hydrazine, N-salicyloyl-N′-salicylide Hydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis (2- (3- (3,5-di-butyl-4-hydroxyphenyl) propionyloxy) ethyl) Among these hindered phenolic antioxidants, triethylene glycol bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate), tetrakis- (methylene-3 -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate methane is preferred.

  Examples of scavengers for formaldehyde and formic acid include (a) compounds and polymers containing formaldehyde-reactive nitrogen, (b) alkali metal or alkaline earth metal hydroxides, inorganic acid salts, and carboxylates. (I) Compounds and polymers containing formaldehyde-reactive nitrogen include dicyandiamide, melamine, cocondensates of melamine and formaldehyde, polyamide resins (for example, nylon 4-6, nylon 6, nylon 6-6, nylon 6-10). Nylon 6-12, Nylon 12, Nylon 6 / 6-6, Nylon 6 / 6-6 / 6-10, Nylon 6 / 6-12, etc.), poly-β-alanine, polyacrylamide and the like. Among these, a co-condensate of melamine and formaldehyde, polyamide resin, poly-β-alanine, and polyacrylamide are preferable, and polyamide resin and poly-β-alanine are more preferable.

  (B) Alkali metal or alkaline earth metal hydroxides, inorganic acid salts, and carboxylate salts include, for example, hydroxides such as sodium, potassium, magnesium, calcium or barium, carbonates of these metals, Examples include phosphates, silicates, borates, and carboxylates. Specifically, calcium salts are most preferable, and are calcium hydroxide, calcium carbonate, calcium phosphate, calcium silicate, calcium borate, and fatty acid calcium salts (calcium stearate, calcium myristate, etc.), and these fatty acids are substituted with hydrosyl groups. May be. Among these, fatty acid calcium salts (calcium stearate, calcium myristate, etc.) are preferable.

As the light-resistant stabilizer, (i) a benzotriazole-based material, (b) an oxalic acid anilide-based material, and (c) a hindered amine-based material are preferable.
(I) Examples of the benzotriazole-based substance include 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole and 2- (2′-hydroxy-3,5-di-t-butyl-phenyl). Benzotriazole, 2- (2′-hydroxy-3,5-di-isoamyl-phenyl) benzotriazole, 2- (2′-hydroxy-3,5-bis- (α, α-dimethylbenzyl) phenyl) -2H -Benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole and the like, preferably 2- (2'-hydroxy-3,5-bis- (α, α-dimethylbenzyl) Phenyl) -2H-benzotriazole, 2- (2′-hydroxy-3,5-di-t-butyl-phenyl) benzotriazole, and the like.
(B) Examples of oxalic acid anilide-based substances include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2 -Ethoxy-3'-dodecyl oxalic acid bisanilide and the like. These substances may be used alone or in combination of two or more.

  (C) As hindered amine substances, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy 2,2 , 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2, 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamo Ruoxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidine) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetramethyl- 4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl-piperi Ruoxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl- 4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate , Preferably bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate.

The above hindered amine materials may be used alone or in combination of two or more. The combination of the benzotriazole-based material, oxalic acid anilide-based material and hindered amine-based material is most preferable.
A preferred combination of stabilizers in the polyacetal resin of the present invention is “hindered phenol (particularly triethylene glycol-bis- (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate), tetrakis- ( Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane)), “polymers containing formaldehyde-reactive nitrogen (especially polyamide resins, poly-β-alanine) And “alkaline earth metal fatty acid salts (particularly fatty acid calcium salts)”. The added amount is 0.1 to 0.5% by weight of “hindered phenol”, 0.1 to 0.5% by weight of “polymer containing formaldehyde-reactive nitrogen”, and “alkaline earth” with respect to the polyacetal resin. Metal fatty acid salt (particularly fatty acid calcium salt) ”is in the range of 0.1 to 0.3% by weight.
The polycarbonate resin in the present invention has a main chain composed of a repeating unit represented by the following formula (4).

(In the formula, Ar is a divalent C5-200 aromatic residue, for example, phenylene, naphthylene, biphenylene or pyridylene, which may be unsubstituted or substituted, or alternatively, (5) is mentioned.)

(In the formula, Ar ₁ and Ar ₂ are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, pyridylene, etc., which may be unsubstituted or substituted, and Y represents the following formula (6) Is an alkylene group or a substituted alkylene group.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, carbon An aralkyl group of 7 to 31 optionally substituted with a halogen atom or an alkoxyl group of 1 to 10 carbon atoms, k is an integer of 3 to 11, and R ₅ and R ₆ are for each X Individually selected and independently of each other a hydrogen atom, or a lower alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, optionally substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms And X represents a carbon atom.)
Among them, one represented by the following formula (7) is a preferable example.

In particular, a polycarbonate resin containing 85 mol% or more (based on all monomer units in the polycarbonate resin) of a repeating unit in which Ar represented by the above formula (7) is Ar is particularly preferable.
Moreover, the polycarbonate-type resin which can be used for this invention may have a branched structure which uses a trivalent or more aromatic group as a branch point.
The weight average molecular weight (Mw) of the polycarbonate-based resin used in the present invention is usually 5,000 to 500,000, preferably 10,000 to 100,000, more preferably 13,000 to 50,000, and particularly preferably 15,000 to 30,000.

The polycarbonate resin used in the present invention is also preferably used in combination of two or more polycarbonate resins having different molecular weights.
What was manufactured by the well-known method can be used for the polycarbonate-type resin used by this invention. Specifically, a known method of reacting an aromatic dihydroxy compound and a polycarbonate precursor, for example, an interface in which an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. Solid-state polymerization of crystallized carbonate prepolymers obtained by polymerization methods (for example, phosgene method), transesterification methods (melting method) in which aromatic dihydroxy compounds react with carbonic acid diesters (for example, diphenyl carbonate), phosgene methods or melting methods (Japanese Unexamined Patent Publication No. 1-158033 (corresponding to US Pat. No. 4,948,871), Japanese Unexamined Patent Publication No. 1-271426, Japanese Unexamined Patent Publication No. 3-68627 (corresponding to US Pat. No. 5,204,377)), etc. Use products manufactured by the method described in 1. It can be.

As a preferable polycarbonate-based resin, a polycarbonate resin containing substantially no chlorine atom produced by a transesterification method from a divalent phenol (aromatic dihydroxy compound) and a carbonic acid diester can be exemplified.
Further, the phenol group terminal amount of the polycarbonate resin is determined by the method described in, for example, U.S. Pat. No. 4,763,013 in the phosgene method, while it is aromatic in the transesterification method such as the melting method or the solid phase polymerization method. It is possible to adjust the molar ratio of the dihydroxy compound and diphenyl carbonate, or the method described in JP-B-7-98862.
In the present invention, the polycarbonate-based resin is preferably a polycarbonate-based resin having a branched structure in the main chain from the viewpoint of improving molding processability. As a method for obtaining such a polycarbonate-based resin having a branched structure, a production method in which a trivalent or higher polyvalent hydroxy compound is added as a copolymerization component, for example, US Pat. Nos. 4,677,162 and 4,562,242, Germany Although there is a method described in Japanese Patent No. 3149812, etc., a polycarbonate resin having a particularly preferable branched structure that can be used in the present invention can be produced by a method described in US Pat. No. 5,932,683. it can.

  The ABS resin used in the present invention is a graft polymer obtained by graft-polymerizing a rubber-like polymer with a monomer mixture containing an aromatic vinyl monomer and an unsaturated nitrile monomer, or the graft polymer. And a vinyl copolymer obtained by polymerizing a monomer mixture containing an aromatic vinyl monomer and an unsaturated nitrile monomer, and the ratio of the unsaturated nitrile compound unit to the vinyl compound unit is 15 It is a resin that is ˜45% by weight. The ABS resin is composed of only a graft polymer obtained by graft polymerization of a monomer mixture containing an aromatic vinyl monomer and an unsaturated nitrile monomer to a rubber polymer, and the graft polymer and the aromatic resin. It may be composed of a mixture with a polymer obtained by copolymerizing a monomer mixture containing a vinyl monomer and an unsaturated nitrile monomer. A vinyl copolymer obtained by copolymerizing a monomer containing an aromatic vinyl monomer and an unsaturated nitrile monomer may be polymerized in the process of producing the graft polymer, May be manufactured in a different process.

A specific ABS resin is made of a styrene / acrylonitrile / butadiene copolymer resin. The ABS resin of the present invention includes ABS resin-like AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), AAS resin (acrylonitrile-acrylic system). Elastic polymer-styrene copolymer) is also included.
The polystyrene resin used in the present invention is a styrene homopolymer or a copolymer of a mixture of a styrene monomer and another copolymerizable vinyl monomer. Other vinyl monomers copolymerizable with styrene include methyl methacrylate, methyl acrylate, butyl acrylate, ethyl methacrylate, halogen-containing vinyl monomers, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene Acrylonitrile and the like, and one or more of these can be used. The resin made of an aromatic vinyl monomer may contain polybutadiene, styrene-butadiene copolymer, polyisoprene, nitrile rubber, natural rubber, or the like as a rubber component. The method for producing these polystyrene resins is not particularly limited, and can be produced by any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization well known to those skilled in the art.

The polyolefin resin used in the present invention is a polymer having a polyethylene and / or polypropylene chain.
Polyethylene resins include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), copolymers of acrylic vinyl monomers and ethylene (EEA, EMMA, etc.) or vinyl acetate. A copolymer of monomers and ethylene (EVA) can be used. However, among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE) are particularly preferable because they are available at low cost. These polyethylene resins may be used alone or in combination of two or more.

When a polyethylene resin is used as the olefin resin, the density is desirably 0.89 g / cm ³ or more and 0.95 g / cm ³ or less from the viewpoint of transparency, and the density is 0.90 g / cm ³ or more and 0.94 g / cm. more desirably ³ or less, it is particularly desirable density 0.91 g / cm ³ or more 0.94 g / cm ³ or less. Even when alone or in combination of two or more, transparency is preferable if the density falls within this range. In addition, polyethylene having a density of 0.94 to 0.97 g / cm ³ is preferable from the viewpoint of rigidity and chemical resistance, and among them, the higher the density, the more preferable from the viewpoint of rigidity and chemical resistance.
The molecular weight of the polyethylene resin is not particularly specified, but a viscosity average molecular weight of 10,000 or more is preferable from the viewpoint of heat resistance. In addition, when using in combination with a thermoplastic resin other than polyethylene, the use of ultra-high molecular weight polyethylene having a viscosity average molecular weight of 200,000 or more should cause the heat conductive filler to be present in a high concentration in the thermoplastic resin other than polyethylene. Is possible and preferable. The viscosity average molecular weight here refers to the following intrinsic viscosity (η (dl / g)) obtained by dissolving polyethylene in decalin at different concentrations and extrapolating the solution viscosity obtained at 135 ° C. to a concentration of 0: This is a value obtained by an expression.
Mv = 5.34 × 10 ⁴ η ^1.49

When a polypropylene resin is used, the thermoplastic resin composition and the molded body obtained in the present invention are excellent in molding processability such as fluidity, mechanical properties such as rigidity, hinge characteristics and vibration characteristics, and excellent in rigidity.
Examples of the polypropylene-based resin include homopolypropylene, copolymer resins of propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1 (including blocks and random). .
As described above, the olefin resin used in the present invention includes a polyethylene resin and / or a polypropylene resin, and the polypropylene resin is preferable because it has higher heat resistance than the polyethylene resin. Of these, homopolypropylene resins and block copolymerized polypropylene have the highest heat resistance and are more preferable.

  The methacrylic resin used in the present invention is a methyl methacrylate homopolymer or a copolymer of a mixture of methyl methacrylate and another monomer having a copolymerizable vinyl group. Other monomers copolymerizable with methyl methacrylate include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2,2,2-trifluoroethyl methacrylate And methacrylic acid esters such as acrylonitrile and styrene, acid anhydrides such as maleic anhydride and itaconic anhydride, and maleimide compounds such as cyclohexylmaleimide and phenylmaleimide. The production method of the methacrylic resin is not particularly limited, and can be produced by an existing polymerization method.

The thermoplastic elastomer used in the present invention includes polyester elastomer, polyurethane elastomer, polybutadiene, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, ethylene / 1-butene copolymer, ethylene / octene copolymer. Polymers, olefinic elastomers such as ethylene / α-olefin copolymers, and vinyl aromatic-conjugated diene block copolymers such as isoprene / styrene block copolymers and butadiene / styrene block copolymers and their hydrogen An additive etc. are mentioned. In particular, a hydrogenated vinyl aromatic-conjugated diene block copolymer is preferred.
The vinyl aromatic-conjugated diene block copolymer used in the present invention was hydrogenated to the extent that the degree of unsaturation of the block S mainly composed of vinyl aromatic compound and the conjugated diene compound portion did not exceed 20%. And a polymer E mainly composed of an olefin compound.

The polymer block S mainly composed of a vinyl aromatic compound has a weight ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 100/0 to 51/49, preferably 100/0 to 70/30. When a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), and part It can be either in block form or any combination thereof.
The polymer block E mainly composed of a conjugated diene compound has a composition ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 49/51, preferably 0/100 to 30/70. When the polymer block is a copolymer of a conjugated diene compound and a vinyl aromatic compound, the distribution of the vinyl aromatic compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), It may be either partially blocky or any combination thereof. As the vinyl aromatic compound provided here, one or more of styrene, α-methylstyrene, alkylstyrene such as p-methylstyrene and p-tertiarybutylstyrene, paramethoxystyrene, vinylnaphthalene, and the like may be used. Among them, styrene and p-methylstyrene are particularly preferable.

As the conjugated diene compound, one or more of butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc. Two or more are selected, and butadiene and isoprene are particularly preferable.
The content of the vinyl aromatic compound is preferably 10 to 60% by weight, more preferably 10 to 50% by weight. If it exceeds 60% by weight, the resin itself becomes resinous and the impact resistance of the composition becomes low. The molecular structure of the block copolymer may be any of linear, branched, radial, or a combination thereof. Each of the polymer block S mainly composed of a vinyl aromatic compound or the block E mainly composed of a conjugated diene may have the same structure, the monomer component content, the distribution in the molecular chain, the block Each structure such as molecular weight and microstructure may be different.

Examples of the method for producing the vinyl aromatic-conjugated diene block copolymer include the methods described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, Japanese Patent Publication No. 49-36957, and the like. These use organolithium compounds as anionic polymerization initiators in hydrocarbon solvents, ether compounds such as diethyl ether and tetrahydrofuran as vinylating agents, triethylamine, N, N, N ′, N′-tetramethylethylenediamine and the like. Tertiary amine, a method of block copolymerizing a vinyl aromatic compound and a conjugated diene compound using a polyfunctional compound such as epoxidized soybean oil or silicon tetrachloride as a coupling agent, if necessary, It is obtained as a block copolymer having a branched or radial structure. In the present invention, any polymer obtained by any polymerization method can be used as long as it is as described above.
Hydrogenated vinyl aromatic-conjugated diene block copolymer by hydrogenating the above-mentioned vinyl aromatic-conjugated diene block copolymer by a known method, for example, the method described in JP-B-42-8704. Is obtained. In the present invention, it is preferable to hydrogenate 80% or more of the conjugated diene moiety. The higher the rate of hydrogenation, the better the compatibility with the polyolefin resin composition and the less the composition is susceptible to thermal degradation, so that an excellent composition can be obtained. The hydrogenation rate can be analyzed by instrumental analysis using a nuclear magnetic resonance apparatus (NMR).

  The vinyl aromatic-conjugated diene block copolymer is then modified by an addition reaction with at least one modifier selected from unsaturated carboxylic acids and derivatives thereof, and the acid-modified hydrogenated block used in the present invention. A copolymer is obtained. Examples of the unsaturated carboxylic acid and its derivatives as modifiers are maleic acid, maleic anhydride, maleic acid ester, maleic acid amide, maleic acid imide, fumaric acid, fumaric acid ester, fumaric acid amide, fumaric acid imide, itacone Acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, halogenated maleic anhydride, halogenated maleic acid ester, halogenated maleic acid amide, halogenated maleic acid imide, cis-4 -Cyclohexene-1,2-dicarboxylic acid, anhydrous cis-4-cyclohexene-1,2-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid ester, cis-4-cyclohexene-1,2-dicarboxylic acid Amido, cis-4-cyclohexene-1,2-dicar Acid imide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, anhydrous endo-cis-bicyclo (2,2,1) -5-heptene-2,3- Dicarboxylic acid, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid ester, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Acid amide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic imide, acrylic acid, acrylic ester, acrylic amide, methacrylic acid, methacrylic ester, methacrylic amide, etc. Is mentioned. These can be used not only by 1 type but by mixing 2 or more types. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic anhydride is particularly preferable.

  Acid-modified vinyl aromatic-conjugated diene block copolymer hydrogenated block copolymer is a radical initiator in the solution state or melt state of the above modifier in the vinyl aromatic-conjugated diene block copolymer hydrogenated product of the substrate. Can be obtained by adding or not using. The method for producing these acid-modified hydrogenated block copolymers is not particularly limited in the present invention, but the obtained acid-modified hydrogenated block copolymer contains an undesirable component such as a gel or its melt viscosity. A manufacturing method in which the processability is remarkably increased and the workability is deteriorated is not preferable. As a preferable method, for example, a method in which the hydrogenated vinyl aromatic-conjugated diene block copolymer of the substrate is reacted with the above modifier in the presence of a radical initiator in an extruder can be mentioned.

The amount of the molecular unit containing the carboxylic acid group or derivative group thereof contained in the acid-modified hydrogenated block copolymer, that is, the amount of the unsaturated carboxylic acid or derivative thereof added is the same as the acid-modified hydrogenated block copolymer used in the present invention. The average value of the entire polymer is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight of the acid-modified hydrogenated block copolymer of the base. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, the improvement effect is hardly recognized as compared with the unmodified styrene copolymer hydrogenated product, and the amount exceeds 10 parts by weight. However, the improvement effect is not remarkable as compared with the case of less than it.
The content of the molecular unit containing a carboxylic acid group or a derivative group thereof in the acid-modified hydrogenated block copolymer can be easily grasped by a method such as infrared spectrophotometry or titration. Further, in the present invention, the unmodified vinyl aromatic-conjugated is within the range where the addition amount of the unsaturated carboxylic acid or derivative thereof in the acid-modified hydrogenated block copolymer used satisfies the above range as the overall average value. A diene block copolymer hydrogenated product may be contained. Two or more kinds of acid-modified hydrogenated block copolymer components obtained as described above may be used in combination.
In the present invention, preferred examples of the acid-modified hydrogenated block copolymer include maleic anhydride-modified styrene conjugated diene block copolymer hydrogenated products.

The (II) core part used in the present invention and zinc oxide, which is a needle-like crystal extending from the core part in different four-axis directions, have a core part, and the four-axis directions different from the core part in a tetrapot shape. For example, “trade name: Panatetra” manufactured by Matsushita Amtech Co., Ltd. and the like can be mentioned.
It is preferable that the diameter of the core part of the needle crystal is 0.7 to 14 μm, and the length from the core part to the tip of the needle crystal is 3 to 200 μm. More preferably, the diameter of the core part of the needle crystal is 1 to 14 μm, and the length from the core part to the tip of the needle crystal is 10 to 200 μm.

The zinc oxide can also include zinc oxide surface-treated with a coupling agent in the present invention, and the coupling agent used here is preferably a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. It is done. In order to uniformly disperse the zinc oxide in the resin, it may be subjected to a surface treatment as described above. However, in view of the thermal resistance between the resin and the zinc oxide, those not subjected to the surface treatment are preferable.
There may be acicular zinc oxide in the thermoplastic resin, but this is a breakage of acicular crystal parts extending in different tetraaxial directions in a tetrapot shape. There is no loss.

In the resin composition of the present invention, the blending amount of (I) the thermoplastic resin and (II) zinc oxide is 1 wt% or more and less than 20 wt% of the thermoplastic resin, and (II) zinc oxide exceeds 80 wt%. 99 wt% or less, more preferably (I) the thermoplastic resin is 5 wt% or more and 18 wt% or less.
In addition, it is desirable to add a thermal conductive filler having a thermal conductivity of 10 W / m · K or more to (II) zinc oxide. Examples of the thermally conductive filler having a thermal conductivity of 10 W / m · K or more include metal powder, metal nitride, metal carbide, metal oxide, graphitized hydrocarbon, natural graphite, and spherical graphite particles. Examples of the metal powder include gold, silver, motion, and aluminum. Examples of the metal nitride include boron nitride, silicon nitride, and aluminum nitride. Examples of the metal carbide include silicon carbide. Examples of the metal oxide include aluminum oxide, magnesium oxide, and silicon oxide. The shape of these thermally conductive fillers may be fibrous and / or non-fibrous (plate-like, scale-like, granular, irregular shape, spherical).

Further, (II) a core part which is an essential component of the present invention, zinc oxide which is a needle crystal extending from the core part in different four-axis directions, and zinc oxides other than this zinc oxide, such as granular zinc oxide, spherical oxidation Combination with zinc is also possible.
Among these, metal nitrides and metal oxides are preferable from the viewpoint of workability and cost when filling the thermoplastic resin, and metal oxides are more preferable.
The resin composition of the present invention may contain a flame retardant such as a halogen flame retardant, a phosphoric ester compound, a silicone flame retardant, a metal hydroxide, or red phosphorus.

  Examples of the halogen-based flame retardant include chlorinated paraffin and chlorinated polyethylene as the chlorinated flame retardant, and hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, Tetrabromobisphenol A (TBBA), bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (Bistetrabromophthal) imide (EBTBPI), ethylenebispentabromodiphenyl, tris (tribromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetra Lomobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobisphenol S (DBP-TBBS), tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP), polybromotrimethylphenylindane (PBPI), tris (dibromopropyl) -isocyanurate (TDBPIC) and the like.

  Specific examples of the phosphoric acid ester compound include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], 2,2-bis Examples include {4- [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like, but are not limited thereto. In addition to the above, phosphorus flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, etc. Phosphate ester flame retardant, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4-hydroxy- 3,5-dibromobenzyl phosphonate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2, -Dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, phenyl dinonyl Examples thereof include monophosphate ester compounds such as phenyl phosphate and aromatic condensed phosphate ester compounds.

Specific examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide. It is also possible to use an antimony compound in combination with a flame retardant. Specific examples of the antimony compound include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and sodium antimonate.
The resin composition of the present invention can also contain an anti-drip agent such as polytetrafluoroethylene as a flame retardant aid. The polytetrafluoroethylene has a number average molecular weight of 100,000 or more, preferably about 200,000 to 3,000,000. Thereby, the drip at the time of combustion is suppressed in the resin composition containing polytetrafluoroethylene.

Moreover, antioxidant can be added to the resin composition of this invention. Examples of the antioxidant include hindered phenol antioxidants and amine and hydroxylamine antioxidants. Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate].
An ultraviolet absorber can be added to the resin composition of the present invention. Specific examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber. Particularly preferred are benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.

The resin composition of the present invention can be blended with a filler to give mechanical strength. Specific examples of the filler include calcium carbonate and magnesium carbonate.
The resin composition of the present invention can be blended with a softener as necessary for adjusting the hardness and fluidity of the product. Specific examples of softeners include various kinds such as castor oil and linseed oil.
The hydrogenated copolymer composition or the modified hydrogenated copolymer composition of the present invention is a flame retardant, a flame retardant aid, an antioxidant, an ultraviolet absorber, if necessary within the range not impairing the object of the present invention. As other additives, for example, additives such as a heat stabilizer, an antistatic agent, a light stabilizer, an anti-aging agent, a colorant, and a lubricant can be blended.

The amount of these additives added is based on (I) the thermoplastic resin, (II) the core part, and 100 parts by weight of the total amount of zinc oxide, which is needle-like crystals extending in different four-axis directions from the core part. The total amount does not exceed 100 parts by weight.
In the present invention, in order to produce a composition of (I) a thermoplastic resin, (II) a core part, and zinc oxide which is an acicular crystal extending from the core part in different four-axis directions, In the case of kneading, since there is a concern that air bubbles are generated in the resulting composition, it is more preferable that the water absorption rate of the thermoplastic resin is 100 ppm or more and 800 ppm or less before kneading. Is more preferably 200 ppm or more and 700 ppm or less. The water absorption is measured by collecting 1 g of thermoplastic resin pellets before melt-kneading and using a Karl Fischer moisture meter (MKC-210 / ADP-351) manufactured by Kyoto Electronics Industry Co., Ltd. to absorb the water in the thermoplastic resin pellets. The rate can be determined.

As a method for obtaining the resin composition in the present invention, it can be easily produced by a conventional known technique such as Brabender, kneader, Banbury mixer, twin-screw or single-screw extruder, and the obtained resin composition is obtained by general injection molding, Molding can be performed by a known molding method such as injection press molding or gas injection molding. Further, as a molding method for obtaining the resin composition as a sheet, the resin composition of the present invention is obtained by kneading by the above method, and then molded by extrusion molding, calendar molding, roll molding, press molding, or the like. be able to.
The thickness of the heat radiating resin sheet in the present invention is usually 0.005 to 3 mm, preferably 0.01 to 1 mm. The heat-dissipating resin sheet preferably has a smooth surface, and the 60 ° surface gloss value on the surface of the heat-dissipating resin sheet measured according to JIS · K-7105 is preferably 10 or more.

The heat-dissipating resin sheet in the present invention attaches a cooling component such as a heat sink to the above-mentioned electronic element for the purpose of suppressing heat generation of the electronic element such as LSI or CPU that performs electronic control, and makes the contact between the two close to make the heat effective. It can be used for the purpose of transmitting to the cooling component.
The heat-dissipating resin sheet of the present invention is excellent in thermal conductivity, has less volatile components due to heating, and has excellent surface smoothness. Heat-dissipating parts of computers such as personal computers and home-use game machines, DVD players, DVD recorders Heat-dissipating parts for HDDs, heat-dissipating parts for HDD recorders, heat-dissipating parts such as display power supply units for home TVs, plasma displays, liquid crystal TVs, etc. It is suitably used for applications that require high thermal conductivity, such as heat dissipation parts used in car electrical equipment for car stereos, car navigation systems, inverters, lighting, and air conditioners.
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by these.

(I) Thermoplastic resin (Ii) is a hydrogenated block copolymer of styrene / butadiene block copolymer synthesized by the method described in JP-A-60-220147 (number average molecular weight 65000, bonded styrene). The amount of 1,2-vinyl bonds in the polybutadiene part before hydrogenation was 36% by weight, and the hydrogenation rate of the polybutadiene part was 99%).
As the thermoplastic resin (I-ii), a PBT (polybutylene terephthalate) resin obtained by the method described in Reference Example 1 thermoplastic resin in Examples of JP-A-2004-175812 was used.
(II) Zinc oxide is a zinc oxide A (made by Matsushita Amtech Co., Ltd., trade name: Panatetra, WZ-0501) which is a needle-like crystal that has not been subjected to surface treatment and extends in different four-axis directions from the core. , The diameter of the base of the needle-like crystal part is 0.7 to 14 μm, the length from the base to the tip of the needle-like crystal part is 3 to 200 μm), zinc oxide B having a spherical structure (made by Toho Zinc Co., Ltd., trade name) : Silver candy A, particulate, average particle diameter 0.2 μm) was used.
(I) Thermoplastic resin and (II) A twin screw extruder (ZSK-25 25 mmφ with a compounding composition as shown in Table 1 and a cylinder temperature set at 260 ° C. and a screw rotation speed of 500 rpm, as shown in Table 1. L / D = 52, total length of heated portion 1300 mm, manufactured by WERNER & PFLEIDERE), and kneaded to obtain a resin composition. A test piece was obtained as a resin sheet having a thickness of 2 mm, a length of 120 mm and a width of 220 mm by press-molding the obtained resin composition. The heating temperature at this time was 200 ° C. when the thermoplastic resin (I-i) was used, and 290 ° C. when the thermoplastic resin (I-ii) was used.

Evaluation was performed according to the following items.
<Amount of chips generated during melt extrusion>
After passing through a strand bath installed at the spinneret of the twin screw extruder during melt-kneading, the take-up speed of the pelletizer was adjusted so that the diameter of the strand in front of the pelletizer was 2 mm to 3 mm. At this time, the length of the strand in which the strand was immersed in the water tank was 100 cm. The water temperature was between 18 ° C and 22 ° C.
At this time, about 100 g of the pellets coming out of the pelletizer were taken out and weighed precisely. The value at this time is W1. Next, the precisely weighed pellets were spread on a 60 mesh wire mesh and shaken well to separate the pellets and chips, and then the weight of the pellets remaining on the wire mesh was precisely weighed. Let this value be W2. From the obtained W1 and W2, the ratio of the chips (% by weight) was calculated using the following formula. The results are shown in Table 1.
Weight% of cutting powder = (1−W2 / W1) × 100

<Thermal conductivity>
Rapid thermal conductivity measuring instrument QTM-500 (thin wire heating) equipped with thin film measurement software (SOFT-QTM5W) manufactured by Kyoto Electronics Industry Co., Ltd. using the sheet of thickness 2 mm (120 mm x 220 mm) obtained above. Method) was used to measure the thermal conductivity. The measurement is a method (described in Japanese Patent Publication No. 5-12361) in which a thermal conductivity is obtained with a box probe (PD-11) using a reference plate (foamed polyethylene, silicone rubber, quartz glass) having a known thermal conductivity. The thermal conductivity of the heat radiating resin sheet was determined. The results are shown in Table 1.

<Volatile component of heat-dissipating resin sheet>
In the sheet having a thickness of 2 mm (120 mm length × 220 mm width) obtained as described above, a part of this sheet was taken out, and the weight reduction rate with respect to heat was measured using a thermogravimetric measuring device (AXS manufactured by BRUKER). In the measurement, in the air, the heating temperature was increased at a rate of 5 ° C./min in the range from 30 ° C. to 200 ° C., and the weight reduction rate of the composition at 150 ° C. was determined. The results are shown in Table 1.

  The resin composition in the present invention and the heat-dissipating resin sheet obtained by using the resin composition are excellent in thermal conductivity, have few volatile components due to heating, and are excellent in sheet surface smoothness, and are used in computers such as personal computers and consumer game machines. Heat radiating parts, heat radiating parts for DVD players and DVD recorders, heat radiating parts for HDD recorders, heat radiating parts such as display power supply units for home TVs, plasma displays, liquid crystal TVs, mobile phones, various computers, various AV equipment It is suitably used for applications that require high thermal conductivity, such as heat dissipating parts used in office automation equipment, car stereos, car navigation systems, inverters, lighting, and heat dissipating parts used in automotive electrical components of air conditioners.

Claims (10)

  (I) One or more kinds of heat selected from polyamide resin, polyacetal resin, polyphenylene ether resin, polycarbonate resin, ABS resin, polyolefin resin, polystyrene resin, methacrylic resin, and thermoplastic elastomer Resin comprising 1% by weight or more and less than 20% by weight of a plastic resin, and (II) zinc oxide which is a needle-like crystal extending in a four-axis direction different from the core part and more than 80% by weight. Composition.   (I) Thermoplastic resin is 5% by weight or more and 18% by weight or less, and (II) Zinc oxide which is a needle-like crystal extending in the four-axis directions different from the core part and this core part is 82% by weight or more and 95% by weight or less. The resin composition according to claim 1, comprising:   The resin composition according to claim 1 or 2, wherein the thermoplastic resin is at least one selected from polyamide resins, polyacetal resins, polyphenylene ether resins, polyolefin resins, and thermoplastic elastomers.   The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin is one or more selected from polyolefin resins and thermoplastic elastomers.   The resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin is a thermoplastic elastomer.   (II) A thermal conductive filler having a thermal conductivity of 10 W / m · k or more is further added to a core and zinc oxide which is a needle-like crystal extending in different four-axis directions from the core. The resin composition of any one of -5.   A heat-dissipating resin sheet obtained by molding the resin composition according to claim 1 into a sheet shape.   The heat-dissipating resin sheet according to claim 7, wherein the heat-dissipating resin sheet is formed into a sheet by injection molding.   The heat-radiating resin sheet according to claim 7 or 8, wherein the surface gloss value on the surface is 10 or more.   A thermoplastic resin in which the water absorption of the thermoplastic resin (I) is in a state of 800 ppm or less, and (II) a core part and zinc oxide, which is a needle-like crystal extending in different four-axis directions from the core part, are melt-kneaded. The manufacturing method of the resin composition of any one of Claims 1-5 characterized by the above-mentioned.