JP2007321138A - Thermoplastic resin composition with high thermal conductivity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic substance-containing thermoplastic resin composition having excellent thermal conductivity while practically retaining various properties inherent in general-purpose resins, such as mechanical properties and moldability. <P>SOLUTION: The resin composition is a polymer alloy comprising a polycarbonate resin, a thermoplastic silicone resin, and a highly thermally conductive inorganic compound. In the polymer alloy, the thermoplastic silicone resin forms a continuous phase, and the highly thermally conductive inorganic compound is present preferentially in phases other than the polycarbonate resin. As a result, by adding a relatively small amount of the highly thermally conductive inorganic compound, the thermal conductivity of the composition can be efficiently improved. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a high thermal conductivity thermoplastic resin composition having both high thermal conductivity and good moldability and also having good practical physical properties such as impact strength.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance and the like, and is widely used for parts in the fields of machinery, automobiles, electricity, and electronics taking advantage of these characteristics. However, there is a drawback that it is inferior in molding processability, chemical resistance and the like. On the other hand, the thermoplastic silicone resin is excellent in mechanical characteristics, electrical characteristics, chemical resistance, molding fluidity, and the like. Therefore, various techniques for alloying a polycarbonate-based resin and a thermoplastic silicone resin have been proposed for the purpose of having both advantages and preserving the drawbacks.

  On the other hand, when resin compositions are used in various applications such as PC and display casings, electronic device materials, and interior and exterior of automobiles, plastics have low thermal conductivity compared to inorganic materials such as metal materials. In order to solve such problems, it is widely attempted to obtain a highly heat conductive resin composition by blending a large amount of highly heat conductive inorganic substance into the resin. Has been made. For example, Patent Document 1 reports a thermally conductive resin composition obtained by blending an inorganic material such as carbon fiber with an alloy of a polycarbonate resin and a polyethylene terephthalate resin.

  When an inorganic substance is blended as described above to obtain a highly thermally conductive resin composition, a method of adding a conductive substance such as carbon fiber is usually used. However, in such a method, since the resin composition exhibits conductivity, its use is limited in applications that require electrical insulation such as electronic device materials. On the other hand, when trying to obtain a highly heat conductive resin composition by a method of adding an electrically insulating and highly heat conductive inorganic material, the high heat conductive inorganic material is usually blended into the resin at a high content of 50% by volume or more. There is a need.

  However, when such a large amount of highly heat-conductive inorganic substance is blended in the thermoplastic resin, the molding processability of the thermoplastic resin is drastically lowered, and it may be difficult to injection mold a complicated shape. In addition, due to a large amount of inorganic material, practical physical properties such as impact strength of the resin are extremely lowered, resulting in a very brittle material. For this reason, there is a problem that application to a large molded article or the like becomes difficult and uses are limited.

In order to solve such a problem, for example, Patent Document 2 discloses that a composite resin composition having a polyamide resin as a sea structure and a polyphenylene ether resin as an island structure is more thermally conductive in a polyamide resin as a sea phase. It is shown that the dispersion density is increased by dispersing the material particles, and a resin composition having more excellent thermal conductivity can be obtained. Patent Document 3 reports a highly thermally conductive material in which thermally conductive powder is selectively dispersed in a flexible block phase of a block copolymer having a flexible phase.
JP 2005-298552 A Japanese Patent Laid-Open No. 9-59511 JP 2004-71385 A

  If a method of obtaining a highly heat conductive resin composition by placing a highly heat conductive inorganic material only in a specific place as described above can be realized with a polycarbonate resin or a thermoplastic silicone resin, the amount of expensive heat conductive inorganic material used can be reduced. However, a high thermal conductivity material having good thermal conductivity can be obtained. As a result, the amount of thermally conductive inorganic materials can be reduced, so that material costs can be kept low, and the mixing process of thermally conductive inorganic materials can be reduced to maintain the molding processability of materials, and complex shapes can be molded. It is possible to obtain a highly electrically insulating and highly heat conductive material, which is very useful.

  In view of the above situation, the present invention is an electrical insulation excellent in thermal conductivity while maintaining excellent properties such as mechanical properties and molding processability inherent in polycarbonate resins and thermoplastic silicone resins without substantially deteriorating. It aims at providing the thermoplastic resin composition containing an inorganic substance.

  The present inventor uses a small amount of a highly heat-conductive inorganic compound in a polymer alloy composed of a polycarbonate-based resin and a thermoplastic silicone resin by preferentially placing the highly heat-conductive inorganic compound in a phase other than the polycarbonate-based resin. Only by this, the thermal conductivity of the resin composition can be greatly improved. In addition, as a result of reducing the amount of the highly heat-conductive inorganic compound added, the present inventors have found that the mechanical properties and molding processability of the obtained composition are hardly sacrificed, and the present invention has been reached.

That is, the present invention comprises a polycarbonate-based resin (A), a thermoplastic silicone resin (B), a high thermal conductivity inorganic compound (C) having a thermal conductivity of 5 W / m · K or more as a simple substance and exhibiting electrical insulation. Become
1) The volume ratio of (A) and (B) is a ratio of 15/85 to 75/25,
2) The volume ratio of (C) / {(A) + (B)} is 10/90 to 75/25,
3): The ratio in which (C) is present in the phase of (A) is (A) volume fraction × 0.4 or less,
4): A high thermal conductive thermoplastic resin composition (Claim 1), wherein at least (B) forms a continuous phase structure.

  The high thermal conductive thermoplastic resin composition according to claim 1, wherein the (C) is a high thermal conductive inorganic compound exhibiting electrical insulation.

  3. The high thermal conductivity according to claim 1, wherein the (C) is a metal oxide fine particle and / or a metal nitride fine particle having a volume average particle diameter of 1 nm or more and 12 μm or less. Thermoplastic resin composition (Claim 3).

  The said (C) contains at least 1 sort (s) chosen from boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, beryllium oxide, The any one of Claims 1-3 characterized by the above-mentioned. A high thermal conductive thermoplastic resin composition (claim 4).

The thermoplastic silicone resin (B) has an average composition formula (1)
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(Wherein R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R Each of ² may be present in two or more types, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.05 ≦ n / m ≦ 10. The high thermal conductivity thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin composition is characterized in that (Claim 5). It is.

  By using the method of the present invention, it is possible to greatly reduce the amount of inorganic compound used in the field of high thermal conductive resin compositions, which conventionally required a large amount of high thermal conductive inorganic compound. A highly thermally conductive resin composition can be obtained at low cost without sacrificing the inherent properties.

  The composite materials obtained in this way are in various forms such as resin films, resin molded products, resin foams, paints and coating agents, electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, etc. It can be widely used for various applications such as materials, automobile materials, and building materials. The polymer material obtained in the present invention can be used for general plastic molding machines such as injection molding machines and extrusion molding machines that are widely used at present, and can be molded into products having complicated shapes. Easy. In particular, it has an excellent balance of important properties such as moldability, impact resistance, chemical resistance, and thermal conductivity, so it is extremely useful as a housing resin for displays and computers that have a heat source inside. Useful for.

The thermoplastic resin composition of the present invention essentially comprises three components: a polycarbonate-based resin (A), a thermoplastic silicone resin (B), and a highly thermally conductive inorganic compound (C).
The polycarbonate resin (A) to be blended in the thermoplastic resin composition of the present invention is a polycarbonate obtained by polymerizing a divalent or higher valent phenol compound and phosgene or a carbonic acid diester by a known method.

  The divalent phenol compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A], bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenyl Methane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4 -Hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ) Ethane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis 3,5-dimethyl-4-hydroxyphenyl) propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4 -Methyl-2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4- Hydroxyphenyl) nonane, 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -3,3,5-tri Dihydroxydiarylalkanes such as tilcyclohexane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone Dihydroxydiaryl sulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; dihydroxydiaryl ethers such as bis (4-hydroxyphenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether Dihydroxydiaryl ketones such as 4,4′-dihydroxybenzophenone and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3 -Dihydroxydiaryl sulfides such as methyl-4-hydroxyphenyl) sulfide and bis (3,5-dimethyl-4-hydroxyphenyl) sulfide; Dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide; Dihydroxy diphenyls such as dihydroxydiphenyl; dihydroxyaryl fluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone; 1,5-dihydroxynaphthalene, 2, Dihydroxynaphthalene such as 6-dihydroxynaphthalene; and the like. These may be used alone or in combination of two or more.

  Of these, bisphenol A is preferred. The carbonic acid diester is not particularly limited, and examples thereof include diaryl carbonates such as diphenyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; These may be used alone or in combination of two or more.

  The polycarbonate resin (A) is not limited to a linear polycarbonate, and may be a branched polycarbonate. The branching agent used for obtaining this branched polycarbonate is not particularly limited.

  Specifically, for example, phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β Resorcinic acid, resorcinaldehyde, isatin bis (o-cresol), benzophenone tetracarboxylic acid, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,4' -Trihydroxyphenyl ether, 2,2 ', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl-2-propane, 2,2'-bis (2,4-dihydroxyphenyl) Propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2 , 4,4′-trihydroxydiphenylmethane, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -3- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, α, α ′, α ″ -tris ( 4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-2,4,6- Tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptane, 1,3,5-tris (4'-hydroxyphenyl) Ben Zen, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2'-hydroxy-) 5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2 '-Hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2', 4 ', 7-trihydroxyflavan, 2 , 4,4-trimethyl-2 ', 4', 7-trihydroxyflavan, 1,3-bis (2 ', 4'-dihydroxyphenyl) Sulfonyl) benzene, tris (4'-hydroxyphenyl) - amyl -s- triazine.

In some cases, the polycarbonate-based resin (A) may be a polycarbonate-polyorganosiloxane copolymer composed of a polycarbonate portion and a polyorganosiloxane portion. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.
Further, the polycarbonate resin (A) is obtained by copolymerizing a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. It may be a coalescence.

  As a terminal stopper used when polymerizing the polycarbonate resin (A), various known ones can be used. Specific examples include monohydric phenols such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, and nonylphenol.

  When flame retardancy is required, the polycarbonate resin (A) may be a polycarbonate copolymer with a phosphorus compound, or may be a polycarbonate resin end-capped with a phosphorus compound. Good. Moreover, in order to improve a weather resistance, the polycarbonate-type copolymer with the bihydric phenol which has a benzotriazole group may be sufficient.

  The viscosity average molecular weight of the polycarbonate resin (A) blended in the thermoplastic resin composition of the present invention is preferably 10,000 to 60,000. When it is less than 10,000, the strength, heat resistance, etc. of the resulting resin composition are often insufficient. On the other hand, if it exceeds 60000, the moldability is often insufficient. More preferably, it is 15000-45000, More preferably, it is 18000-35000.

  In the thermoplastic resin composition of the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. For example, different monomer units, different copolymer molar ratios, different molecular weights, and the like can be arbitrarily combined.

The thermoplastic silicone resin as component (B) of the present invention comprises an aromatic group-containing organosiloxane compound, and is composed of Q unit (SiO ₂ ), T unit (RSiO _1.5 ), D unit (R ₂ SiO) and M unit ( R ₃ SiO _0.5 ) is used which is composed of an arbitrary combination of the four types of structural units and exhibits thermoplasticity.

  The component soluble in methyl isobutyl ketone at 23 ° C. is preferably 80% by weight or more, and the number average molecular weight of this soluble component is preferably 1500 or more, more preferably 85% by weight or more. The number average molecular weight of the soluble component is 2000 or more. If an insoluble component exceeding 20% by weight is contained or the number average molecular weight is less than 1500, the dispersion state necessary for obtaining the effects of the present invention may not be obtained.

Among these, the average composition formula (1)
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(Wherein R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R Each of ² may be present in two or more types, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.05 ≦ n / m ≦ 10. It is preferable.

The thermoplastic silicone resin represented by the average composition formula (1) has a monovalent aliphatic hydrocarbon group R ¹ having 1 to 4 carbon atoms and a monovalent aromatic carbon atom having 6 to 24 carbon atoms in the molecule. Having both hydrogen groups R ² , the molar ratio m + n of all hydrocarbon groups to the number of Si atoms is 1.1 ≦ m + n ≦ 1.7, monovalent aliphatic having 1 to 4 carbon atoms The molar ratio n / m between the hydrocarbon group R ¹ and the monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms satisfies 0.05 ≦ n / m ≦ 10. The ratio of each element and each hydrocarbon group can be calculated using NMR of hydrogen, carbon, and silicon.

The aliphatic hydrocarbon group R ¹ having 1 to 4 carbon atoms is not particularly limited. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, t -A butyl group etc. are illustrated. Among these, a methyl group and an ethyl group are preferred because of their excellent flame retarding effect, and a methyl group is more preferred. The plurality of R1 may all be the same or different groups may be mixed. If the aliphatic hydrocarbon group has 5 or more carbon atoms, the flame retardancy of the aromatic group-containing organosiloxane compound itself tends to decrease, and the flame retarding effect tends to be reduced.

The monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a naphthyl group, and an anthracenyl group. Is done. Among these, an aromatic group having no substituent on the aromatic ring is preferable because of its excellent flame retarding effect, and a phenyl group is more preferable. The plurality of R ² may be all the same or different groups may be mixed.

  The molar ratio m + n between the total hydrocarbon groups and the number of Si atoms is in the range of 1.1 ≦ m + n ≦ 1.7. The value of m + n is preferably in the range of 1.15 ≦ m + n ≦ 1.65, more preferably 1.18 ≦ m + n ≦ 1.6, and even more preferably 1.20 ≦ m + n ≦ 1.55. Even if the value of m + n is less than 1.1 or above 1.7, the flame retarding effect of the aromatic group-containing organosiloxane compound is lowered, which is not preferable. Construction of the structure in the above range can be achieved by introducing T units and / or Q units into the skeleton of the organosiloxane compound. In general, the above range is easily achieved as the amount of introduction of these units increases. it can. The total amount of T unit and Q unit introduced is preferably 20 mol% or more, more preferably 25 mol% or more, and most preferably 30 mol% or more in all Si atoms.

The molar ratio n / m between the monovalent aliphatic hydrocarbon group R ¹ having ¹ to 4 carbon atoms and the monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is 0.05 ≦ n / m. It is preferable that m ≦ 10. When n / m is less than 0.05, the monovalent aliphatic hydrocarbon group R ¹ increases in the molecule. At this time, the compatibility between the thermoplastic silicone resin and the polycarbonate resin decreases, Cause phase separation and the like. On the other hand, even if n / m is 10 or more, the compatibility between the thermoplastic silicone resin and the polycarbonate resin is reduced. The value of n / m is preferably 0.1 ≦ n / m ≦ 7, more preferably 0.12 ≦ n / m ≦ 4, and further preferably 0.15 ≦ n / m ≦ 2.

Such a thermoplastic silicone resin can be easily synthesized by a known silicone synthesis method. That is, a monofunctional silicon compound represented by R ₃ SiX, a bifunctional silicon compound represented by R ₂ SiX ₂ , a trifunctional silicon compound represented by RSiX ₃ , silicon tetrahalide, tetraalkoxysilane, And a condensation reaction of at least one, preferably at least two silicon compounds selected as necessary from organic silicon compounds which are condensates thereof and inorganic silicon compounds such as water glass and metal silicates. Can be synthesized. In the formula, R represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group. X represents a group that can be condensed to form a siloxane bond, such as a halogen, a hydroxyl group, or an alkoxy group.

  The reaction conditions vary depending on the substrate used and the composition and molecular weight of the target compound. In general, the reaction can be carried out by mixing the silicon compound with heating, if necessary, in the presence of water, an acid and / or an organic solvent as necessary. The proportion of each silicon compound used should be appropriately set in consideration of the content of each unit and the ratio of aromatic hydrocarbon groups to aliphatic hydrocarbon groups so that the resulting aromatic group-containing organosiloxane compound satisfies the above conditions. That's fine.

  Further, (B) the thermoplastic silicone resin may have one or more silanol groups or alkoxy groups in the molecule as necessary. By having such a functional group in the molecule, the highly thermally conductive inorganic compound (C) can be more easily present in the thermoplastic silicone resin (B). Moreover, depending on the case, it can also have functional groups, such as an epoxy group, a vinyl group, an acryl group, a methacryl group, in a molecule | numerator. In the thermoplastic resin composition of the present invention, the thermoplastic silicone resin (B) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited and can be arbitrarily combined.

In the thermoplastic resin composition of the present invention, the ratio [(A) / (B)] of the polycarbonate resin (A) and the thermoplastic silicone resin (B) is 15/85 to 75/25 by volume ratio. is there. If it is less than 15/85, the dimensional stability, impact resistance and the like tend to decrease, and if it exceeds 75/25, the thermal stability and solvent resistance of the resulting molded product tend to decrease.
The mixing ratio [(A) / (B)] of the polycarbonate resin (A) and the thermoplastic silicone resin (B) is such that at least the thermoplastic silicone resin (B) is continuous in the microphase separation structure in the resin composition. It is necessary to form a phase structure. And each ratio should just be determined so that the polycarbonate-type resin (A) which is another resin component may form an island structure or a substantially continuous phase structure.

  By having such a phase structure, highly thermally conductive inorganic compounds dispersed in a large amount in the thermoplastic silicone resin are in contact with each other to transmit heat, thereby improving the thermal conductivity of the entire composition. Become. The upper limit of the volume ratio required to realize such a structure is 75/25, preferably 70/30, more preferably 65/35, still more preferably 60/40, Preferably it is 55/45. On the other hand, the lower limit of the volume ratio is 15/85, but from the viewpoint of dimensional stability and impact resistance, it is more preferably 20/80, further preferably 25/75, and most preferably 30/70. is there. In addition, when A and B components are compared as in 30/70 to 49/51, it is preferable that the ratio of the B component is large because the effect of improving the thermal conductivity is good.

  Most of the high thermal conductive inorganic compound (C) is present in the phase of the thermoplastic silicone resin (B). Therefore, when the obtained composition is observed with an electron microscope or the like, the thermoplastic silicone resin (B) appears to occupy a larger proportion than the mixing ratio in the obtained photograph. For example, when mixing at a volume ratio of (A) / (B) / (C) = 35/35/30 and (C) component is all present in the (B) component, the apparent volume ratio is ( A) / {(B) + (C)} = 35/65.

  However, the ratio [(A) / (B)] between the polycarbonate resin (A) and the thermoplastic silicone resin (B) referred to in this patent is a volume ratio excluding the component (C). Even in this case, it is defined that [(A) / (B)] = 50/50. Therefore, the volume ratio of [(A) / (B)] is almost the same as the mixing ratio of both resins.

  Preferably, the polycarbonate resin (A) which is another resin component also forms a continuous phase structure and forms a mutual continuous phase structure together with the thermoplastic silicone resin (B). By forming such a phase structure, an effect of improving the impact strength of the obtained resin composition can be obtained.

  As the high thermal conductivity inorganic compound (C) to be blended in the thermoplastic resin composition of the present invention, one having a single thermal conductivity of 1.5 W / m · K or more can be used. Less than 1.5 W / m · K is not preferable because the effect of improving the thermal conductivity of the composition is inferior. The thermal conductivity of the single substance is preferably 4 W / m · K or more, more preferably 9 W / m · K or more, most preferably 20 W / m · K or more, particularly preferably 30 W / m · K or more. It is done. The upper limit of the thermal conductivity of the high thermal conductivity inorganic compound (C) alone is not particularly limited, and it is preferably as high as possible. Generally, it is 2000 W / m · K or less, more preferably 1500 W / m · K or less. Is preferably used.

  As the high thermal conductive inorganic compound (C), various well-known inorganic compounds can be used. For example, metals such as gold, silver, copper, aluminum, iron, magnesium, nickel, and alloys of these metals, metals such as aluminum oxide, magnesium oxide, silicon oxide, zinc oxide, beryllium oxide, copper oxide, cuprous oxide, etc. Examples thereof include metal nitrides such as oxide, boron nitride, aluminum nitride, and silicon nitride, metal carbides such as silicon carbide, carbon materials such as carbon, graphite, and diamond.

  However, among these various exemplified high thermal conductivity inorganic compounds, it is necessary to select and use those which are more dispersed in the thermoplastic silicone resin (B) and are less likely to be dispersed in the polycarbonate resin (A). These inorganic compounds may be natural products or synthesized ones. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate.

On the other hand, when these high thermal conductive resin compositions are used for electronic devices, electrical insulation is often required. In order to use the resin composition of the present invention for such applications, a compound exhibiting electrical insulation is used as the highly thermally conductive inorganic compound (C). Specifically, the electrical insulating property indicates an electrical resistivity of 1 Ω · cm or more, preferably 10 Ω · cm or more, more preferably 10 ⁵ Ω · cm or more, and further preferably 10 ¹⁰ Ω · cm or more. It is preferable to use a material having a size of cm or more, most preferably 10 ¹² Ω · cm or more. The upper limit of the electrical resistivity is not particularly limited, but is generally 10 ¹⁸ Ω · cm or less. It is preferable that the electrical insulation of the molded product obtained from the high thermal conductivity thermoplastic resin composition of the present invention is also in the above range.

  Specifically, metal oxides such as aluminum oxide, magnesium oxide, silicon oxide, zinc oxide, beryllium oxide, copper oxide, and cuprous oxide, metal nitrides such as boron nitride, aluminum nitride, and silicon nitride, silicon carbide Metal carbides such as can be preferably used.

  Among these, metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, copper oxide, and cuprous oxide, and metal nitrides such as boron nitride, aluminum nitride, and silicon nitride are more preferably used because of excellent electrical insulation. be able to. These can be used alone or in combination. Of these metal oxides and metal nitrides, characteristics as a semiconductor may be exhibited depending on the type of metal, but even in that case, it is preferable to select a metal having the lowest electrical conductivity.

  About the shape of a highly heat conductive inorganic compound (C), the thing of a various shape is applicable. For example, particles, fine particles, nanoparticles, aggregated particles, tubes, nanotubes, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined Various shapes such as a complex particle shape and a liquid can be exemplified.

  However, in order to efficiently mix these highly heat-conductive inorganic compounds with the resin, it is preferable to use fine particles having a nearly spherical shape or a liquid compound. In particular, when metal oxide fine particles and / or metal nitride fine particles having a volume average particle diameter of 1 nm or more and 12 μm or less are used, the high thermal conductive inorganic compound (C) has a phase structure size of the thermoplastic silicone resin (B). Since it becomes small in comparison, the high thermal conductive inorganic compound (C) can be preferentially present in the phase of the thermoplastic silicone resin (B), which is preferable. Moreover, by setting it as such a size, the melt-kneading operation | work of a resin composition and a highly heat conductive inorganic compound can be implemented easily.

  When the volume average particle diameter exceeds 12 μm, the appearance of the resulting molded product tends to be impaired, the impact strength of the resin composition tends to decrease, and the particle size is the phase of the thermoplastic silicone resin (B). Since it becomes large compared with the size of the structure, it tends to be difficult to make the particles selectively exist in the thermoplastic silicone resin (B). Further, when the volume average particle diameter is less than 1 nm, the surface area of the inorganic compound becomes enormous, so that the thermal resistance on the surface of the inorganic compound increases and the thermal conductivity tends to decrease.

  The volume average particle diameter is preferably 5 nm to 11 μm, more preferably 20 nm to 10 μm, particularly preferably 40 nm to 8 μm, and most preferably 100 nm to 6 μm. The volume average particle diameter in the present invention refers to the diameter of the circle after observing the appearance of the powder with an electron microscope or an optical microscope, and when the observed appearance is not circular, it is converted to a circle with the same area. Is defined by the value measured by the method of measuring the volume average.

  When adding these highly heat-conductive inorganic compounds (C), the surface is treated with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion at the interface between the resin and the inorganic compound or to facilitate workability. It may have been processed. It does not specifically limit as a surface treating agent, For example, conventionally well-known things, such as a silane coupling agent and a titanate coupling agent, can be used.

  Among them, silane coupling agents are preferable, specifically, unsaturated bond-containing silane coupling agents such as methacryloxysilane, acryloxysilane, vinylsilane, styrylsilane, chlorosilane, ureidosilane, mercaptosilane, sulfide silane, isocyanate silane, Epoxy silanes, amino silanes, and polyoxyethylene silanes are preferable because they hardly reduce the physical properties of the resin. The surface treatment method of the inorganic compound is not particularly limited, and a normal treatment method can be used.

  These high heat conductive inorganic compounds (C) may be used alone or in combination of two or more different in average particle diameter, type, surface treatment agent and the like.

  The amount of the high thermal conductive inorganic compound (C) used in the thermoplastic resin composition of the present invention is (C) / {relative to the total of the two components of the polycarbonate resin (A) and the thermoplastic silicone resin (B). It is necessary to contain so that the volume ratio of (A) + (B)} is 10/90 to 75/25. If the volume ratio is less than 10/90, the effect of improving thermal conductivity is inferior, which is not preferable. The lower limit of the volume ratio is preferably 15/85 or more, more preferably 20/80 or more, and most preferably 23/77 or more.

  On the other hand, when the volume ratio is more than 75/25, the impact resistance, surface property and molding processability of the obtained molded product are lowered, and kneading with a resin during melt kneading tends to be difficult. The upper limit of the volume ratio is preferably 72/28 or less, more preferably 69/31 or less, still more preferably 67/33 or less, and most preferably 65/35 or less.

  In the thermoplastic resin composition of the present invention, the ratio of the total volume of the high thermal conductivity inorganic compound (C) in the phase of the (A) polycarbonate resin is {volume of (A)} / It is necessary that {volume of (A) + volume of (B)} × 0.4 or less. As a result, the thermal conductivity of the obtained thermoplastic resin composition is efficiently increased. As a result, the thermal conductivity of the entire composition can be increased by adding a small amount of a high thermal conductivity inorganic compound, and mechanical properties can be obtained. And various properties such as moldability can be maintained with almost no deterioration.

  Especially, the ratio which exists in the phase of (A) polycarbonate-type resin among the total volume of an inorganic compound (C) is {volume of (A)} / {volume of (A) + (B). Volume} × 0.3 or less is preferable.

  More preferably, the ratio of the total volume of the inorganic compound (C) present in the phase of the (A) polycarbonate resin is (A) volume / {(A) volume + (B) volume. } × 0.25 or less. Most preferably, the ratio of the total volume of the inorganic compound (C) present in the phase (A) is {volume of (A)} / {volume of (A) + volume of (B)}. × 0.2 or less. The smaller the proportion of the inorganic compound (C) present in the polycarbonate resin phase, the more efficiently the thermal conductivity of the composition can be improved with a small amount of highly thermally conductive inorganic material.

  The measurement of the abundance ratio of the high thermal conductive inorganic compound (C) is carried out by observing a cut product obtained by cutting the thermoplastic resin composition of the present invention with a transmission electron microscope, and measuring the total volume of the inorganic compound (C) found in the visual field , And the volume of the highly heat-conductive inorganic compound (C) present in the polycarbonate-based resin phase, respectively (where the polycarbonate-based resin phase and the other phases are an electron microscope) Can be identified).

  At this time, if there is a high thermal conductive inorganic compound (C) in the vicinity of the interface between the polycarbonate resin (A) and the other resin, the polycarbonate resin (A) and the other resin are present. The high thermal conductivity inorganic compound (C) exists by setting the apparent interface between the two by smoothly extending the interface with the resin to the location where the high thermal conductivity inorganic compound (C) exists. The ratio shall be calculated.

  In order to further increase the heat resistance and mechanical strength of the resin composition, the thermoplastic resin composition of the present invention is further added with an inorganic compound other than the high thermal conductivity inorganic compound (C) within a range not impairing the characteristics of the present invention. can do. Such a reinforcing filler is not particularly limited. However, since the addition of these inorganic compounds may affect the thermal conductivity and insulation, the addition amount may be determined according to the desired characteristics such as thermal conductivity.

  These inorganic compounds may also be surface treated. When these reinforcing fillers are used, the addition amount can be exemplified as a preferable amount of 100 weight parts or less with respect to a total of 100 weight parts of the polycarbonate resin (A) and the thermoplastic silicone resin (B). When the addition amount exceeds 100 parts by weight, impact resistance is lowered, and molding processability and flame retardancy may be lowered. Preferably it is 50 weight part or less, More preferably, it is 10 weight part or less. In addition, as the addition amount of these reinforcing fillers increases and the surface properties and dimensional stability of the molded product tend to deteriorate, when these characteristics are emphasized, the addition amount of the reinforcing filler is reduced. It is preferable to reduce as much as possible.

  To the thermoplastic resin composition of the present invention, a thermoplastic resin or a thermosetting resin other than the component (A) or the component (B) may be further added as long as the object of the present invention is not impaired. Such optional resin is not particularly limited, and for example, polyolefin resin, polyamide resin, polystyrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, thermoplastic polyester resin Resins; Fluorinated polyolefin resins such as polytetrafluoroethylene are listed. These may be used alone or in combination of two or more.

  When these optional resin components are added, the inorganic compound (C) may be present in these optional resin components in the thermoplastic resin composition of the present invention.

  Further, in order to make the thermoplastic resin composition of the present invention have higher performance, an antioxidant such as a phenolic antioxidant and a thioether antioxidant; a thermal stabilizer such as a phosphorus stabilizer, etc. Or it is preferable to add 2 or more types in combination. Furthermore, as required, generally well-known stabilizers, lubricants, mold release agents, plasticizers, flame retardants other than phosphorus, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, charging An inhibitor, a conductivity imparting agent, a dispersant, a compatibilizing agent, an antibacterial agent and the like may be added alone or in combination of two or more.

  It does not specifically limit as a manufacturing method of the thermoplastic resin composition of this invention. For example, it can be produced by drying the above-described components, additives and the like and then melt-kneading them in a melt-kneader such as a single-screw or twin-screw extruder. Moreover, when a compounding component is a liquid, it can also manufacture by adding to a melt-kneader on the way using a liquid supply pump etc.

  As a preferred production method, in producing the thermoplastic resin composition of the present invention in a kneading apparatus, a first supply port provided at the root of the kneading apparatus, a second supply port provided downstream of the first supply port, and Using a kneading device provided with at least a vent port provided at a position closer to the second supply port between the first supply port and the second supply port and opened to atmospheric pressure. 30% by weight or more of the addition amount of the high thermal conductivity inorganic compound (C) among the raw materials is supplied from the second supply port, while the remaining raw materials are supplied from the first supply port. .

  The production method of the present invention can typically be performed using, for example, the apparatus shown in FIG. In FIG. 1, when the component (A), the component (B), and the component (C) of 70% by weight or less are charged into the first supply port 1, the charged raw material is conveyed downstream in the kneading apparatus. Kneaded and moved. Preferably, 30% by weight or more of the component (C) is supplied from the second supply port 3. It is preferable that the vent port 2 is provided between the first supply port 1 and the second supply port 3 at a position close to the second supply port 3 and is opened to the atmospheric pressure. The raw material is conveyed downstream while being kneaded and taken out from the take-out port 5.

  By using such a production method, the high thermal conductive inorganic compound (C) is contained in the polycarbonate resin phase while sufficiently kneading the polycarbonate resin (A) and the thermoplastic silicone resin (B). Since it becomes difficult to enter, the thermoplastic resin composition having the dispersed state of the high thermal conductive inorganic compound (C) as described above can be easily produced. In particular, when supplying all of the high thermal conductivity inorganic compound (C) from the same supply port as the component (A) and the component (B), or supplying the high thermal conductivity inorganic compound (C) from the second supply port. Even if it does not use the vent port open | released by atmospheric pressure, dispersion | distribution control within the resin phase of a highly heat conductive inorganic compound (C) can be performed easily.

  In this production method, the amount of the highly thermally conductive inorganic compound (C) supplied from the second supply port is preferably 30% by weight or more of the total amount of the highly thermally conductive inorganic compound (C), more preferably It is 50 weight% or more, More preferably, it is 70 weight% or more. The total addition amount of the inorganic compound (C) can also be supplied from the second supply port.

  In the kneading apparatus, the position of the vent port 2 opened to atmospheric pressure is preferably a position closer to the second supply port 3 between the first supply port 1 and the second supply port 3. Further, a vent port 4 having a reduced pressure can be further provided downstream from the second supply port 3.

  The kneading apparatus used in the production method of the present invention is not particularly limited, and a known kneading apparatus can be used. Specific examples include a same-direction meshing twin screw extruder. Especially, in order to fully knead | mix knead | mixing a polycarbonate-type resin (A) and a thermoplastic silicone resin (B), a twin-screw extruder is preferable. It does not specifically limit as a twin-screw extruder, A conventionally well-known thing can be used.

  The rotation of the screw may be in the same direction or in the opposite direction. This twin-screw extruder has a structure for retaining the resin between the first supply port 1 and the second supply port 3, such as a kneading disk or a reverse screw structure, and a narrow space between the screw and the wall surface. What it has is more preferable. You may provide the vent port 2 open | released by atmospheric pressure in the immediately downstream part of the structure which makes such resin retain.

In the production method of the present invention, the screw rotation speed of the kneading apparatus is generally 20 to 2000 rpm. The set temperature is generally appropriately set in the range from room temperature to 300 ° C. in the section from the first supply port to the second supply port, and is 250 to 300 ° C. after the second supply port. The residence time of the resin in the kneading apparatus is not particularly limited, but may be about 0.5 to 15 minutes.
The method for molding the thermoplastic resin composition of the present invention is not particularly limited. For example, a molding method generally used for thermoplastic resins, such as injection molding, blow molding, extrusion molding, vacuum molding, press molding, Calendar molding can be used.

  The present invention preferentially arranges a highly heat-conductive inorganic compound in one phase of a polymer alloy having a specific phase structure, so that even if the amount of the high heat-conductive inorganic compound is small, The thermal conductivity can be improved efficiently. With this technology, high heat conductive resin compositions that have been limited in fields of use due to their inferior moldability and impact resistance and are expensive can now be applied to various fields. It was.

Moreover, the resin composition obtained by this invention is highly heat conductive, and also has insulation. Conventional high heat conductive materials have conductivity, so the range of use is limited for electronic materials. However, the present invention has succeeded in solving such problems at the same time.
The high thermal conductive resin composition of the present invention can be suitably used for injection molded products such as home appliances, OA equipment parts, AV equipment parts, automobile interior and exterior parts, and the like. In particular, it can be suitably used as an exterior material in home appliances and office automation equipment that generate a lot of heat.

  Furthermore, in an electronic device having a heat source inside but difficult to be forcibly cooled by a fan or the like, it is suitably used as an exterior material for these devices in order to dissipate the heat generated inside to the outside. Among these, small or portable electronic devices such as portable computers such as notebook computers, PDAs, cellular phones, portable game machines, portable music players, portable TV / video devices, portable video cameras, and the like are preferable devices. It is very useful as a resin for housings, housings, and exterior materials.

In addition, taking advantage of the properties of resin with both insulation and thermal conductivity, it is very useful as a resin for battery peripherals in automobiles, trains, etc., as a resin for portable batteries in household appliances, and as a resin for power distribution parts such as breakers. Can do.
In addition, the high thermal conductive resin composition of the present invention has better molding processability, impact resistance, and surface properties of the resulting molded body than the conventional inorganic compounded composition, and the components or It has characteristics useful for a housing.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Reference Production Example 1): Production of thermoplastic silicone resin (SI-1) Dichlorodiphenylsilane (4.68 kg), dichlorodimethylsilane (0.8 kg), M silicate 51 (2.91 kg) manufactured by Tama Chemical Industry Co., Ltd. After weighing into a 50 L reaction vessel and adding MIBK (12 kg), water (3.36 kg) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. After returning to room temperature, chlorotrimethylsilane (2.68 kg) and then water (0.44 kg) were added dropwise, followed by reaction at 60 ° C. for 3 hours.

The obtained reaction mixture was washed with water until neutral, and the separated organic phase was evaporated under reduced pressure to obtain the desired thermoplastic silicone resin (SI-1). From NMR analysis, R ¹ represented by the average composition formula (1) is a methyl group, R ² is a phenyl group, and the constituent ratios are m = 0.74 and n = 0.56, and therefore m + n = 1. 30 and n / m = 0.76.

(Reference Production Example 2): Production of thermoplastic silicone resin (SI-2) Methyltrichlorosilane (6.37 kg), phenyltrichlorosilane (2.50 kg), and methyl isobutyl ketone 25 L as a solvent were weighed in a 50 L reaction vessel, Pure water (1.04 kg) was gradually added over 4 hours while adjusting the internal temperature to the range of 0 to 10 ° C. After completion of the addition, trimethylchlorosilane (3.21 kg) was added dropwise, and then stirred at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until neutrality, and the target organic silicone resin (SI-2) was obtained by distilling off the solvent of the separated organic phase under reduced pressure. From the NMR analysis, R ¹ represented by the average composition formula (1) is a methyl group, R ² is a phenyl group, and the constituent ratios are m = 1.10 and n = 0.19. Therefore, m + n = 1 29, n / m = 0.17.

Example 1
As the polycarbonate resin (A), Teflon A-2200 (PC-1), which is a polycarbonate resin made by Idemitsu Kosan Co., Ltd., is used as the thermoplastic silicone resin (B). Using SI-1), both were mixed so that the volume ratio was (A) / (B) = 50/50. As a stabilizer, 0.2 parts by weight of Adeka Stub AO-60 and Adeka Stub HP-10 (both trade names manufactured by Asahi Denka) were mixed in a super floater with respect to 100 parts by weight of both (raw material 1)).

Separately, aluminum oxide powder (ASFP-20 manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity 35 W / m · K alone, volume average particle size 200 nm, electrical insulation, volume resistivity as high thermal conductivity inorganic compound (C) 10 ¹⁶ Ω · cm) (FIL-1) 100 parts by weight, Shin-Etsu Chemical's epoxy silane KBM-303 5 parts by weight, ethanol 10 parts by weight were mixed with a super floater and stirred for 5 minutes. Dried at 4 ° C. for 4 hours (raw material 2)).

  The raw material 1) was charged from a hopper which is a first supply port provided in the vicinity of the screw base of a TEX44 same-direction meshing twin screw extruder manufactured by Nippon Steel Works. A kneading disc having an angle of 90 ° C. was inserted into the screw at a position before the second supply port, and a vent port opened to atmospheric pressure was provided at a position where the kneading disc portion was completed. A side feeder was installed right next to the vent port, and the raw material 2) was forcibly injected from the second supply port with the side feeder. The ratio of the high thermal conductive inorganic compound (C) to the total of the polycarbonate resin (A) and the thermoplastic silicone resin (B) is (C) / {(A) + (B)} volume ratio = 40 / 60 was set.

  A decompression vent port connected to a decompression pump was provided at an intermediate portion between the second supply port and the screw tip. The screw rotation speed was set to 150 rpm and the discharge amount per hour was set to 20 kg / hr. The set temperature was 100 ° C. in the vicinity of the first supply port, and the set temperature was sequentially increased, and the front of the kneading disk was set to 270 ° C. The temperature from the kneading disk part to the atmospheric pressure release vent port was set to 270 ° C., the pressure from the atmospheric pressure release vent port to the second supply port was set to 265 ° C., and the distance from the second supply port to the screw tip was set to 260 ° C. Sample pellets for evaluation were obtained under these conditions.

(Examples 2-7, Comparative Examples 1-5)
Sample pellets for evaluation were obtained in the same manner as in Example 1 except that the type and amount of the resin used were changed as shown in Table 1. In Comparative Example 5, the raw material is not charged from the second supply port. The raw materials used in Examples and Comparative Examples are as follows.

Polycarbonate resin (A)
(PC-1): Toughlon A-2200 (made by Idemitsu Kosan Co., Ltd.)
(PC-2): Toughlon FN-2500A (manufactured by Idemitsu Kosan Co., Ltd.)
Bisphenol A type polycarbonate resin thermoplastic silicone resin (B) having a viscosity average molecular weight of 25000
(SI-1): Thermoplastic silicone resin produced in Reference Production Example 1 (SI-2): Thermoplastic silicone resin produced in Reference Production Example 2.

High thermal conductivity inorganic compound (C)
(FIL-1) Aluminum oxide powder (ASFP-20 manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity of 35 W / m · K alone, volume average particle diameter of 200 nm, electrical insulation, volume resistivity of 10 ¹⁶ Ω · cm )
(FIL-2): Aluminum oxide powder (DAW-05, manufactured by Denki Kagaku Kogyo Co., Ltd., single body thermal conductivity 36 W / m · K, volume average particle diameter 5.0 μm, specific gravity 4.0, electrical insulation , Volume resistivity 10 ¹⁶ Ω · cm)
(FIL-3): Boron nitride powder (HP-P1 manufactured by Mizushima Alloy Iron Co., Ltd., single body thermal conductivity 60 W / m · K, volume average particle diameter 2.0 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm)
(FIL-4): Aluminum nitride powder (H grade manufactured by Tokuyama Corporation, single body thermal conductivity 170 W / m · K, volume average particle diameter 1.1 μm, electrical insulation, volume resistivity 10 ¹² Ω · cm ).
(FIL-5): Silicon nitride powder (SN-E10 manufactured by Ube Industries, Ltd., single body thermal conductivity 50 W / m · K, volume average particle diameter 500 nm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm ).

[Molding processability] Using the obtained pellets, using a capillary rheometer manufactured by Toyo Seiki, melt viscosity was adjusted under the conditions of a set temperature of 280 ° C, a preheating time of 5 minutes, a capillary size of 1 mmφ x 10 mm, and a shear rate of 608 sec ^-1. It was measured.

  [Measurement of abundance ratio of highly heat-conductive inorganic compound (C), confirmation of continuous phase structure] The obtained pellet having a diameter of about 3.6 mm was cut at the center, and an ultrathin section was prepared at the center of the pellet, and then stained with ruthenium. After observation, observation was performed with a transmission electron microscope. Whether or not the thermoplastic silicone resin forms a continuous phase was confirmed by a method of observing the phase structure of the stained and non-stained portions based on the electron micrograph of the pellet central section. High heat present in the phase of the polycarbonate-based resin (A) by measuring the area of the inorganic particles present in the polycarbonate phase and the area of the inorganic particles other than the polycarbonate phase and converting the area ratio to the volume. The abundance ratio of the conductive inorganic compound (C) was calculated from the volume ratio.

  [Molding of Specimen] After each sample pellet obtained was dried, it was 127 mm x 12.7 mm x 1.0 mm thick test piece, 127 mm x 12.7 mm x 3.2 mm thick test piece with an injection molding machine, And 120 mm × 120 mm × 3 mm thick flat plate.

  [Impact resistance] A non-notched Izod impact strength was measured according to ASTM D256 using a sample obtained by cutting a test piece having a thickness of 3.2 mm at the center.

[Thermal conductivity] After applying a graphite spray on both sides of the sample using a 1.0 mm thick test piece, the specific heat of the sample in the room temperature atmosphere using a laser flash method thermal constant measuring device TC-7000 manufactured by ULVAC-RIKO Co., Ltd. And the thermal diffusivity was measured. The thermal conductivity of the composition was calculated by calculating based on the density of the test piece measured separately.
The results are shown in Table 1.

  [Electrical Insulation] Volume resistivity was measured according to ASTM D-257 using a flat plate of 120 mm × 120 mm × thickness 3 mm.

  In Comparative Example 1, the volume ratio of (A) / (B) is out of the range of the present invention, and the presence ratio in the (A) phase of (C) is high, so the effect of improving the thermal conductivity is inferior. . In Comparative Example 2, the volume ratio of (A) / (B) was increased as it was to further improve the thermal conductivity, but the volume ratio of (C) was increased, but the presence ratio in the (A) phase of (C) was high, Molding processability and impact resistance are greatly deteriorated. In Comparative Example 3, the volume ratio of (C) was outside the range of the present invention, so that molding was difficult. In Comparative Example 4, the volume ratio of (A) / (B) was outside the range of the present invention, and thus the thermal conductivity at which impact resistance and the like were lowered did not improve as expected. In Comparative Example 5, since the volume ratio of (C) is outside the range of the present invention, the thermal conductivity is low.

From the above, the thermoplastic resin composition of the present invention can improve the thermal conductivity of the composition efficiently only by adding a small amount of high thermal conductive inorganic compound compared to the known compositions so far, It can be seen that a low-cost and electrically insulating composition having an excellent balance between various physical properties and thermal conductivity can be obtained.

It is a side view which shows an example of the kneading apparatus which can be used for the manufacturing method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; 1st supply port 2; Vent port 3 open | released to atmospheric pressure; 2nd supply port 4; Vent port 5 decompressed; Extraction port 6; Drive motor

Claims (5)

A polycarbonate-based resin (A), a thermoplastic silicone resin (B), a single thermal conductivity of 5 W / m · K or more, and a highly thermally conductive inorganic compound (C) that exhibits electrical insulation,
1) The volume ratio of (A) and (B) is a ratio of 15/85 to 75/25,
2) The volume ratio of (C) / {(A) + (B)} is 10/90 to 75/25,
3): The ratio in which (C) is present in the phase of (A) is (A) volume fraction × 0.4 or less,
4): A highly heat-conductive thermoplastic resin composition, wherein at least (B) forms a continuous phase structure.   The high thermal conductive thermoplastic resin composition according to claim 1, wherein the (C) is a high thermal conductive inorganic compound exhibiting electrical insulation.   3. The high thermal conductivity according to claim 1, wherein the (C) is a metal oxide fine particle and / or a metal nitride fine particle having a volume average particle diameter of 1 nm or more and 12 μm or less. Thermoplastic resin composition.   The said (C) contains at least 1 sort (s) chosen from boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, beryllium oxide, The any one of Claims 1-3 characterized by the above-mentioned. High thermal conductive thermoplastic resin composition. The thermoplastic silicone resin (B) has an average composition formula (1)
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(Wherein R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms. R ¹ , R Each of ² may be present in two or more types, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.05 ≦ n / m ≦ 10. The high thermal conductivity thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is high in thermal conductivity.

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