JP5794863B2 - Thermoplastic resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition.

  Thermoplastic resin compositions are generally used in many applications because they are generally excellent in heat resistance and impact resistance. Examples include electrical / electronic related parts, office equipment parts, automotive parts applications, various exterior materials, industrial products, and the like. In recent years, with high performance, downsizing, and weight reduction in electrical / electronic equipment and office equipment, resin rigidity is reduced due to heat generated inside the equipment, and deformation and contraction are likely to occur. Yes. When such deformation or contraction occurs, a reduction in device accuracy may be a problem. For this reason, it is important to take measures to dissipate heat generated inside the device efficiently.

  In general, as a method of diffusing and dissipating the heat inside the device, a method using a metal or ceramic material with good thermal conductivity or a method of dissipating heat using a metal heat sink or a heat dissipation fan is used. It has been.

On the other hand, as a member of the above-mentioned equipment, development of a resin composition having a high degree of freedom in shape selection, easy to be reduced in weight and size, and having thermal conductivity is required, and various studies have been made. Yes. For example, aluminum oxide, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, zinc oxide, silicon carbide, quartz, aluminum hydroxide and other metal oxides, metal nitrides, metal carbides, metal hydroxides with high thermal conductivity The resin composition which mix | blended etc. is examined. In addition to these, materials that impart thermal conductivity to the resin composition include powdery substances such as graphite powder, fibrous substances, and the like, and in Patent Document 1, the apparent density is 0.15 g / cm ³ or less. A resin composition using a certain graphite powder is disclosed.

JP 2007-031611 A

  However, since the internal components of electrical / electronic equipment and office equipment often require not only thermal conductivity but also high flame retardancy, the resin composition described in Patent Document 1 It is difficult to satisfy both flame retardancy. Even in conventional resin compositions other than Patent Document 1, both thermal conductivity and flame retardancy are not sufficient.

  This invention is made | formed in view of the said situation, and makes it a main objective to provide the thermoplastic resin composition excellent in thermal conductivity and a flame retardance.

  As a result of intensive studies to solve the above problems, the present inventors have formulated (A) a thermoplastic resin, (B) graphite, and (C) a flame retardant at a specific ratio, and also conducts heat according to JIS R2618. It has been found that the above-mentioned problems can be solved by using a thermoplastic resin composition in which the rate and the flame retardant level of the UL-94 standard satisfy specific conditions, and the present invention has been completed.

That is, the present invention is as follows.
[1]
(A) 100 parts by mass of a thermoplastic resin;
(B) 10 to 200 parts by mass of graphite;
(C) 5 to 50 parts by mass of a flame retardant,
A thermoplastic resin composition having a thermal conductivity in accordance with JIS R2618 of 1.0 W / m · K or higher and a flame retardant level of UL-94 standard of Rank V-1 or higher.
[2]
From the polymer alloy containing (i) a polyphenylene ether resin, (ii) a polycarbonate resin, or (iii) a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin) as the (A) thermoplastic resin. The thermoplastic resin composition according to [1], comprising at least one selected from the group consisting of:
[3]
The thermoplastic resin composition according to [1] or [2], which includes a polyphenylene ether-based resin as the (A) thermoplastic resin.
[4]
The thermoplastic resin composition according to any one of [1] to [3], further including (D) 10 to 50 parts by mass of an inorganic filler with respect to 100 parts by mass of the (A) thermoplastic resin.
[5]
The thermoplastic resin composition according to any one of [1] to [4], which contains a compound represented by the following formula (I) or formula (II) as the flame retardant (C).
(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² represent a methyl group, and R ³ and R ⁴ represent Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 each independently Represents an integer of 0 to 3).
[6]
The thermoplastic resin composition according to any one of [1] to [5], including 50 to 150 parts by mass of the (B) graphite with respect to 100 parts by mass of the (A) thermoplastic resin.
[7]
(B) the apparent density of the graphite is 0.20g / cm ³ ~1.20g / cm ³ (1) The thermoplastic resin composition according to any one of to [6].
[8]
(B) the apparent density of the graphite is ^{0.30g / cm 3 ~1.00g / cm 3} , and said (B) the average particle size of the graphite is 50μm~1000μm [1] to [7] The thermoplastic resin composition according to any one of the above.
[9]
(B) the apparent density of the graphite is ^{0.50g / cm 3 ~0.80g / cm 3} , and said (B) the average particle size of the graphite is 300μm~800μm [1] to [8] The thermoplastic resin composition according to any one of the above.

  According to the present invention, a thermoplastic resin composition having excellent thermal conductivity and flame retardancy can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

The thermosetting resin composition of the present embodiment is
(A) 100 parts by mass of a thermoplastic resin;
(B) 10 to 200 parts by mass of graphite;
(C) 5 to 50 parts by mass of a flame retardant,
It is a thermoplastic resin composition having a thermal conductivity in accordance with JIS R2618 of 1.0 W / m · K or higher and a flame retardance level of UL-94 standard of Rank V-1 or higher. The thermoplastic resin composition of this embodiment is excellent in thermal conductivity and flame retardancy. Hereinafter, each component will be described.

<(A) Thermoplastic resin>
The (A) thermoplastic resin used in the present embodiment is not particularly limited, and known ones can also be used. Specific examples of (A) thermoplastic resins include, for example, polyphenylene ether resins, polycarbonate resins, acrylonitrile-butadiene-styrene copolymer (ABS) resins, polymer alloys of polycarbonate resins and ABS resins, and polybutylene terephthalate systems. Examples thereof include resins, polyethylene terephthalate resins, polyphenylene sulfide resins, and the like.

  As internal parts of electrical / electronic equipment and office equipment, it is preferable that they have excellent electrical characteristics, flame retardancy, and the like. From this point of view, (A) the thermoplastic resin contains at least one selected from the group consisting of (i) polyphenylene ether-based resin, (ii) polycarbonate, and (iii) polymer alloy containing polycarbonate and ABS resin. Is preferred. Among these, it is more preferable that (i) polyphenylene ether resin is included. Thermoplastic resin compositions containing such components tend to be more excellent in electrical properties and flame retardancy.

[Polyphenylene ether resin]
The phenylene ether resin is a homopolymer or copolymer having a repeating unit represented by the following formula (III) and / or formula (IV).
(In the formula (III) and formula ^{(IV), R 5, R} 6, R 7, R 8, R 9 and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 6 carbon atoms Represents an aryl group of ˜9 or a halogen atom, provided that R ⁹ and R ¹⁰ are not hydrogen at the same time.

  Specific examples of the polyphenylene ether homopolymer 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-chloroethyl-1, 4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) Ether and the like.

  The polyphenylene ether copolymer is a copolymer having a repeating unit represented by the formula (III) and / or the formula (IV) as a main repeating unit. The main repeating unit here means a repeating unit contained in the copolymer at 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.

  Specific examples of the polyphenylene ether copolymer include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, 2, Examples include copolymers of 6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol.

  Among the above polyphenylene ether resins, poly (2,6-dimethyl-1,4-phenylene) ether, 2- (dialkylaminomethyl) -6-methylphenylene from the viewpoints of productivity, mechanical properties and flame retardancy Polyphenylene ether copolymers having ether monomer units and polyphenylene ether copolymers having 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether monomer units are preferred. Among these, a polyphenylene ether copolymer having a 2- (dialkylaminomethyl) -6-methylphenylene ether monomer unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether monomer A polyphenylene ether copolymer having a unit is more preferred. As such a polyphenylene ether copolymer, for example, those described in JP-A No. 63-301222 can be used.

  The reduced viscosity (unit dL / g, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin is preferably 0.25 to 0.60 dL / g, more preferably 0, from the viewpoint of the balance between mechanical properties and molding fluidity. The range is from 35 to 0.55 dL / g.

  As the polyphenylene ether resin, a modified polyphenylene ether resin partially or entirely modified with an unsaturated carboxylic acid or a derivative thereof can be used. The modified polyphenylene ether resin is excellent in hydrolysis resistance, and has excellent impact strength even in a high temperature and high humidity environment. Therefore, the thermoplastic resin composition of the present embodiment is particularly suitable as a component of equipment used in a high temperature and high humidity environment. It is suitable when using a product. The production method of the modified polyphenylene ether-based resin is not particularly limited, and JP-A Nos. 02-276823 (US Pat. Nos. 5,159,027 and 0035695) and JP-A Nos. 63-108059 (US Pat. Nos. 5,214,109 and 5216089). ), And JP-A-59-059724. The modified polyphenylene ether resin is produced by, for example, melting and kneading an unsaturated carboxylic acid or a derivative thereof with a polyphenylene ether resin in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving a polyphenylene ether resin and an unsaturated carboxylic acid or a 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 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. .

  Moreover, although it is saturated carboxylic acid, the compound which itself can thermally decompose at the reaction temperature at the time of manufacturing modified polyphenylene ether-type resin, and can become the derivative | guide_body of the unsaturated carboxylic acid used by this embodiment can also be used. Specific examples include malic acid and citric acid. These may be used individually by 1 type and may be used in combination of 2 or more type.

  When (A) a polyphenylene ether resin is used as the thermoplastic resin, it is preferable that a styrene resin is further included as the (A) thermoplastic resin. Here, the styrene resin is obtained by polymerizing a styrene compound or a styrene compound and another compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer ( Co) polymer.

  Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Among these, styrene is preferable from the viewpoint of compatibility with the polyphenylene ether resin. Specific examples of other compounds copolymerizable with styrenic compounds include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. Etc. The amount of the other copolymerizable compound used is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount of the styrene-based compound.

  Examples of the rubbery polymer used for the polymerization reaction include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Among these, from the viewpoint of heat resistance stability, polybutadiene is preferable as the conjugated diene rubber, and styrene-butadiene copolymer is preferable as the ethylene-propylene copolymer rubber. Among these, partially hydrogenated polybutadiene having an unsaturation degree of 20 to 80% and polybutadiene containing 90% or more of 1,4-cis bonds are more preferable. Here, the degree of unsaturation and the 1,4-cis bond can be measured by a nuclear magnetic resonance apparatus (NMR).

  Specific examples of the styrene resin thus obtained include polystyrene, rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), ABS resin, and other styrene copolymers. Among these, from the viewpoint of heat resistance stability, a combination of polystyrene and partially hydrogenated polybutadiene having an unsaturation degree of 20 to 80%, and polybutadiene containing 90% or more of polystyrene and 1,4-cis bonds are used. A combination with rubber reinforced polystyrene is preferred.

  The content of the styrene resin is not particularly limited, but from the viewpoint of heat resistance, flame retardancy, and processability, a range of 0 to 50 parts by mass is preferable with respect to 100 parts by mass of the polyphenylene ether resin, and 5 to 30 is preferable. The range of parts by mass is more preferable. (A) When a polyphenylene ether resin and a polystyrene resin are used in combination as the thermoplastic resin, the styrene resin is used in a form that replaces a part of the polyphenylene ether resin, and the polyphenylene ether is contained by the amount of the styrene resin. The content of the system resin is reduced. When the content of the styrene resin increases, the fluidity of the thermoplastic resin composition tends to improve. When the content of the styrenic resin is 50 parts by mass or less, the thermoplastic resin composition tends to be excellent in heat resistance and flame retardancy.

[Polycarbonate resin]
As the polycarbonate-based resin, it is possible to use a bisphenol A type polycarbonate generally used and various polycarbonates polymerized using other dihydric phenols. The manufacturing method of polycarbonate-type resin is not specifically limited, A well-known method is also employable. For example, when a polycarbonate resin is produced by interfacial polycondensation, a monohydric phenol end-stopper can usually be used. The polycarbonate resin may be a branched polycarbonate obtained by polymerizing trifunctional phenols, or an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a divalent aliphatic alcohol or an alicyclic alcohol is copolymerized. A polycarbonate copolymer may be used.

The polycarbonate-based resin in the present embodiment has a main chain composed of a repeating unit represented by the following formula (V).
(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, (The thing represented by (VI) is mentioned.)
(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, Ar ¹ and Ar ² represent groups such as phenylene, naphthylene, biphenylene, and pyridylene, which may be unsubstituted or substituted, and Y represents the following formula (VII): An alkylene group represented by any of the above, or a substituted alkylene group.)
(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a carbon number of 6 Represents a 30 to 31 aryl group or a C7 to 31 aralkyl group, optionally substituted with a halogen atom or a C1 to C10 alkoxyl group, k is an integer of 3 to 11, R ¹⁷ and R ¹⁸ is individually selected for each X, and each independently represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 30 carbon atoms, optionally a halogen atom or an alkoxy group having 1 to 10 carbon atoms. And X represents a carbon atom.)

Among the above, what is represented by the following formula (VIII) is a preferred example.

  In particular, a polycarbonate resin containing 85 mol% or more of repeating units having a structure represented by the above formula (VIII) (based on all monomer units in the polycarbonate resin) is particularly preferable.

  Moreover, the polycarbonate-type resin which can be used for this embodiment 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 embodiment is usually 5000 to 500000, preferably 10000 to 100000, more preferably 13,000 to 50000, and particularly preferably 15000 to 30000. The polycarbonate resin used in the present embodiment 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 embodiment. 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-phase polymerization of crystallized carbonate prepolymers obtained by polymerization methods (for example, phosgene method), transesterification methods (melting method) for reacting aromatic dihydroxy compounds with carbonic acid diesters (for example, diphenyl carbonate), phosgene methods or melting methods (Japanese Unexamined Patent Publication No. 01-158033 (corresponding to US Pat. No. 4,948,871), Japanese Unexamined Patent Publication No. 01-271426, Japanese Unexamined Patent Publication No. 03-068627 (corresponding to US Pat. No. 5,204,377)), etc. Use the product manufactured by the method described in 1. Door can be.

  As a preferable polycarbonate-based resin, a polycarbonate resin containing substantially no chlorine atom produced by a transesterification method from a dihydric 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 Japanese Patent Publication No. 07-098862.

  In the present embodiment, the polycarbonate resin is preferably a polycarbonate resin having a branched structure in the main chain in order to improve molding processability. As a method for obtaining a polycarbonate-based resin having such 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, Although there is a method shown in German Patent No. 3149812, etc., a polycarbonate resin having a particularly preferable branched structure that can be used in this embodiment is produced by the method described in US Pat. No. 5,932,683. be able to.

[Polymer alloy containing polycarbonate resin and ABS resin]
(A) When using a polycarbonate-type resin as a thermoplastic resin, it is preferable to further contain an ABS resin as a (A) thermoplastic resin. In this case, it can be set as the polymer alloy containing a polycarbonate-type resin and ABS resin.

  The content of the ABS resin is not particularly limited, but from the viewpoint of heat resistance and flame retardancy, the total content of the ABS resin is preferably 0 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate. Part by mass is more preferable. The thermoplastic resin composition in such a blending range tends to be more excellent in both heat resistance and flame retardancy.

[Polybutylene terephthalate resin]
The polybutylene terephthalate resin may be produced by either a transesterification reaction between dimethyl terephthalate and ethylene glycol or a direct esterification reaction between terephthalic acid and ethylene glycol.

[Polyethylene terephthalate resin]
The polyethylene terephthalate resin may be produced by either a DMT method by transesterification of dimethyl terephthalate and 1,4-butanediol or a direct polymerization method of terephthalic acid and 1,4-butanediol.

  In any case of polybutylene terephthalate resin and polyethylene terephthalate resin, together with terephthalic acid or its dialkyl ester, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, Dibasic acids such as trimellitic acid and their dialkyl esters, tribasic acids and the like, and their dialkyl esters can be used. It is preferable that these usage-amounts are the range of 40 mass parts or less with respect to 100 mass parts of terephthalic acid or its dialkyl ester.

  Similarly, during the polycondensation reaction, together with ethylene glycol or 1,4-butanediol, as other aliphatic glycols, for example, ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, etc., aliphatic In addition to glycol, for example, other diols such as cyclohexanediol, cyclohexanedimethanol, xylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol, and polyhydric alcohols can be used in combination. The amount of these diols or polyhydric alcohols used is preferably in the range of 40 parts by mass or less with respect to 100 parts by mass of the aliphatic glycol. It is preferable that these usage-amounts are the range of 40 mass parts or less with respect to 100 mass parts of terephthalic acid or its dialkyl ester.

  The molecular weight of the polyester resin is an intrinsic viscosity measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethane (weight ratio = 50/50), preferably 0.5 to 1.8, more preferably 0. .7 to 1.5.

[Polyphenylene sulfide resin]
The polyphenylene sulfide-based resin is a polymer containing an arylene sulfide repeating unit represented by the following formula (IX) usually at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%.

[—Ar—S—] (IX)

(In the formula, Ar represents an arylene group.)

  Examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms, and a phenyl group), a p, p′-diphenylene sulfone group, A p, p'-biphenylene group, a p, p'-diphenylenecarbonyl group, a naphthylene group, etc. can be mentioned. Here, the polyarylene sulfide resin may be a homopolymer having one type of arylene group as a structural unit, but from the viewpoint of processability and heat resistance, a copolymer in which two or more types of arylene groups are mixed may be used. .

  Among these polyarylene sulfide resins, polyphenylene sulfide resins mainly composed of repeating units of p-phenylene sulfide are excellent in processability, heat resistance and dimensional stability, and are easily available industrially. Is particularly preferred. In addition, the polyarylene sulfide resin used in the present invention can be arbitrarily selected from a melt viscosity (shear rate of 1000 / second) at 320 ° C. from 100 to 10,000 poises, and the structure of the polyarylene sulfide resin is linear. The polyarylene sulfide resin having a linear structure is preferred, although it may be either in the form of a ring or branched and may be a mixture of these structures.

[Polyolefin resin]
The thermoplastic resin composition used in the present embodiment preferably further contains a polyolefin resin. By adding the polyolefin-based resin, the releasability during molding of the thermoplastic resin composition is improved, and the impact resistance of the thermoplastic resin composition is also improved. Examples of the polyolefin resin used in the present embodiment include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, or ethylene. -An acrylic ester copolymer etc. are mentioned. Among these, low density polyethylene and ethylene-propylene copolymer are preferable. The ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer or ethylene-acrylic acid ester copolymer is generally an amorphous or low-crystalline copolymer. These copolymers may be copolymerized with other monomers as long as the performance is not affected. For example, the component ratio of ethylene and propylene, butene, or octene is not particularly limited, but usually the components of propylene, butene, or octene in the polyolefin resin are 5 to 50 mol% in total. The above-mentioned polyolefin-based resins may be used alone or in combination of two or more.

  The melt flow rate (MFR; measured at a cylinder temperature of 230 ° C. in accordance with ASTM D1238) of the polyolefin-based resin is preferably 0.1 to 50 g / 10 minutes from the viewpoint of dispersibility, and 0.2 to 20 g / 10 minutes is more preferable.

  The content of the polyolefin-based resin in the thermoplastic resin composition of the present embodiment is not particularly limited, but is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of (A) the thermoplastic resin. More preferably, it is 1-6 mass parts, and it is still more preferable that it is 0.5-2 mass parts. If the content of the polyolefin resin is 0.05 parts by mass or more, the release effect at the time of molding tends to be further excellent, and if it is 10 parts by mass or less, there is no problem of peeling at the time of molding, and mechanical properties are improved. It tends to be even better.

<(B) Graphite>
The (B) graphite used in the present embodiment is not particularly limited, and known ones can also be used. Specific examples of (B) graphite include, for example, artificial graphite obtained by heat treatment of flaky graphite, massive graphite, earthy graphite, petroleum coke, petroleum pitch, amorphous carbon, and the like. Among these, scaly graphite is preferable.

  (B) Content of graphite is 10-200 mass parts with respect to 100 mass parts of (A) component, 50-150 mass parts is preferable, and 60-100 mass parts is more preferable. (B) If the graphite content is less than 10 parts by mass, the thermal conductivity of the thermoplastic resin composition is inferior, and if it exceeds 200 parts by mass, the flame retardancy and injection moldability are significantly impaired.

(B) graphite preferably has a lower limit of the apparent density is 0.16 g / cm ³ or more, more preferably 0.20 g / cm ³ or more, still be at 0.30 g / cm ³ or more Preferably, it is more preferably 0.50 g / cm ³ or more. When the apparent density is 0.16 g / cm ³ or more, the flame retardancy and the handleability tend to be further improved. Also, (B) the upper limit of the apparent density of the graphite is preferably at 1.50 g / cm ³ or less, more preferably 1.20 g / cm ³ or less, it is 1.00 g / cm ³ or less Is more preferable, and 0.80 g / cm ³ or less is even more preferable. When the apparent density is 1.50 g / cm ³ or less, flame retardancy and thermal conductivity tend to be further improved. The apparent density here can be measured according to JIS K7365. The apparent density can be adjusted, for example, by appropriately controlling the particle diameter and shape of graphite. For example, a method of controlling the particle diameter by pulverizing graphite, a method of treating with an acid or an alkali, It can be controlled by inflating, etc. (but not limited to this).

  (B) Although the average particle diameter of graphite is not particularly limited, it is preferably 50 to 1000 μm, more preferably 100 to 900 μm, still more preferably 300 to 800 μm, and 500 to 700 μm. Is even more preferable. (B) Since the average particle diameter of graphite is 50 μm or more, (B) graphite can be more uniformly dispersed in the thermoplastic resin composition, and therefore, the extrusion stability during the production of the thermoplastic resin composition is excellent. As a result, productivity is further improved and handling is further improved. (B) When the average particle diameter of graphite is 1000 μm or less, the appearance of the molded product is further improved. For the average particle size, an integrated distribution curve is prepared according to the dry screening test method described in JISK0069, and the value when the integrated percentage is 50% is defined as the average particle size. (B) The shape of the graphite is not particularly limited, but scaly graphite is preferable from the viewpoint of rigidity.

In view of the above, specific examples of suitable (B) graphite, an apparent density of ^{0.30g / cm 3 ~1.00g / cm 3} , and include graphite average particle size of 50μm~1000μm and more specific examples of suitable (B) graphite, an apparent density of ^{0.50g / cm 3 ~0.80g / cm 3} , and a 300μm~800μm average particle diameter of (B) graphite graphite Is mentioned.

  The surface of the graphite of this embodiment is subjected to surface treatment, for example, epoxy treatment, urethane treatment, silane coupling treatment, oxidation treatment, etc., as long as the properties of the thermoplastic resin composition of this embodiment are not impaired. Also good.

(C) <Flame retardant>
The (C) flame retardant used in the present embodiment is selected from at least one selected from the group consisting of inorganic flame retardants, silicone compounds, and organic phosphorus compounds.

  As inorganic flame retardants, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing water of crystallization, which are generally used as flame retardants for synthetic resins, boric acid A zinc compound and a zinc stannate compound are mentioned.

  Examples of the silicone compound include organopolysiloxane and modified products thereof, which may be liquid at normal temperature or solid. The skeleton structure of the organopolysiloxane may be either a linear structure or a branched structure, but preferably includes a branched structure obtained by having a trifunctional structure or a tetrafunctional structure in the molecule, and further a three-dimensional structure. By including such a structure, char tends to be formed during combustion, and the combustibility tends to be further improved. The substituent present in the main chain or branched side chain is hydrogen or a hydrocarbon group, and is preferably a phenyl group, a methyl group, an ethyl group, or a propyl group, but other hydrocarbon groups may be used. . The terminal linking group may be any of a hydroxyl group, an alkoxy group, and a hydrocarbon group.

The silicone compound here is composed of four types of siloxane units (M unit: R ₃ SiO _0.5 , D unit: R ₂ SiO _1.0 , T unit: RSiO _1.5 , Q unit: SiO _2.0 , where R is a bonded hydrocarbon group. Is a polymer obtained by polymerization. The organopolysiloxane, in the total amount of the conditions (a) above of the four siloxane units, siloxane units of the formula RSiO _1.5 (T units) and preferably 60 mol% or more, more preferably 90 mol% or more, further Preferably 100 mol% or more, and in the condition (b) silicone compound, the total amount of hydrocarbon groups in all siloxane units represented by R is preferably 60 mol% or more, more preferably 80 mol% or more. Have a phenyl group. The organopolysiloxane that satisfies the conditions (a) and (b) may be a modified silicone compound in which a bonding group is substituted with an amino group, an epoxy group, a mercapto group, or another modifying group. A modified product obtained by chemically or physically adsorbing organopolysiloxane on an inorganic filler such as silica or calcium carbonate that can be used as the component (D) described above can also be used.

  Examples of organic phosphorus compounds include phosphate ester compounds and phosphazene compounds. The phosphate ester compound is added for the purpose of improving flame retardancy, and an organic phosphate ester compound generally used as a flame retardant can be used.

  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. Further, as phosphate compounds other than the above, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate Phosphate ester flame retardants such as diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4- Hydroxy-3,5-dibromobenzyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroquinonyl Examples thereof include monophosphate compounds such as phosphate and phenyldinonylphenyl phosphate, and aromatic condensed phosphate compounds.

  Among these, an aromatic condensed phosphate ester compound is preferable from the viewpoint of less gas generation during processing and excellent thermal stability. As the aromatic condensed phosphate ester compound, a commercially available product can be used. For example, “CR741”, “CR733S”, “PX200” manufactured by Daihachi Chemical Industry, “FP600” manufactured by ADEKA, “FP700”, “FP800” or the like can be used.

Among them, the flame retardant (C) is preferably a phosphate ester compound (condensed phosphate ester) represented by the formula (I) or the formula (II) from the viewpoint of moisture resistance. A phosphoric acid ester compound (condensed phosphoric acid ester) is more preferable.
(In Formula (I) and Formula (II), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, and R ¹ and R ² represent a methyl group. , R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, m1, m2, m3 and m4 each independently represents an integer of 0 to 3.)

  In the condensed phosphate esters represented by the above formulas (I) and (II), n is an integer of 1 or more, preferably an integer of 1 to 3, in each molecule.

In the condensed phosphate esters represented by the above formulas (I) and (II), preferred condensed phosphate esters are those in which m1, m2, m3, m4, n1 and n2 in formula (I) are 0, and R ^A condensed phosphate ester in which ³ and R ⁴ are methyl groups; Q ¹ , Q ² , Q ³ , Q ⁴ , R ³ and R ⁴ in formula (I) are methyl groups; n1 and n2 are 0; m1, m2, m3 and m4 are condensed phosphates whose integers are 1 to 3, wherein n is an integer of 1 to 3, particularly n is 1. In particular, it is preferable that (C) the flame retardant contains 50% by mass or more of such a condensed phosphate ester.

  These aromatic condensed phosphate esters are preferably aromatic condensed phosphate esters having an acid value of 0.1 or less (value obtained in accordance with JIS K2501) from the viewpoint of thermal stability.

  Moreover, as a phosphazene compound, a phenoxy phosphazene and its crosslinked body are preferable, and a phenoxy phosphazene compound whose acid value (based on JIS K2501) is 0.1 or less is more preferable from the viewpoint of thermal stability.

Examples of the phenoxyphosphazene compound include those having a structure represented by the formula (X), and cyclic structure compounds are preferable, and n = 3 and 4 6-membered and 8-membered phenoxyphosphazene compounds are particularly preferable. preferable.
(Here, R ¹⁹ and R ²⁰ each independently represents an aliphatic group or aromatic group having 1 to 20 carbon atoms, and n is an integer of 3 or more.)

Furthermore, these compounds are crosslinked by a crosslinking group selected from the group consisting of, for example, a phenylene group, a biphenylene group, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, and —O—. May be.

  The phosphazene compound represented by the formula (X) is a known compound, for example, James E. et al. Mark, Harry R. Allcock, Robert West, “In-rgical Polymers” Pretice-Hall International, Inc. , 1992, p61-p140. Synthesis examples for obtaining these phosphazene compounds are disclosed in JP-B-03-073590, JP-A 09-071708, JP-A 09-183864, JP-A 11-181429, and the like. For example, in the synthesis of non-crosslinked cyclic phenoxyphosphazene compounds, R. According to the method described by Allcock, “Phosphorus-Nitrogen Compounds”, Academic Press, (1972), dichlorophosphazene oligomer (mixture of 62% trimer and 38% tetramer) 1.0 unit mole (115 0.9 g) of a 20% chlorobenzene solution containing sodium phenolate in toluene with stirring, followed by reaction at 110 ° C. for 4 hours. After purification, an uncrosslinked cyclic phenoxyphosphazene compound is obtained.

  The content of the flame retardant (B) varies depending on the required flame retardant level, but is 5 to 50 parts by mass and 5 to 30 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin. Preferably, it is 10-25 mass parts. (C) When the content of the flame retardant is less than 5 parts by mass, the flame retardancy of the thermoplastic resin composition is inferior, and when it exceeds 30 parts by mass, the heat resistance is inferior.

<(D) Inorganic filler>
The thermoplastic resin composition of the present embodiment preferably further includes (D) an inorganic filler. Inorganic fillers include silica, diatomaceous earth, pumice powder, pumice balloon, basic magnesium carbonate, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, glass fiber, glass flakes, glass beads, silicic acid Examples include calcium, montmorillonite, bentonite, molybdenum sulfide, and aluminum borate. These may be used alone or in combination of two or more. Among these, glass fiber, glass flake, talc, and mica are preferable from the viewpoint of rigidity.

  The content of the (D) inorganic filler is not particularly limited, but it is preferably 0 to 100 parts by mass and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin. .

  In addition to the above-described components, other plastic additives that are generally used are added to the thermoplastic resin composition used in the present embodiment in order to further impart other characteristics, so long as the effects of the present embodiment are not impaired. An agent (for example, an anti-dripping agent, a plasticizer, an antistatic agent, a lubricant, a release agent, a dye / pigment, various inorganic fillers for plastics, etc.) can be added. As the dripping preventive agent, for example, a dripping preventive agent at the time of combustion such as polytetrafluoroethylene can be used, and as a plasticizer, an antistatic agent, a lubricant, a release agent, a dye / pigment, various inorganic fillers for plastics. Those generally used can be appropriately used.

  Other polymers and oligomers can be further added to the thermoplastic resin composition used in the present embodiment. Examples of the impact resistance improver include a hydrogenated block copolymer, a petroleum resin as a fluidity improver, a terpene resin and its hydrogenated resin, a coumarone resin, and a coumarone indene resin.

[Characteristics of thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment has a thermal conductivity according to JIS R2618 of 1.0 W / m · K or higher, and a flame retardance level of UL-94 standard is rank V-1 or higher.

(1) Thermal conductivity The resin composition of this embodiment has a thermal conductivity of 1.0 W / m · K or more. The value of thermal conductivity can be measured according to JIS R2628. Specifically, it can be measured by a probe method using a thermal conductivity measuring instrument such as “QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd. using a flat plate of 100 mm × 100 mm × 2.0 mm. In order to improve thermal conductivity, metal oxides and metal nitrides such as aluminum oxide, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, zinc oxide, silicon carbide, quartz, and aluminum hydroxide with high thermal conductivity are used. In addition, it is known that a powdery substance such as a metal carbide, a metal hydroxide, or a graphite powder, a fibrous substance, or the like is blended. Among these, graphite is used in the resin composition of the present embodiment. Among these, from the viewpoint of flame retardancy described later, it is preferable to use graphite having a relatively high apparent density.

(2) Flame retardancy The thermoplastic resin composition of the present embodiment has a flame retardance level of the UL-94 standard of rank V-1 or higher. Specifically, the flame retardancy level can be obtained by performing a combustion test using an injection molded test piece having a thickness of 1.5 mm based on a vertical combustion test defined in UL-UL UL-94. (A) Depending on the type of thermoplastic resin, it can be achieved at a higher level by blending a suitable (C) flame retardant. (C) If a flame retardant is mix | blended in large quantities, the flame retardance of a thermoplastic resin composition can be improved, but coexistence with the above-mentioned heat conductivity is not achieved. In the present embodiment, the thermoplastic resin composition having a further excellent balance between thermal conductivity and flame retardancy by using (B) graphite having a relatively high apparent density and blending a specific amount of (C) flame retardant. It can be a thing.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is preferably obtained by melt-kneading the above-described raw material components with an extruder. The conditions for melt-kneading can be appropriately adjusted depending on the type of raw material components used. The extruder used for melt-kneading is preferably a biaxial extruder that rotates in the opposite direction or rotates in the same direction. The extruder is preferably provided with a device (side feed) capable of adding a material in the middle of the extruder and a vent port capable of vacuum devolatilization, and more preferably provided with a plurality of side feeds and vent ports.

  As a method of blending the raw materials of the resin composition of the present embodiment, the raw materials can be added all at once upstream of the extruder, but the thermoplastic resin is added from the upstream of the extruder, and graphite and inorganic fillers are added. A method of adding a flame retardant from a side feed and a side feed different from graphite and an inorganic filler is preferable. Graphite and the inorganic filler may be added from the same side feed or may be added separately. The side feed position can be appropriately changed according to the addition amount. As described above, the graphite to be used preferably has a high apparent density and preferably has a relatively large particle size. By adding graphite from the side feed, a relatively large particle size of graphite can be maintained even in the composition, and both thermal conductivity and flame retardancy can be achieved. The method of side-feeding the liquid flame retardant is to feed from the injection nozzle to the side of the extruder using a gear pump, a plunger pump or the like. The solid flame retardant is supplied together with other components from the upstream side of the extruder, or side-fed from a supply port provided on the downstream side.

  After the thermoplastic composition resin is melt-kneaded, it is preferable to perform vacuum deaeration for removing volatile components and decomposition products from the molten resin. For vacuum deaeration, it is preferable to provide a decompression vent port and depressurize more strongly than -0.08 MPa. Two or more decompression vents may be installed.

  The barrel set temperature is preferably set to 240 to 330 ° C. More preferably, it is 250-300 degreeC. If the set temperature exceeds 330 ° C., the resin temperature increases and the resin deteriorates. When the set temperature is 240 ° C. or higher, polyphenylene ether is easily melted, so that not only the mechanical properties are improved, but also the torque during extrusion can be lowered. It can be effectively suppressed.

  The temperature of the resin composition extruded from the die outlet is preferably controlled to be less than 380 ° C. When the resin temperature becomes 380 ° C. or higher, problems such as deterioration in mechanical properties and impact resistance after exposure to heat occur due to deterioration and decomposition of the resin. Therefore, the temperature is preferably 360 ° C. or lower, more preferably 350 ° C. or lower. To do. In order to suppress the resin temperature to 380 ° C. or less, the length of the unmelted mixing zone and the melting zone, the screw configuration, the barrel set temperature, and the screw rotation speed are within the scope of the present invention according to the quantity ratio and type of the resin composition. It is necessary to adjust to. When the barrel set temperature is 240 ° C or less, or when the screw rotation speed is lowered and the discharge rate is increased, the polyphenylene ether powder cannot be melted sufficiently, so the extruder is overloaded and stable production is achieved. There are problems that not only can not be produced, but mechanical properties are deteriorated due to generation of unmelted material, and the surface appearance of the molded product is deteriorated.

  The thermoplastic resin composition of the present embodiment can be formed into a molded body by being appropriately molded, and internal parts of electric / electronic relations such as personal computers and mobile phones; internal parts of office equipment such as copying machines and printers; It can be suitably used as an internal part of an audio-visual device such as a TV, a video, a projector, or a stereo; an automobile part used for a chassis of an automobile, and other various exterior materials and industrial articles.

  The present invention will be described in more detail based on examples and the like, but the present invention is not limited to the following examples. Each component used in Examples and Comparative Examples is as follows.

[(A) Thermoplastic resin]
[Polyphenylene ether resin]
(A-1; PPE)
Poly-2,6-dimethyl-1,4-phenylene ether: manufactured by Asahi Kasei Chemicals Corporation, trade name “Zylon S201A”, 30 ° C., reduced viscosity measured with chloroform solution is 0.48 dL / g

[Polystyrene resin]
(A-2; HIPS)
High impact polystyrene: manufactured by PS Japan, trade name “PSJ-polystyrene H9302”

[Polycarbonate resin]
(A-3; PC)
Polycarbonate resin: manufactured by Teijin Chemicals Ltd., trade name “Panlite L-1225WP”, viscosity average molecular weight 22,500
(A-4; ABS)
Acrylonitrile-butadiene-styrene resin: manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “Stylac A4130”

[Polyolefin resin]
(A-5; EP)
Ethylene-α-olefin copolymer: manufactured by Mitsui Chemicals, trade name “Tuffmer P-0680J”, MFR 230 ° C. 0.7 g / 10 min (ASTM D1238), density 870 kg / m ³ (ASTM D1505)

[(B) Graphite]
(B-1)
Scale-like graphite (apparent density 0.53 g / cm ³ , average particle diameter 650 μm), and the apparent density was measured according to the test method described in JIS K7365. For the average particle size, an integrated distribution curve was prepared according to the dry screening test method described in JISK0069, and the value when the integrated percentage was 50% was taken as the average particle size.
Product name “F # 1” manufactured by Nippon Graphite
(B-2)
Scale-like graphite (apparent density 0.39 g / cm ³ , average particle diameter 130 μm)
Product name “F # 2” manufactured by Nippon Graphite
(B-3)
Scale-like graphite (apparent density 0.30 g / cm ³ , average particle diameter 60 μm)
Product name “F # 3” manufactured by Nippon Graphite
(B-4)
Artificial graphite (apparent density 0.80g / cm ³ , average particle size 350μm)
Product name “PAG-60” manufactured by Nippon Graphite Co., Ltd.
(B-5)
Spherical graphite (apparent density 0.55 g / cm ³ , average particle size 50 μm)
Product name "CGC-50", manufactured by Nippon Graphite
(B-6)
Scale-like graphite (apparent density 0.09 g / cm ³ , average particle diameter 5 μm)
Product name "J-CBP", manufactured by Nippon Graphite
(B-7)
Scale-like graphite (apparent density 0.20 g / cm ³ , average particle diameter 19 μm)
Product name “CBP” manufactured by Nippon Graphite
(B-8)
Exfoliated graphite (apparent density 0.10 g / cm ³ , average particle size 20 μm)
Product name “UP-20” manufactured by Nippon Graphite Co., Ltd.

[(C) Flame retardant]
The following phosphate ester flame retardants were used.
(C-1; CR741)
Bisphenol A-based condensed phosphate ester: Daihachi Chemical Co., Ltd., trade name “CR-741”
In the following formula (i), a phosphoric acid ester flame retardant containing n = 1 as a main component (about 85% by area ratio according to liquid chromatography analysis).

(C-2; CR733S)
Resorcinol-based condensed phosphate ester, manufactured by Daihachi Chemical Co., Ltd., trade name “CR-733S”
A phosphate ester flame retardant containing a compound represented by the following formula (ii) as a main component (about 70% by area ratio by liquid chromatography analysis).

(C-3; FP800)
Bifer-based condensed phosphate ester: ADEKA, trade name “ADK STAB FP-800”
In the following formula (iii), a phosphoric acid ester flame retardant containing n = 1 as a main component (about 85% by area ratio according to liquid chromatography analysis).

[(D) Inorganic filler]
(D-1; GFL)
Glass flake: manufactured by Nippon Sheet Glass Co., Ltd., trade name “Fureka REFG-315”, average particle size: 500 μm
(D-2; mica)
Mica: Hayashi Kasei Co., Ltd., trade name “Muscobite Mica MC100”, average particle size: 60 μm

[Characteristic evaluation methods]
The characteristic evaluation of the obtained resin composition was performed by the following methods and conditions.
(Preparation of test piece)
The obtained resin composition pellets were dried at 100 ° C. for 2 hours. Test pieces were prepared from the dried resin composition pellets using an IS-100GN type injection molding machine (cylinder temperature set at 290 ° C. and mold temperature set at 80 ° C.) manufactured by Toshiba Machine Co., Ltd.

(1) Thermal conductivity Using a flat plate of 100 mm × 100 mm × 2.0 mm, the thermal conductivity was measured by the probe method using “QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd. according to JIS R2618.

(2) Flame retardancy (UL-94)
Based on the vertical combustion test defined in UL standard UL-94, a combustion test was performed using a 1.5 mm-thick injection molded test piece. About five test pieces, flame contact was performed twice, 10 times in total, and the average number of seconds and the maximum number of seconds of the flame extinguishing time were measured and ranked as follows.
(Rank)
In a set of five tests, a total of 10 burning times were measured, all burning times were within 10 seconds, the total of 10 burning times was within 50 seconds, and the drop was cotton Those that did not ignite "V-0"; all combustion times were within 30 seconds, the total of 10 combustion times was within 250 seconds, and the dripping material did not ignite cotton "V-1"; any burning time is within 30 seconds, the total of 10 burning times is within 250 seconds, and the dripping material ignited cotton is "V-2"; Those below this evaluation standard were defined as “not ranked”.

(3) Heat-resistant temperature (DTUL)
Using a test piece prepared according to ISO-15103, the heat resistance was evaluated under 1.80 Pa in accordance with ISO-75-2.

(4) Flexural modulus (FM)
Using a test piece prepared according to ISO-15103, the flexural modulus was measured at 2 mm / min according to ISO-178.

(5) Releasability A molded product with a boss with a thickness of 3 mm and an inner diameter of 3.6 mmφ on a 150 mm × 150 mm × 3 mm flat plate is injection-molded, and the quality of mold release from the test piece mold is visually checked. Judged.
Evaluation of quality of releasability was good in three stages: good, normal: Δ, bad: x.

(6) Extrusion stability (feeding and biting)
When the thermoplastic resin was melt-kneaded using an extruder, the feed stability of the side-fed graphite and the biting into the thermoplastic resin were visually evaluated.
Evaluation of quality of extrusion stability Good: ○ Slightly bad: △ Bad: Evaluated in three stages.

(7) High-temperature and high-humidity resistance After performing heat aging for 500 hours in a high-temperature and high-humidity tank set at 85 ° C. and a relative humidity of 85% using a test piece prepared according to ISO-15103, a room temperature of 23 ° C. After leaving for 24 hours at a humidity of 50%, the bending strength was measured in accordance with ISO-178, and the degree of change in bending strength (retention rate with respect to bending strength before aging) was calculated.
The retention was evaluated in three stages: 75% or more: ◯, 50 to 75%: Δ, 50% or less: x.

[Example 1]
Using a twin screw extruder with a screw diameter of 40 mm, a barrel number of 12, a side feeder and a vacuum vent (ZSK40: manufactured by Werner Pfleiderer), each component was melt-kneaded, and the extruded strand was cooled and cut to give a resin composition Pellets were obtained. The operating conditions of the extruder at the time of melt kneading are as follows: the upstream temperature of the heating cylinder is 300 ° C., the downstream temperature is 280 ° C., the screw rotation speed is 300 rpm, the discharge rate is 100 kg / hour, Melt kneaded.
As the composition shown in Table 1, the supply method of each component was as follows.
First, as component (A), 0.3 parts by mass of tris (2,4-di-t-butylphenyl) phosphite as a heat stabilizer is blended with 100 parts by mass of the total amount of thermoplastic resin, and the flow direction of the extruder After supplying from the first supply port on the upstream side, as a component (B), 70 parts by mass of graphite is supplied to the side of the extruder from the second supply port on the downstream side from the first supply port using the side feeder. did. Furthermore, as a component (C), a flame retardant was supplied from an injection nozzle to the side of the extruder from a third (liquid) supply port downstream of the second supply port using a gear pump to obtain resin composition pellets. About the obtained resin composition pellet, it evaluated by the said evaluation method. The evaluation results are shown in Table 1.

[Examples 2 to 7, Reference Examples 3, 4, and 6, Comparative Examples 1 to 5]
Except for the composition shown in Table 1 and Table 2 and the glass flake as the component (D) provided with a fourth supply port between the second supply port and the third supply port and supplied to the side of the extruder using a side feeder. The resin composition pellets were obtained in the same manner as in Example 1 and evaluated. The evaluation results are shown in Tables 1 and 2.

[Example 8]
(C) As a component, except changing the flame retardant into C-2 and supplying from the 3rd supply port, the resin composition pellet was obtained by the method similar to Example 2, and the evaluation was performed. The evaluation results are shown in Table 1.

[Example 9]
(C) As a component, the flame retardant was changed to C-3, and a resin composition pellet was obtained in the same manner as in Example 2 except that the feed position was changed to the first supply port, and the evaluation was performed. . The evaluation results are shown in Table 1.

[Example 10]
(E) Resin composition pellets were obtained in the same manner as in Example 2 except that polyolefin was supplied from the first supply port as a component, and the evaluation was performed. The evaluation results are shown in Table 1.

[Example 11]
As component (D), resin composition pellets were obtained and evaluated in the same manner as in Example 2 except that mica was supplied from the fourth supply port instead of glass flakes. The evaluation results are shown in Table 1.

[Example 12]
(A) Except having used PC and ABS as a component, the resin composition pellet was obtained by the method similar to Example 1, and the evaluation was performed. The evaluation results are shown in Table 1.

[Comparative Example 6]
(C) Except having supplied the graphite of the component from the 1st supply port, the resin composition pellet was obtained by the method similar to Example 3, and the evaluation was performed. The evaluation results are shown in Table 2.

  As shown in Table 1 and Table 2, it was confirmed that the thermoplastic resin composition of the present example was excellent in thermal conductivity and flame retardancy. In particular, it was confirmed that Example 10 was excellent in all of releasability, extrudability, and high temperature and high humidity resistance.

  The thermoplastic resin composition of the present invention has industrial applicability as a material suitable for electrical / electronic related parts, office equipment parts, automobile parts, other various exterior materials, industrial articles, and the like.

Claims (6)

(A) 100 parts by mass of a thermoplastic resin;
(B) 10 to 200 parts by mass of graphite;
(C) 5 to 50 parts by mass of a flame retardant,
(B) the apparent density of the graphite is ^{0.50g / cm 3 ~0.80g / cm 3} , and an average particle diameter of the (B) graphite is 300Myuemu～800myuemu,
A thermoplastic resin composition having a thermal conductivity in accordance with JIS R2618 of 1.0 W / m · K or higher and a flame retardant level of UL-94 standard of Rank V-1 or higher.   From the polymer alloy containing (i) a polyphenylene ether resin, (ii) a polycarbonate resin, or (iii) a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin) as the (A) thermoplastic resin. The thermoplastic resin composition according to claim 1, comprising at least one selected from the group consisting of:   The thermoplastic resin composition according to claim 1 or 2, comprising a polyphenylene ether resin as the (A) thermoplastic resin.   The thermoplastic resin composition according to any one of claims 1 to 3, further comprising 10 to 50 parts by mass of (D) an inorganic filler with respect to 100 parts by mass of the (A) thermoplastic resin. The thermoplastic resin composition according to any one of claims 1 to 4, comprising a compound represented by the following formula (I) or formula (II) as the flame retardant (C).
(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² represent a methyl group, and R ³ and R ⁴ represent Each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 each independently Represents an integer of 0 to 3).   The thermoplastic resin composition according to any one of claims 1 to 5, comprising 50 to 150 parts by mass of the (B) graphite with respect to 100 parts by mass of the (A) thermoplastic resin.