WO2008062844A1

WO2008062844A1 - Radiating resin compositions, process for producing the same, and molded article

Info

Publication number: WO2008062844A1
Application number: PCT/JP2007/072583
Authority: WO
Inventors: Shinsuke Fujioka; Fusamichi Kitada
Original assignee: Techno Polymer Co., Ltd.
Priority date: 2006-11-24
Filing date: 2007-11-21
Publication date: 2008-05-29

Abstract

A radiating resin composition having excellent radiating properties, an excellent balance between moldability and impact resistance, and excellent electromagnetic-shielding properties; a process for producing the composition; and a molded article thereof. Also provided are: a radiating resin composition which has excellent radiating properties and an excellent balance between moldability and impact resistance and is excellent also in thermal conductivity and electromagnetic-shielding properties; and a molded article comprising the composition. These compositions comprise a thermoplastic resin (ABS, PC, etc.) and carbon fiber structures which each comprises carbon fiber parts having an outer diameter of 15-100 nm and a connection part connecting many of the carbon fiber parts and which has a three-dimensional network structure. The content of the carbon fiber structures is 1-80 parts by mass per 100 parts by mass of the thermoplastic resin. The compositions can further contain graphite particles.

Description

Specification

Heat dissipation resin composition, method for producing the same, and molded product

Technical field

[0001] The present invention relates to a heat-dissipating resin composition containing a thermoplastic resin and a carbon fiber structure having a specific structure and a method for producing the same, a thermoplastic resin, graphite particles, and a carbon fiber structure. Regarding the heat-dissipating resin composition to be contained, and molded products containing these compositions, more specifically, it has excellent heat dissipation and excellent balance of molding processability and impact resistance, and further, electromagnetic shielding properties, Alternatively, the present invention relates to a heat-dissipating resin composition excellent in thermal conductivity and electromagnetic shielding properties, a method for producing the same, and a molded product.

Background art

[0002] In recent years, with the increase in integration density and speed of semiconductor elements such as LSIs and the high density implementation of electronic components, heat generation from these semiconductor elements and electronic components has increased, and countermeasures for heat dissipation are a major issue. It has become. In addition, for example, mobile phones and mopile personal computers are becoming smaller and lighter in product and more complicated in shape, and a molding material excellent in molding processability and impact resistance is required. Furthermore, countermeasures against electromagnetic waves generated from electronic components that may cause radio interference and malfunctions to peripheral devices are also a major issue.

[0003] For example, Patent Document 1 discloses a highly thermally conductive resin composition containing a thermoplastic resin such as PBT and PEEK, and inorganic fibers and inorganic powders such as aluminum nitride. Patent Document 2 discloses a resin composition containing a specific block copolymer or hydrogenated block copolymer, a rubber softener, and a heat conductive material such as magnesium hydroxide! /, The Further, in Patent Document 3, a filler made of aluminum nitride sintered powder or the like is dispersed in a matrix resin and is formed into a network by a low melting point metal or eutectic alloy having a melting point power of ¾00 ° C. or less. A high thermal conductive composite is disclosed in which the filler is continuously welded to each other through the formed metal network.

[0004] Patent Documents 4 and 5 each disclose a conductive resin composition containing graphite having a specific shape or size.

[0005] Further, carbon-based fillers have been proposed as other materials imparting thermal conductivity! Charcoal In order to obtain high thermal conductivity by blending an elemental filler, it has become clear that refinement of the filler, increase of the paste ratio, increase of the specific surface area, etc. are effective. For example, carbon fibers (Patent Document 6) in which the fiber diameter of the fibrous filler is reduced to increase the specific surface area, carbon black and carbon nanotubes (hollow carbon fibers) having a very large specific surface area are known.

[0006] However, resin compositions containing metal fibers, metal powders, inorganic fibers, inorganic powders, and the like sometimes have insufficient moldability and impact resistance. In addition, environmental stability may be insufficient, which may cause corrosion of the product. Furthermore, there was a risk of causing electrical failure to the molding machine, deterioration of slidability, and abrasion of the screw of the molding machine.

Also, in order to increase the thermal conductivity of the resin composition containing the carbon-based filler, if the proportion of the carbon-based filler to the matrix resin is increased, the small bulk density and strong cohesive force of the carbon-based filter Further, it became difficult to uniformly disperse in the resin, and the moldability, impact resistance, and surface appearance might be deteriorated.

[0007] Further, Patent Document 7 has preferable characteristics as a composite material filter, and physical properties such as electrical characteristics, mechanical characteristics, and thermal characteristics can be obtained with a small addition amount without damaging the characteristics of the matrix resin. A composite material comprising a novel carbon fiber structure that can improve properties is disclosed. The resin composition of Patent Document 7 can obtain a high thermal conductivity with a small blending amount with respect to the matrix resin by blending a carbon fiber structure having a specific structure. However, the range of use was limited, where the balance between moldability and impact resistance was not sufficient.

Patent Document 1: Japanese Patent Application Laid-Open No. 8-283456

Patent Document 2: Japanese Patent Application Laid-Open No. 2001_106865

Patent Document 3: Japanese Patent Laid-Open No. 6-196884

Patent Document 4: Japanese Patent Laid-Open No. 2001-60413

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-253127

Patent Document 6: JP-A-8-27279

Patent Document 7: Japanese Unexamined Patent Application Publication No. 2006-265315 Disclosure of the invention

Problems to be solved by the invention

[0009] An object of the present invention is a heat-dissipating resin composition excellent in heat dissipation, excellent in balance between molding processability and impact resistance, and further excellent in electromagnetic shielding properties, and a method for producing the same, and molding. Is to provide goods.

Another object of the present invention is a heat dissipating resin composition excellent in heat dissipation, excellent in moldability and impact resistance, and further excellent in thermal conductivity and electromagnetic shielding properties, and the same. It is providing the molded article containing this.

Means for solving the problem

[0010] As a result of earnest research to solve the above problems, the present inventors have excellent heat dissipation and molding by blending a thermoplastic resin and a carbon fiber structure having a specific structure. The present inventors have found a heat-dissipating resin composition excellent in the balance between workability and impact resistance, and further excellent in electromagnetic shielding properties, a manufacturing method thereof, and a molded product.

In addition, the present inventors blended a thermoplastic resin, graphite particles, and a carbon fiber structure to provide excellent heat dissipation, a good balance between molding processability and impact resistance, and heat. A heat-dissipating resin composition excellent in conductivity and electromagnetic shielding properties and a molded product containing the same were found.

[0011] The present invention is described below.

1. [A] a thermoplastic resin, and [B] an outer diameter of 15 to; carbon having a carbon fiber part of OOnm and a joining part for joining a large number of the carbon fiber parts, and having a three-dimensional network structure The carbon fiber structure [B] is contained in an amount of! To 80 parts by mass when the thermoplastic resin [A] is 100 parts by mass. A heat-dissipating resin composition.

2. The thermoplastic resin [A] is a rubber-reinforced bull resin obtained by polymerizing a bull monomer (bl) containing an aromatic bull compound in the presence of a rubber polymer, or A rubber-reinforced resin and a mixture comprising a (co) polymer of a bull-based monomer (b2), which contains a rubber-reinforced resin and a polycarbonate resin, and the rubber-reinforced resin and the polycarbonate resin The heat-dissipating resin according to 1 above, wherein the total content of these is 100% by mass;! ~ 80% by mass and 99-20% by mass, respectively Composition.

3. Mixture or kneaded material composed of 50 to 95% by mass of the above polycarbonate resin and 50 to 5% by mass of the carbon fiber structure [B] (the total of which is 100% by mass), and the above rubber reinforcement The above-mentioned carbon fiber structure [B] has a content of! -80 mass parts when the resin is melt-kneaded and the total of the polycarbonate resin and the rubber-reinforced resin is 100 mass parts. 2. The heat dissipating resin composition according to 2.

4. In addition, any one of the above 1 to 3, further comprising a flame retardant, wherein the content of the flame retardant is 100 to 30 parts by mass when the thermoplastic resin [A] is 100 parts by mass; The heat-dissipating resin composition described in 1.

5. The heat-dissipating resin composition as described in any one of 1 to 4 above, which has a thermal conductivity of 3 W / (m′K) or more.

6. The heat-dissipating resin composition according to any one of 1 to 5 above, wherein the Charpy impact strength is 5 kj / m ² or more and the melt mass flow rate is 5 g / l 0 minutes or more.

7. The heat-dissipating resin composition according to 1 to 6 above, wherein the electromagnetic wave shielding property at a frequency of 100 MHz is 30 dB or more.

8. A method for producing a heat-dissipating resin composition as described in 1 above, wherein a part of the thermoplastic resin [A] and at least a part of the carbon fiber structure [B] are melt kneaded. A mixing step, a kneaded product obtained by the first mixing step, a second mixing step of melt-kneading the remainder of the thermoplastic resin [A] and the remainder of the carbon fiber structure [B]. The manufacturing method of the heat-radiating resin composition characterized by providing these.

9. In the first mixing step, the total amount of the carbon fiber structure [B] is used, and the use ratio of the thermoplastic resin [A] and the carbon fiber structure [B] is 50 to 95 quality, respectively. In the second mixing step, and the kneaded product obtained in the first mixing step and the heat in the second mixing step. 9. The method for producing a heat-dissipating resin composition as described in 8 above, wherein the remainder of the plastic resin [A] is melt-kneaded.

10. A method for producing a heat-dissipating resin composition as described in 2 above, wherein the polycarbonate resin and at least a part of the carbon fiber structure [B] are melt-kneaded in a first mixing step. And a second mixing step of melt-kneading the kneaded material obtained in the first mixing step, the rubber-reinforced resin, and the remaining part of the carbon fiber structure [B]. A method for producing a heat-dissipating resin composition.

11. In the first mixing step, the total amount of the carbon fiber structure [B] is used, and the usage ratios of the polycarbonate resin and the carbon fiber structure [B] are 50 to 95% by mass and 50 to 50%, respectively. 5% by mass (however, the total of these is 100% by mass), and in the second mixing step, the kneaded product obtained in the first mixing step and the rubber-reinforced resin are 11. The method for producing a heat-dissipating resin composition as described in 10 above, which is melt-kneaded.

12. Further, [C] graphite particles are contained, and the content of the graphite particles [C] is 10 to 300 parts by mass when the thermoplastic resin [A] is 100 parts by mass. 8. The heat dissipating resin composition according to any one of 7 above.

13. Graphite particles (C1) having an aspect ratio of 10 to 20, a weight average particle size of 10 to 2 OO ^ m, and a fixed carbon content of 98% by mass or more. 13. The heat dissipating resin composition as described in 12 above.

14. The heat-dissipating resin composition as described in 13 above, wherein the graphite particles (C1) have a scaly shape.

Yes

15. Ratio D of particle diameters D and D when the cumulative weights obtained by measuring the particle size distribution of the graphite particles (C1) are 20% and 80%, respectively. Above 13

20 80 80 20

Or the heat-radiating resin composition of 14.

16. The graphite particles [C] are graphite particles (C2) having an aspect ratio of 3 or less, a weight average particle diameter of !! to 70 m, and a fixed carbon content of 98% by mass or more. 13. The heat dissipating resin composition as described in 12 above.

17. The heat-dissipating resin composition as described in any one of 13 to 16 above, wherein the graphite particles [C] include the graphite particles (C1) and the graphite particles (C2).

18. The content ratio of the carbon fiber structure [B] and the graphite particles [C] is 20 to 95 mass% and 80 to 5 mass%, respectively, when the total of these contents is 100 mass%. The heat-dissipating resin composition according to any one of 12 to 17 above, wherein

19. A heat-dissipating resin composition as described in any one of 1 to 7 and 12 to 18 above. A molded product characterized by

The invention's effect

[0012] According to the heat-dissipating resin composition of the present invention containing the thermoplastic resin [A] and the carbon fiber structure [B] having a specific structure, the heat-dissipating resin composition is excellent in heat dissipating property, Excellent balance of impact resistance, and excellent electromagnetic shielding properties.

When the thermoplastic resin [A] contains a rubber reinforced resin and a polycarbonate resin, it is particularly excellent in molding processability, heat dissipation and impact resistance. In addition, the heat-dissipating resin composition produced by subjecting these resins to a specific kneading method is excellent in the compatibility of the thermoplastic resin [A] and the carbon fiber structure [B]. The molded product of the present invention, which is excellent in heat dissipation and contains the above-mentioned thermoplastic resin [A] and a carbon fiber structure [B] having a specific structure, has heat dissipation, molding processability, impact resistance and electromagnetic wave shielding. Excellent in properties.

[0013] According to the method for producing a heat dissipating resin composition of the present invention, which includes a thermoplastic resin [A] and a carbon fiber structure [B] having a specific structure, the heat dissipating resin composition has excellent heat dissipation and is molded. It is possible to easily obtain a heat-dissipating resin composition having an excellent balance of workability and impact resistance and also having excellent electromagnetic shielding properties.

[0014] When the heat-dissipating resin composition of the present invention further contains graphite particles [C], the heat-dissipating resin composition is excellent in heat dissipating property, excellent in the balance of molding processability and impact resistance, and further in heat conduction. And excellent electromagnetic shielding properties.

When the graphite particles [C] have a specific size or shape, they are particularly excellent in heat dissipation, thermal conductivity, and electromagnetic shielding properties.

When the thermoplastic resin [A] contains a rubber-reinforced resin and a polycarbonate resin, and these are in a specific content ratio, in particular, moldability, heat dissipation, thermal conductivity, impact resistance and Excellent electromagnetic shielding properties.

[0015] The above thermoplastic resin [A], carbon fiber structure [B] having a specific structure, and graphite particles [

The molded product of the present invention containing C] is excellent in heat dissipation, molding processability, impact resistance, thermal conductivity and electromagnetic wave shielding properties. Brief Description of Drawings

[0016] FIG. 1 is a longitudinal cross-sectional explanatory view of a thermal fogging test apparatus.

Explanation of symbols

[0017] 1: Polycarbonate (PC) frame member

2: Flat plate for evaluation

3: Silicone rubber heater

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, the present invention will be described in detail.

In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and methacrylic.

[0019] The heat-dissipating resin composition of the present invention comprises [A] a thermoplastic resin (hereinafter also referred to as “component [A]”), and [B] a carbon fiber portion having an outer diameter of 15 to 100 nm, A carbon fiber structure having a three-dimensional network structure (hereinafter, also referred to as “component [B]”), and the component [B]. The content of is 1 to 80 parts by mass, when the component [A] is 100 parts by mass.

Further, the heat dissipating resin composition of the present invention may be a resin composition containing [C] graphite particles (hereinafter also referred to as “component [C]”).

Hereinafter, the composition containing the above components [A] and [B] and not containing the above component [C] is referred to as “heat dissipating resin composition [S]”, and the above components [A], [B ] And the composition containing [C] are referred to as “heat-dissipating resin composition [T]”.

[0020] The component [A] is not particularly limited as long as it is a thermoplastic polymer. Polystyrene, styrene / acrylonitrile copolymer, styrene / maleic anhydride copolymer, (meth) acrylic acid Esters. Styrene (co) polymers such as styrene copolymers; Rubber-reinforced resins such as ABS resin, AES resin and ASA resin; Polyethylene, polypropylene, ethylene 'propylene copolymer, etc. 2 to 10 carbon atoms; 10 Α-olefin (co) polymers composed of at least one of α-olefins and modified resins (chlorinated polyethylene, etc.), olefin resins such as cyclic olefin copolymers; ionomers, ethylene Polymers, Ethylene Copolymers such as Ethylene 'Buyl Alcohol Copolymers; Polychlorinated Bull, Ethylene Copolymer 'Buluric chloride resins such as poly (vinyl chloride) and polyvinylidene chloride; acrylics such as (co) polymers using one or more (meth) acrylic acid esters such as poly (methyl methacrylate) (PMMA) Resin: Polyamide, polyamide, 6, polyamide, 6, 6, polyamide, 6, 12, etc. polyamide, resin (PA); Polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate; Polyacetal Resin (POM); Polycarbonate resin (PC); Polyarylate resin; Polyphenylene ether; Polyphenylene sulfide; Fluororesin such as polytetrafluoroethylene and polyvinylidene fluoride; Liquid crystal polymer; Polyimide, Polyamideimide Imide resins such as polyetherimide; polyetherketone, polyetherether Ketone resins such as ruketone; Sulfone resins such as polysulfone and polyethersulfone; Urethane resins; Polyacetate butyl; Polyethylene oxide; Polybulol alcohol; Polybulul ether; Polybulbutyral; Phenoxy resin; Photosensitive resin; And other plastics. These can be used alone or in combination of two or more. Of these, rubber reinforced resin, polycarbonate resin, olefin resin, polyester resin, polyamide resin and the like are preferred, and a combination of rubber reinforced resin and polycarbonate resin is particularly preferred.

[0021] The rubber-reinforced resin polymerizes a bulle monomer (bl) containing an aromatic bur compound in the presence of a rubbery polymer (hereinafter referred to as "rubbery polymer (a)"). The rubber-reinforced vinyl resin (hereinafter referred to as “rubber-reinforced vinyl resin (Al)”), or the rubber-reinforced vinyl resin (A1) and the rubber monomer (b2) A mixture of (co) polymer (hereinafter referred to as “(co) polymer (A2)”).

[0022] The rubbery polymer (a) may be a homopolymer as long as it is rubbery at room temperature! /, And may be a copolymer. (Gen-based rubber polymer) and non-gen-based polymer (non-gen rubber-based polymer) are preferred. Further, the rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

[0023] Examples of the gen-based polymer (gen-based rubbery polymer) include homopolymers such as polybutadiene, polyisoprene, polychloroprene; styrene 'butadiene copolymer, styrene' butadiene, styrene copolymer, Acrylonitrile 'butadiene copolymer, acrylonitrile. Styrene / butadiene copolymer rubber such as styrene / butadiene copolymer; styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer / styrene / isoprene copolymer Combined rubber; natural rubber and the like. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The above gen-based polymers can be used singly or in combination of two or more.

[0024] The non-gen-based polymer (non-gen-based rubbery polymer) is an ethylene'a-olefin-based copolymer rubber containing an ethylene unit and a unit comprising α-olefin having 3 or more carbon atoms; Examples include urethane rubbers; acrylic rubbers; silicone rubbers; silicone 'acrylic IPN rubbers; polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The non-gen-based polymers can be used singly or in combination of two or more.

[0025] The rubber-reinforced vinyl resin (A1) obtained when a gen-based polymer is used as the rubber polymer (a) is a gen-based rubber-reinforced resin. "It is said that. Further, as the rubbery polymer (a), the rubber-reinforced bur resin (A1) obtained when ethylene'a-olefin and / or ethylene'a-olefin'nonconjugated-gen copolymer is generally used, It is said to be “AES resin”. Furthermore, the rubber-reinforced bull resin (A 1) obtained when acrylic rubber is used as the rubbery polymer (a) is an acrylic rubber-reinforced bull resin, generally referred to as “ASA resin”. It is said

[0026] The shape of the rubbery polymer (a) used for the formation of the rubber-reinforced bull resin (A1) is not particularly limited, but when it is particulate, its weight average particle diameter is preferably 50 to 3,000 stomachs, more preferably 100 to 2,000 stomachs, and still more preferably 120 to 800 stomachs. When the weight average particle diameter is less than 50 nm, the heat-dissipating resin compositions [S] and [T] of the present invention and molded products containing them tend to be inferior in impact resistance. The surface appearance of the molded product tends to be inferior. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

[0027] When the rubbery polymer (a) is in the form of particles, as long as the weight average particle diameter is within the above range, for example, JP-A-61-233010, JP-A-59-93701, Those enlarged by a known method described in JP-A-56-167704 and the like can also be used.

[0028] The method for producing the rubbery polymer (a) is preferably emulsion polymerization in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting production conditions such as the type and amount of emulsifier, the type and amount of initiator used, polymerization time, polymerization temperature, and stirring conditions. Another method for adjusting the average particle size (particle size distribution) may be a method of blending two or more of the rubbery polymers (a) having different particle sizes.

[0029] The bull monomer (bl) used for forming the bull rubber polymer (A1) includes an aromatic bull compound. This bull monomer (bl) may be an aromatic bull compound alone, and this bull monomer, for example, cyanide bull compound, (meth) acrylate compound, maleimide compound, acid anhydride It may be a combination of a compound that can be copolymerized with an aromatic bur compound such as a product. The compounds that can be copolymerized with the above aromatic bur compound can be used singly or in combination of two or more. Therefore, as the bulle monomer (bl), one kind of aromatic bur compound is used. A monomer (χ) consisting of the above, or a monomer (y) that is a combination of one or more aromatic bull compounds and one or more compounds copolymerizable with this aromatic bull compound. Can be used

[0030] The aromatic bur compound is not particularly limited as long as it is a compound having at least one butyl bond and at least one aromatic ring. Examples thereof include styrene, α-methyl styrene, ο-methyl styrene. , Ρ-methyl styrene, butyl toluene, β-methyl styrene, ethyl styrene, p- tert-butyl styrene, butyl xylene, vinyl naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dib-mouthed styrene And fluorostyrene. These can be used singly or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

[0031] Examples of the cyanide bur compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

[0032] Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) alkyl. Examples include η-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylate phenyl. These can be used alone or in combination of two or more. Of these, methyl (meth) acrylate is preferred.

[0033] The maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenylenole) maleimide, N- (4-hydroxyphenyl) maleimide, N —Cyclohexylmaleimide and the like. These can be used alone or in combination of two or more. As another method for introducing maleimide-based compound, such a unit, for example, maleic anhydride is copolymerized and then imidized.

[0034] Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

[0035] In addition to the above compounds, if necessary, it is possible to use a bur compound having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group. For example, (meth) acrylic acid 2-hydroxyethyl, hydroxystyrene, (meth) acrylic acid N, N-dimethylaminomethyl, N, N-jetyl-p-aminomethylstyrene, (meth) acrylic acid glycidyl, ( Examples include meth) acrylic acid 3,4-oxycyclohexyl, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylolamide, attalinoleamide, (meth) acrylic acid, buroxazoline and the like. This These can be used alone or in combination of two or more.

[0036] The bull monomer (bl) is a combination of one or more aromatic bull compounds and one or more compounds copolymerizable with the aromatic bull compounds, that is, the above monomers. It is preferable to use the body (y). In this case, the mass ratio between the aromatic bur compound and the other compounds is usually (2 to 95) when the total is 100% by mass. % By mass / (98 to 5)% by mass, preferably (10 to 90)% by mass / (90 to 10)% by mass. If the ratio of the above aromatic bur compound is too small, the moldability tends to be inferior, and if it is too large, the resulting molded article may not have sufficient chemical resistance, heat resistance and the like.

[0037] The monomer (y) is preferably a combination of an aromatic bull compound and a cyanide bull compound (hereinafter referred to as "monomer (yl)"), and an aromatic bull compound. , A combination of a cyanated bur compound and another compound (such as a (meth) acrylate compound) (hereinafter referred to as “monomer (y2)”). Use of cyanide bur compound improves the balance of physical properties such as chemical resistance and heat resistance.

[0038] The rubber-reinforced bull resin (A1) is obtained by polymerizing the vinyl monomer (bl) in the presence of the rubber polymer (a). Illustrated.

[1] One or more rubber-reinforced bull resins obtained by using only the monomer (X) as the bull monomer (b 1).

[2] One or more rubber-reinforced bull resins obtained by using only the monomer (yl) as the bull monomer (bl).

[3] One or more rubber-reinforced bull resins obtained using only the monomer (y2) as the bull monomer (bl).

As the rubber-reinforced bull resin (A1), the above embodiments [2] and [3] are preferable. Further, it may be a combination of two or three of these embodiments [1], [2] and [3].

[0039] As described above, the rubber reinforced resin may be only the rubber reinforced bull resin (A1), or the rubber reinforced bull resin (A1) and the bull monomer (b2 ) (Co) polymer (hereinafter referred to as “(co) polymer (A2)”).

As the bull monomer (b2) used for the formation of the (co) polymer (A2), the compounds exemplified as the bull monomer (bl) can be used. Therefore, the above (co) polymer (A2) May be a polymer obtained by polymerizing components having the same composition as the above-mentioned bull monomer (M) used for the formation of the rubber-reinforced bull resin (A1), or a different composition. It may be a polymer obtained by polymerizing the same type of monomer, or may be a polymer obtained by polymerizing different types of monomers with different compositions. . These polymers may contain two or more types! /.

[0040] The (co) polymer (A2) is a homopolymer or copolymer obtained by polymerization of the bull monomer (b2), and is exemplified below. As described above, the compounds used for forming the rubber-strengthened bull resin (al) can be applied to the respective compounds, and preferable compounds are also the same.

[4] One or more (co) polymers obtained by polymerizing only aromatic bur compounds.

[5] One or more (co) polymers obtained by polymerizing only (meth) acrylic acid ester compounds

[6] One or more types of copolymers obtained by polymerizing aromatic and cyanide bur compounds.

[7] One or more kinds of copolymers obtained by polymerizing an aromatic bur compound and a (meth) acrylic acid ester compound.

[8] One or more kinds of copolymers obtained by polymerizing aromatic bur compound, cyanide bur compound and other compounds.

[9] One or more types of copolymers obtained by polymerizing an aromatic bur compound and other compounds excluding the cyanide bur compound.

The (co) polymer of the above embodiment can be used alone or in combination of two or more.

[0041] As the above (co) polymer (A2), acrylonitrile 'styrene copolymer, acrylonitrile' a-methylstyrene copolymer, acrylonitrile 'styrene' methyl methacrylate copolymer, styrene 'methyl methacrylate copolymer Acrylonitrile 'styrene · スチレン -phenylmaleimide copolymer, and the like.

[0042] Next, a method for producing the rubber-reinforced bull resin (A1) and the (co) polymer (説明 2) will be described. [0043] The rubber-reinforced bull resin (A1) can be produced by polymerizing the vinyl monomer (bl) in the presence of the rubber polymer (a). As the polymerization method, emulsion polymerization, solution polymerization, bulk polymerization, and bulk suspension polymerization are preferable.

[0044] In the production of the rubber-reinforced bull resin (A1), the rubber polymer (a) and the bull monomer (bl) are mixed in the reaction system with the rubber polymer ( a) In the presence of the total amount, the above-mentioned bulle monomer (bl) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. In addition, in the presence or absence of part of the rubber polymer (a), the bulle monomer (bl) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubbery polymer (a) may be added in a batch, divided or continuously during the reaction.

[0045] When producing 100 parts by mass of the rubber-reinforced bull resin (A1), the amount of the rubbery polymer (a) used is usually 5 to 80 parts by mass, preferably 10 to 70 parts by mass, Preferably it is 15-60 mass parts. The amount of the above-mentioned bulle monomer (bl) is usually 25 to 1,900 parts by weight, preferably 60 to 560 parts by weight, based on 100 parts by weight of the rubbery polymer (a). .

[0046] When the rubber-reinforced bull resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

[0047] Examples of the polymerization initiator include organic peroxides such as cumene hydride mouth peroxide, diisopropylbenzene oxide mouth peroxide, and noramentan nanodropperoxide, and reductions such as sugar-containing pyrophosphate prescription and sulfoxylate prescription. Redox initiators combined with other agents; persulfates such as potassium persulfate; benzoyl peroxide (BPO), lauroyl peroxide, tert butinoreperoxylaurate, tert butinoreperoxy monocarbonate, etc. And the like. These can be used alone or in combination of two or more. The amount of the polymerization initiator used is usually from 0.2 to 0.7% by mass, preferably from 0.2 to 0.7% by mass, based on the total amount of the bull monomer (b 1). The polymerization initiator can be added to the reaction system all at once or continuously.

Yes

[0048] Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert- Examples include dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-pinolenes, and a-methylstyrene dimer. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is generally 0.05-2. 0% by mass with respect to the total amount of the bulle monomer (bl).

The chain transfer agent can be added to the reaction system all at once or continuously.

Yes

[0049] Examples of the emulsifier include a canyon surfactant and a noion surfactant. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates and aliphatic phosphates. Salt and the like. Examples of nonionic surfactants include polyethylene glycol alkyl ester type compounds and alkyl ether type compounds. These can be used alone or in combination of two or more. The amount of the emulsifier used is usually 0.3 to 5.0% by mass with respect to the total amount of the vinyl monomer (bl).

[0050] Emulsion polymerization can be carried out under known conditions depending on the type of the bull monomer (bl), the polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually purified by coagulating with a coagulant to form a polymer component in powder form, and then washing and drying. As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.

In the case of a rubber reinforced resin containing two or more kinds of the above rubber reinforced resin (A1), the resin may be isolated from each latex and then mixed. There are methods such as coagulating a mixture of latexes each containing fat.

[0051] Known methods can be applied to the method for producing the rubber-reinforced bull resin (A1) by solution polymerization, bulk polymerization, and bulk suspension polymerization.

[0052] The graft ratio of the rubber-reinforced bull resin (A1) is usually 10 to 200% by mass, preferably 15 to 150% by mass, more preferably 20 to 100% by mass. Graft rate is 10% by mass If it is less than 1, the surface appearance and impact resistance of the molded product containing the heat-dissipating resin composition [S] or [T] of the present invention may be lowered. On the other hand, if the graft ratio exceeds 200%, the moldability may decrease.

[0053] Here, the graft ratio refers to X-gram of the rubbery polymer (a) in 1 gram of the rubber-reinforced bull resin (Al) and 1 gram of the rubber-reinforced bull resin (Al) in acetone. This is the value obtained from the following equation, where y grams is the insoluble content when dissolved. However, when the rubbery polymer (a) is an acrylic rubber, acetonitrile is used instead of acetone.

Yes

The graft ratio (mass ^{_{0/0) = {(y-}} χ) / χ} X 100

[0054] Further, the intrinsic viscosity of a component soluble in acetone of the rubber-reinforced bull resin (A1) (however, when the rubbery polymer (a) is an acrylic rubber, acetonitrile is used). [] (Measured in methyl ethyl ketone at 30 ° C) is usually 0.;! To 1 · 0 dl / g, preferably 0.2 to 0 · 9 dl / g, more preferably 0 · 3 to 0 · 7dl / g. When the intrinsic viscosity []] is within the above range, the molding processability is excellent and the resulting molded article is excellent in impact resistance.

[0055] The above-mentioned graft ratio and intrinsic viscosity [7] are the types of polymerization initiator, chain transfer agent, emulsifier, solvent, etc. used when the rubber-reinforced bull resin (A1) is produced. The amount can be easily controlled by adjusting the polymerization time, polymerization time, polymerization temperature and the like.

[0056] The (co) polymer (A2) is obtained by polymerizing the bull monomer (b2) using a polymerization initiator or the like applied to the production of the rubber-reinforced bull resin (A1). Can be manufactured. As the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. The (co) polymer (A2) may be a method using a polymerization initiator, a thermal polymerization method without using a polymerization initiator, or a combination thereof. .

[0057] The intrinsic viscosity [η] (in methyl ethyl ketone, 30. Measured at C) of the acetone-soluble component of the (co) polymer (A2) is usually 0.1 to 1. Odl / g, Preferably it is 0.15-0.7 dl / g. When the intrinsic viscosity [7] is within the above range, the molding processability is excellent and the resulting molded article is excellent in impact resistance. The intrinsic viscosity [7] of the (co) polymer (A2) can be controlled by adjusting the production conditions, as in the case of the rubber-reinforced resin (A1). it can.

[0058] Soluble in acetone of the rubber-reinforced resin (however, when the rubbery polymer ω used for forming the rubber-reinforced resin (A1) is an acrylic rubber, acetonitrile is used). The intrinsic viscosity [7]] of the component (measured in methyl ethyl ketone at 30 ° C) is usually from 0 ·;! To 0.8 dl / g, preferably 0.15-0. 7 dl / g. When this intrinsic viscosity [7] is within the above range, the balance between physical properties of molding processability and impact resistance is excellent.

[0059] When the component [A] includes the rubber-reinforced resin, and the rubber-reinforced resin is the rubber-reinforced vinyl resin (A1), the rubber-reinforced resin resin (A1) and the ( In any case where the mixture is made of a mixture of (co) polymer (A2), the content of the rubbery polymer (a) in the heat-dissipating resin composition [S] or [T] of the present invention is usually !!-50 mass%, preferably 3-40 mass%, more preferably 3-35 mass%, particularly preferably 5-35 mass%. If the content of the rubbery polymer (a) is within the above range, the molding processability is excellent, and the molded product containing the heat-dissipating resin composition [S] or [Τ] of the present invention has an impact resistance. Excellent surface appearance, rigidity and heat resistance.

[0060] When the rubber-reinforced resin is used as the component [Α], various compositions can be obtained by selecting the type of the rubber-reinforced resin (A1).

[0061] The polycarbonate resin is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, aromatic polycarbonate is preferred from the viewpoints of moldability, impact resistance, and heat resistance. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (wherein R and R ′ each represents an organic group). Good. These polycarbonate resins can be used singly or in combination of two or more.

[0062] Examples of the aromatic polycarbonate include those obtained by melt transesterification (transesterification reaction) of an aromatic dihydroxy compound and carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine. A product obtained by a pyridine method using a reaction product of phosgene and phosgene can be used.

[0063] The aromatic dihydroxy compound is a compound having two hydroxyl groups in the molecule. Dihydrobenzene such as hydroquinone and resorcinol, 4,4'-biphenol, 2,2-bis (4-hydroxyphenol) propane (hereinafter referred to as “bisphenolenore A”), 2,2-bis (3,5-Dibu-Mole 4-Hydroxyphenol) Propane, 2,2-Bis (4-Hydroxyphenol 2-Lu 3-Methylphenol) Propane, 2,2-Bis (3-tert-Butinole 4-hydroxy Phenyleno) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenol) butane, 2,2-bis (p-hydroxyphenol) pentane, 1,1-bis (p-hydroxyphenol) cyclohexane, 1, 1 —Bis (p— Roxyphenyl) 1 4-Isoprovircyclohexane, 1,1-bis (p-hydroxyphenyl) 1,3,3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) ) 1 1-phenylethane, 9, 9-bis (p-hydroxyphenenole) fluorene, 9, 9-bis (p-hydroxy-1-3-methylphenenole) fluorene, 4, 4 '-(p-phenol) Range isopropylidene) diphenanol, 4, 4'-one (m-phenylene diisopropylidene) diphenol, bis (p-hydroxyphenenole) oxide, bis (p-hydroxyphenenole) ketone, bis (p-hydroxyl Enenore) etherenole, bis (p-hydroxyphenenole) estenore, bis (p-hydroxyphenenole) snoreido, bis (p-hydroxy-1-methylphenenole) sulfide, bis p- hydroxy-phenylene Honoré) sulfone, bis (3, 5-dibromo-one 4-hydroxy-phenylene Honoré) sulfone, bis (p - hydroxyphenyl) sulfoxide and the like. These can be used alone or in combination of two or more.

Of the above aromatic hydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. The benzene ring may be substituted with a hydrogen atom force S halogen atom contained in the benzene ring. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dib-mouthed 4-hydroxyphenol) propane, 2,2-bis (4-hydroxyphenyl-1-3-methylphenol) propane. 2,2-bis (3-tert-butyl-4-hydroxyphenol) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenol) methane, Examples include 1-bis (p-hydroxyphenyl) ethane and 2,2-bis (p-hydroxyphenyl) butane. This Of these, bisphenol A is particularly preferred.

[0065] Examples of the carbonic acid diesterate used for obtaining the aromatic polycarbonate by transesterification include dimethylolene carbonate, jetinole carbonate, di-tert-butinocarbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

[0066] The viscosity-average molecular weight of the polycarbonate resin is usually 15,000-40,000, preferably (17,000 to 30,000, more preferably 18,000 to 28,000). The polycarbonate resin may be used by mixing two or more polycarbonate resins having different viscosity average molecular weights as long as the viscosity average molecular weight as a whole is in the above range.

[0067] The polycarbonate resin may be the rubber reinforced resin or the (co) polymer (Α2) used in the preparation of the rubber reinforced resin, for example, acrylonitrile styrene copolymer, talaronitrile, _α- methylstyrene copolymer. It can be used as the above component [A] in combination with a polymer, acrylonitrile 'styrene' methyl methacrylate copolymer or the like. The rubber reinforced resin at this time preferably includes a rubber reinforced resin (gen-based rubber reinforced resin) using a gen-based polymer as the rubber polymer (a).

[0068] In the heat-dissipating resin composition [S] of the present invention, when the component [Α] contains the rubber-reinforced resin and the polycarbonate resin, the content ratio is 100% by mass. 1 to 80% by mass and 99 to 20% by mass, respectively, more preferably;! To 75% by mass and 99 to 25% by mass, more preferably 5 to 75% by mass and 95 to 25% by mass, respectively. %, Particularly preferably 35 to 75% by weight and 65 to 25% by weight. If this content ratio is within the above range, it is possible to obtain a molded product having excellent molding processability, heat dissipation and impact resistance by the force S.

[0069] In the heat-dissipating resin composition [Τ] of the present invention, when the component [Α], the rubber-reinforced resin and the polycarbonate resin are contained, the content ratio thereof is 100% by mass. In this case, it is preferably 1 to 80% by mass and 99 to 20% by mass, more preferably 1 to 75% by mass and 99 to 25% by mass, still more preferably 1 to 65% by mass and 99 to 35% by mass, respectively. It is. If this content ratio is in the above range, moldability, heat dissipation Excellent in heat resistance, thermal conductivity, impact resistance, and electromagnetic shielding properties.

[0070] The olefin-based resin is not particularly limited as long as it is a polymer including a monomer unit composed of α-olefin having 2 or more carbon atoms. A preferred olefin-based resin is a polymer containing a monomer unit composed of α-olefin having 2 to 10 carbon atoms. Therefore, (co) polymer mainly containing one or more monomer units composed of α-olefin having 2 to 10 carbon atoms; one or more monomer units composed of α-olefin having 2 to 10 carbon atoms And a copolymer mainly containing at least one monomer unit composed of a compound copolymerizable with α-olefin. These can be used alone or in combination of two or more.

[0071] Examples of the α-olefin include ethylene, propylene, butene-1, pentene 1, hexene-1, 3-methylbutene 1, 4-methylpentene 1, 3-methylhexene 1, and the like. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 1, 3-methylbutene 1 and 4-methylpentene 1-1 are preferable.

[0072] In addition, compounds used for forming other monomer units constituting the olefin-based resin include 4-methinoleyl 1,4 monohexagen, 5-methinoleyl 1,4 monohexagen, 7-methyl. Non-conjugated gens such as 1, 6 octagens and 1, 9 decadienes. These can be used alone or in combination of two or more.

[0073] Examples of the olefin-based resin include polyethylene, polypropylene, ethylene'propylene copolymer, polybutene 1, ethylene'butene 1 copolymer, and the like. Of these, a polymer containing 50% by mass or more of propylene units preferred by polyethylene, polypropylene and propylene / ethylene copolymers with respect to all monomer units, that is, polypropylene, ethylene and propylene copolymers. Is more preferable. The ethylene / propylene copolymer includes a random copolymer and a block copolymer, and the random copolymer is particularly preferable.

[0074] The olefin-based resin may be crystalline! /, And may be amorphous! /. Preferably, it has a crystallinity of 20% or more by X-ray diffraction at room temperature.

The melting point (based on JIS K7121) of the olefin resin is preferably 40 ° C or higher. Yes

The molecular weight of the olefin-based resin is not particularly limited, but from the viewpoint of moldability, the melt flow rate (based on JIS K7210; hereinafter also referred to as “MFR”) is preferably 0.0;! To 500 g / 10 minutes, more preferred <0.05-; lOOg / 10 minutes, preferably those having a molecular weight corresponding to each value.

[0075] As the above-mentioned olefin-based resin, ionomers, ethylene 'butyl acetate copolymer, ethylene' butyl alcohol copolymer, cyclic olefin copolymer, chlorinated polyethylene, and the like can also be used.

[0076] The polyester resin is not particularly limited as long as it has an ester bond in the main chain of the molecule, and may be a saturated polyester resin or an unsaturated polyester resin. Of these, saturated polyester resins are preferred. Further, it may be a homopolymerized polyester or a copolyester. Further, it may be a crystalline resin or an amorphous resin.

[0077] The polyester resin is obtained by using, for example, a resin obtained by polycondensation of a dicarboxylic acid component and a dihydroxy component, polycondensation of an oxycarboxylic acid component or a rataton component, or the like.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether. Aromatic dicarboxylic acids having 8 to 16 carbon atoms, such as tandicarboxylic acid, diphenyl ketone dicarboxylic acid, etc., or their derivatives, cyclohexanedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, hymic acid, etc. having 8 to 12 carbon atoms; alicyclic dicarboxylic acid having about 12 or its derivatives, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid Aliphatic dicarboxylic acids with 2 to 40 carbon atoms such as acids and dimer acids Its derivatives, and the like.

[0078] The derivatives include derivatives capable of forming an ester, for example, lower alkyl esters such as dimethyl ester, acid anhydrides such as acid anhydride and acid chloride, and the like.

These dicarboxylic acid components can be used alone or in combination of two or more. And force S.

[0079] The dihydroxy component includes linear chains such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4 butanediol, neopentinoglycol, hexanediol, octanediol, and decanediol. Or branched chain aliphatic alkylene diols such as alkylene diols having about 2 to 12 carbon atoms, cyclohexanediols, cyclohexane dimethanols, alicyclic diols such as hydrogenated bisphenol A, hydroquinone, resorcin, dihydroxy Adducts obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to phenyl, naphthalenediol, dihydroxydiphenyl ether, bisphenol A, and bisphenol A (diethoxylated vinyl) Aromatic diols such as phenol A), diethylene glycol, triethylene glycol, polyoxyethylene glycol, ditetramethylene glycol, polytetramethylene etherol glycolol, dipropylene glycolol, tripropylene glycolol, polyoxypropylene glycol, poly And polyoxyalkylene glycols such as tetramethylene ether glycol.

[0080] The dihydroxy component may be, for example, a substitute such as an alkyl group, an alkoxy group, or a halogen.

These dihydroxy components can be used alone or in combination of two or more.

[0081] Examples of the oxycarboxylic acid component include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and derivatives thereof.

These oxycarboxylic acid components can be used alone or in combination of two or more.

[0082] Examples of the rataton component include propiolataton, butyrolataton, valerolataton, ε-force prolataton, and the like.

These latatoic acid components can be used alone or in combination of two or more.

[0083] When the polyester resin is a copolymerized polyester, the copolymerizable monomer used for the formation thereof may be ethylene glycol, propylene glycol, 1, 4 Polyoxyalkylene glycol and adipine having an alkylene glycol unit such as butanediol and other poly (oxyalkylene) units such as linear glycols such as linear alkylene glycols, and ethylene glycol, and having about 2 to 4 repeats Examples thereof include aliphatic dicarboxylic acids such as acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids having an asymmetric structure such as phthalic acid and isophthalic acid.

Furthermore, in addition to the above compounds, polyfunctional monomers such as polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid, and polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol, as necessary. May be used in combination.

[0084] Examples of the polyester resin include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl. Polyalkylene terephthalate such as terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyalkylene naphthalate such as polyalkylene naphthalate, homopolymer polyester, alkylene terephthalate unit and / or alkylene naphthalate unit Mainly included are copolyesters and liquid crystal polyesters. Of these, polybutylene terephthalate is preferred. These can be used alone or in combination of two or more.

[0085] The polyamide-based resin is not particularly limited as long as it is a resin having an acid amide bond (one CO-NH) in the main chain. The polyamide resin is usually produced by polymerization of ratata or amino acid having a ring structure, or condensation polymerization of dicarboxylic acid and diamine. Therefore, it is possible to use homopolyamide, copolyamide or the like as the polyamide resin. Monomers that can be polymerized alone include ε-force prolatatam, aminocaproic acid, enantholatatam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, piperidone, and the like.

Examples of the dicarboxylic acid used for polycondensation of dicarboxylic acid and diamine include adipic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, terephthalic acid, 2-methylterephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. . Diamine includes tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene. Diamine, undecamethylenediamine, dodecamethylenediamine, paraphenylenediamine, metaphenylenediamine and the like.

[0086] As the above-mentioned polyamide type lunar month, nylon 4, 6, 7, 8, 11, 12, 6. 6, 6. 9, 6. 10, 6.11, 6. 12, 6T, 6/6 6、6 / 12、6 / 6Τ 、 6Τ / 6Ι etc.

The terminal of the polyamide resin may be sealed with carboxylic acid, amine or the like. Examples of the carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, strong prillic acid, strong purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of amines include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, normitylamine, stearylamine, and behenylamine.

The above polyamide resins can be used singly or in combination of two or more.

[0087] Next, the component [Β] has a three-dimensional network structure including a carbon fiber part having an outer diameter of 15 to 100 nm and a joint part for joining a large number of carbon fiber parts. This component [B] can be observed with a force S to confirm the specific structure shown below by observing with SEM or TEM.

[0088] The component [B] is a bulky and stable structure in which a plurality of fine carbon fiber portions are extended based on the joint portion. Therefore, when the heat radiating resin composition [S] or [T] of the present invention is produced using the component [B] together with the component [A], the carbon fiber portion of the component [B] is cut or the like. It is distributed in the matrix while maintaining the 3D network structure. Further, even if the content ratio of the component [B] relative to the component [A] is small, the component [B] can be arranged with a uniform spread in the matrix.

In the heat-dissipating resin composition [S] of the present invention, when the component [B] is present adjacent to each other, a good heat conduction path is formed on the whole, so that the heat conductivity is improved, and as a result, heat dissipation is also achieved. improves. When the composition of the present invention is a heat-dissipating resin composition [T] containing graphite particles [C] described later, the graphite particles [C] are disposed in the voids of the component [B]. Thus, a good heat conduction path is formed on the whole, so that the heat conductivity is improved, and as a result, the heat dissipation is also improved. In addition, regarding the mechanical and electrical properties, the component [B] is balanced. Therefore, the characteristics can be improved.

[0089] The cross-sectional shape of the carbon fiber portion constituting the component [B] is preferably a polygon. In addition, the length (the length from the joint portion) is not particularly limited, and is usually 2 to 50 111. Furthermore, the outer diameter is 15 to! OOnm, preferably 20 to 70nm. If this outer diameter is in the above range, the moldability and impact resistance are excellent. If the outer diameter is less than 15 nm, the carbon fiber section does not have a polygonal cross section. On the other hand, due to the physical properties of the carbon fiber part, the smaller the diameter, the greater the number per unit amount and the longer the length of the carbon fiber part in the axial direction, resulting in higher conductivity. It is not suitable as a carbon fiber structure to be provided as a modifier or additive to a matrix such as a resin. In the above outer diameter range, cylindrical graph sheets that are laminated in the direction perpendicular to the axis, that is, those that are multi-layered, are given elasticity that is difficult to bend, that is, the property of returning to the original shape even after deformation. Therefore, even after the carbon fiber structure is once compressed, it becomes easy to adopt a sparse structure after being arranged in a matrix such as a resin. For example, when the above component [B] is annealed at a temperature of 2,400 ° C. or more, the surface spacing of the laminated graph sheets is reduced, and the true density is increased from 1.89 g / cm ³ to 2. lg / cm ³ . In addition to the increase, the carbon fiber part has a polygonal shape in the cross-section perpendicular to the axis of the carbon fiber part. Because it is dense and has few defects, bending rigidity is improved.

[0090] The carbon fiber part desirably has an outer diameter that changes along the axial direction. In this way, if the outer diameter of the carbon fiber portion changes in a constant manner along the axial direction, it is considered that a kind of anchor effect occurs in the carbon fiber portion in the matrix, and the movement in the matrix is As a result, << dispersion stability increases.

[0091] In addition, the joining portion that joins a plurality of carbon fiber portions is preferably longer than the outer diameter of the carbon fiber portion (excluding the carbon fiber portion protruding from the joining portion) This is the part that has the diameter when With the above configuration, when the heat-dissipating resin compositions [S] and [T] of the present invention are produced together with the component [A], the three-dimensional network is maintained even if a certain amount of shearing force is applied. It can be dispersed in a matrix.

[0092] The equivalent-circle average diameter (area basis) of the component [B] is preferably 50 to 100. here The area-equivalent circle-equivalent mean diameter means that the carbon fiber structure is photographed by SEM or the like, and the contour of each carbon fiber structure is traced by using image analysis software in this photographed image. The equivalent circle diameter of each fiber structure is calculated and averaged.

[0093] The component [B] can be produced by the following method.

First, in the presence of a catalyst, organic compound materials such as hydrocarbons such as toluene and xylene, alcohols such as ethanol, etc. are chemically pyrolyzed by CVD to produce a fiber structure (hereinafter referred to as “intermediate”). Thereafter, the above-mentioned component [B] can be produced by further high-temperature heat treatment.

[0094] Examples of the catalyst used for the production of the intermediate include transition metals such as iron, cobalt, and molybdenum; transition metal compounds such as metal salt of pheucene and acetic acid, and sulfur, or sulfur such as thiophene and iron sulfide. The mixture which consists of a compound is mentioned.

In addition, it is preferable to use at least two kinds of organic compounds having different decomposition temperatures as the organic compound raw material.

Examples of the atmospheric gas when performing the CVD method include inert gases such as argon, helium, and xenon, and hydrogen gas.

[0095] For the intermediate, a known CVD apparatus is used to evaporate a mixture of the organic compound raw material and the catalyst, and hydrogen gas or the like is introduced into the reaction furnace as a carrier gas, and the temperature is 800-1 300 ° C. It can be obtained by pyrolyzing. That is, by this pyrolysis, a plurality of carbon fiber structures (intermediates) having a sparse three-dimensional structure in which fibers having an outer diameter of 15 to 100 nm are bonded to granules grown using a catalyst as a nucleus. Contained aggregates of several centimeters to tens of centimeters are synthesized. This aggregate also contains unreacted raw materials, non-fibrous carbides, tar content and catalyst.

[0096] Thereafter, in order to remove these residues from the aggregate and obtain the desired carbon fiber structure with few defects, heat treatment is performed at a higher temperature.

For example, the above aggregate is heated at a temperature of 800 to 1,200 ° C to remove volatile components such as unreacted raw materials and tars, and annealed at a temperature of 2,400-3,000 ° C. As a result, the catalyst contained in the fibrous body is evaporated and removed, and the desired carbon fiber structure is obtained. The body is manufactured. That is, by this annealing treatment, the patch-like sheet pieces made of carbon atoms are bonded to each other to form a plurality of graph-en-sheet-like layers, and constitute the carbon fiber portion of the component [B]. In addition, before or after such high-temperature heat treatment, a step of crushing the equivalent circle average diameter of the carbon fiber structure to several centimeters and a circle equivalent average diameter of the crushed carbon fiber structure of 50 to A carbon fiber structure having a desired circle-equivalent mean diameter can be obtained. Note that a pulverization process may be performed instead of the pulverization process. Furthermore, a process of granulating an aggregate having a plurality of carbon fiber structures into an easy-to-use shape, size, and bulk density may be performed. In order to make effective use of the structure formed during the reaction, annealing treatment in a state where the bulk density is low (a state where the fibers are stretched as much as possible and the porosity is large) further imparts conductivity to the resin. It is effective.

From the above, the component [B] obtained by the above production method is firmly bonded to each other at the joint portion where the fine carbon fiber portions are not merely bonded to the joint portion.

The heat-radiating resin composition [S] and [T] of the present invention may contain a carbon fiber structure other than the component [B].

[0097] In the heat-dissipating resin composition [S] and [T] of the present invention, the content of the component [B] is as follows: when the component [A] is 100 parts by mass; Part, preferably 2 to 70 parts by weight, more preferably 5 to 65 parts by weight. If the content of the component [B] is too small, the thermal conductivity and electromagnetic wave shielding properties may not be sufficient. On the other hand, if the content is too large, productivity, moldability, and surface appearance of the molded product may deteriorate. When the heat-dissipating resin composition [S] and [T] of the present invention contains a carbon fiber structure other than the above component [B], the content thereof is 100 parts by mass of the above component [A]. In general, it is 20 parts by mass or less.

[0098] As an example of a preferable composition as the heat-radiating resin composition [S] of the present invention, the component [A] includes a rubber-reinforced resin and a polycarbonate resin, and the polycarbonate resin 50 to 95 is used. The mixture or kneaded material (melt kneaded material) composed of 50% by mass and the above component [B] 50 to 5% by mass (however, the total of these is 100% by mass) and the rubber-reinforced resin are dissolved. When the total of the polycarbonate resin and the rubber-reinforced resin is 100 parts by mass, the content of the component [B] is;! To 80 parts by mass, preferably 2 to 70 parts by mass, More preferably, the composition is 5 to 65 parts by mass. In the case of this method, details of the production method in which it is particularly preferable to use a kneaded product (melt kneaded product) composed of the polycarbonate resin and the component [B] will be described later.

[0099] Next, a method for producing the heat dissipating resin composition [S] of the present invention will be described.

The method for producing the heat-dissipating resin composition [S] of the present invention (hereinafter referred to as “the first production method of the present invention”) is based on the carbon fiber structure based on 100 parts by mass of the thermoplastic resin [A]. It is a method for producing a heat-dissipating resin composition having a body [B] content of 1 to 80 parts by weight, comprising at least a part of the thermoplastic resin [A] and the carbon fiber structure [B]. A first mixing step (hereinafter referred to as “first mixing step (1)”) in which a part of the mixture is melt-kneaded, and a kneaded product (hereinafter referred to as “kneaded product (1)” obtained by the first mixing step (I). ) "), The remaining portion of the thermoplastic resin [A], and the remaining portion of the carbon fiber structure [B] (used as necessary) are mixed and kneaded (hereinafter referred to as" the second mixing step "). "Second mixing step (1)").

In the first production method of the present invention, when an additive is used, it can be used in both the first mixing step (I) and the second mixing step (I)! ,.

[0100] The raw material to be melt-kneaded in the first mixing step (I) includes a part of the component [A] and at least a part of the component [B].

The amount of the component [B] used may be a part or the total amount. The amount of the component [B] used in the first mixing step (I) is preferably from 50 to 100% by weight based on the total amount of the component [B] to be contained in the heat-dissipating resin composition [S]. 100 mass%, More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%. The greater the amount of component [B] used, the better the heat dissipation of the resin composition [S] obtained after the second mixing step.

In addition, the amount of the component [A] used is any of the above-mentioned component [A] to be contained in the heat-dissipating resin composition [S], when only one type is used, or when two or more types are used. However, a part of the above component [A] is used instead of the total amount. The proportion is selected depending on the amount of the component [B] used in the heat-dissipating resin composition [S]. In order to efficiently advance the melt-kneading in the first mixing step (I), the above-mentioned components [A] and The amount of [B] used is usually in the range of 5 to 100 parts by mass of the above component [B] with respect to 100 parts by mass of the component [A] used in the first mixing step (I). Selected as

When the component [A] is only one kind of thermoplastic resin, rubber reinforced resin, polycarbonate resin, olefin resin, polyester resin, polyamide resin and the like can be used.

In addition, when the component [A] contains two or more thermoplastic resins, examples of combinations suitable for the first production method of the present invention are shown below.

(1) Rubber reinforced resin and polycarbonate resin

(2) Rubber reinforced resin and polyester resin

(3) Polyester resin and polycarbonate resin

The kneading method in the first mixing step (I) may be a method of kneading the raw materials with an extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, or the like. With respect to the kneading conditions, the raw material charging method is not particularly limited, and the components may be mixed and then supplied to the kneader, or may be divided into multiple stages and supplied to the kneader. The kneading temperature is appropriately selected according to the type of the component [A], the blending ratio of the components [A] and [B], and the like.

[0101] Next, the raw materials to be melt kneaded in the second mixing step (I) are the kneaded product (I) obtained in the first mixing step (I), the remainder of the component [A], and the above And the remainder of component [B]. In the first mixing step (I), when the total amount of the component [B] to be contained in the heat-dissipating resin composition [S] is used, the raw material is mixed with the kneaded product (I). And the remainder of the component [A]. The kneading method and conditions can be the same as those in the first mixing step (I).

[0102] As described above, the first production method of the present invention includes the first mixing step (I) and the second mixing step (I), thereby dissipating heat with excellent dispersibility of the component [B]. Can produce a molded product that is further superior in heat dissipation, impact resistance, molding processability, electromagnetic wave shielding properties, productivity, and nodling properties.

In the first production method of the present invention, when two or more kinds of thermoplastic resins are used as the component [A], one kind (the same) resin is used in the first mixing step ( I) and 2nd It is preferable to use the entire amount in either one of the mixing steps, rather than dividing it into both of the mixing steps (I). However, when there is a difference in the composition ratio of the plurality of resins contained in the component [A], for example, two kinds of resins (first resin and second resin) are used, and the composition ratio thereof is 1: 9. In such a case, the method is not limited to the above method.

When a thermoplastic resin having high compatibility with the component [B], such as a polycarbonate resin, is used as the component [A], the first mixing step of the first production method of the present invention ( In I), it is particularly preferable to use the thermoplastic resin.

In the first production method of the present invention, preferably, as the first mixing step (I), the whole amount of the component [B] is used, and the usage ratios of the component [A] and the component [B] are respectively set. 50 to 95% by mass and 50 to 5% by mass (however, the total of these is 100% by mass), and the second mixing step (I) is the first mixing step (I). This is a method of melt-kneading the kneaded product (I) obtained by the above and the remainder of the component [A].

To illustrate this method more specifically, in the first mixing step (I), the total amount of the component [B] is used, and the component [8] is 50 to 95% by mass (preferably 60 to 95% by mass, more (Preferably 65 to 90% by mass) and the above component [B] 5 to 50% by mass (preferably 5 to 40% by mass, more preferably 10 to 35% by mass) (however, the total of these is 100% by mass) In the second mixing step (I), and 100 parts by mass of the kneaded product (1) and the remaining component [ A] 0.! To 4,950 parts by mass (preferably 0 .;! To 4,000 parts by mass, more preferably 0.;! To 3,000 parts by mass). is there. In the first mixing step (I), if the content of the component [B] is less than 5% by mass, the heat conductivity and electromagnetic wave shielding property of the heat-dissipating resin composition [S] cannot be sufficiently obtained! /がある There is a case. On the other hand, when the content exceeds 50% by mass, it may be difficult to produce the kneaded product (I). Further, in the second mixing step (I), finally, a composition in which the content of the component [B] is from! To 80 parts by mass with respect to 100 parts by mass of the total amount of the component [A]. Thus, if the amount of the component [A] used is selected as S, and the amount of the component [A] used relative to 100 parts by mass of the kneaded product (1) is too small, the molding processability and resistance Impact may not be sufficient. On the other hand, if the amount used is too large, the heat conductivity and electromagnetic wave shielding properties of the heat-dissipating resin composition [S] may not be sufficiently obtained. [0104] Another method for producing the heat-dissipating resin composition [S] of the present invention (hereinafter referred to as "the second production method of the present invention") is a heat containing the rubber-reinforced resin and the polycarbonate resin in a predetermined ratio. A method for producing a heat dissipating resin composition [S1] in which the content of the carbon fiber structure [B] is from! To 80 parts by mass with respect to 100 parts by mass of the plastic resin [A]. A first mixing step (hereinafter referred to as “first mixing step (Π)”) in which the polycarbonate resin and at least a part of the carbon fiber structure [B] are melt-kneaded, and the first mixing step ( The kneaded product obtained by II) (hereinafter referred to as “kneaded product (ii)”), the rubber-reinforced resin, and the balance of the carbon fiber structure [B] (used as necessary); And a second mixing step (hereinafter referred to as “second mixing step (11)”).

In the second production method of the present invention, when an additive is used, it may be used in the first mixing step (II) and the second mixing step (II)! ,.

[0105] In the second production method of the present invention, the use ratio of the rubber-reinforced resin and the polycarbonate resin used as the component [A] is, from the viewpoint of melt kneadability, when the total of these is 100% by mass, 20 to 80% by mass and 80 to 20% by mass, preferably 20 to 75% by mass and 80 to 25% by mass, more preferably 25 to 75% by mass and 75 to 25% by mass, respectively.

[0106] The raw material to be melt-kneaded in the first mixing step (II) includes the polycarbonate resin and at least a part of the component [B].

The amount of the component [B] used may be a part or the total amount. The amount of the component [B] used in the first mixing step (II) is preferably from 50 to 100% by weight based on the total amount of the component [B] contained in the heat-dissipating resin composition [S1]. 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass. The higher the amount of component [B] used, the better the heat dissipation of the resulting heat-dissipating resin composition [S 1].

In addition, the polycarbonate resin is usually used in the whole amount. However, particularly when the amount of the rubber-reinforced resin used in the second mixing step (II) is excessive, a part of the polycarbonate resin is added. You may use in 2 mixing process (II). That is, in order to efficiently promote the melt-kneading in the first mixing step (II), the usage ratio of the polycarbonate resin and the component [B] is the same as the poly force used in the first mixing step (II). The amount of the component [B] is usually 5 to 100 parts by mass with respect to 100 parts by mass of the boronate resin.

The kneading method of the first mixing step (II) can be the same as that of the first mixing step (I). The kneading temperature (usually 240 to 320 ° C, preferably 260 to 300 ° C).

Next, the raw material to be melt-kneaded in the second mixing step (II) includes the kneaded product (II) obtained in the first mixing step (II) and the rubber-reinforced resin. As described above, in the first mixing step (II), when the entire amount of the polycarbonate resin is not used, the remainder is included. The kneading method can be the same as in the first mixing step (ii). The kneading temperature is usually 230 to 280. C, preferably 240-260. C.

[0108] According to the second production method of the present invention, in the embodiment where the component [A] is the rubber-reinforced resin and the polycarbonate resin, the first mixing step (II) and the second mixing step (II) are performed. By preparing, a heat-dissipating resin composition [S1] excellent in dispersibility of the component [B] can be produced, and heat dissipation, impact resistance, molding processability, electromagnetic wave shielding properties, productivity, and hand It is possible to obtain a molded product with further excellent ringability. In particular, since it is considered that the compatibility between the component [B] and the polycarbonate resin is excellent, the melt kneading in the second mixing step (II) can proceed smoothly, and the resin has excellent heat dissipation. Manufacture the composition [S 1].

[0109] In the second production method of the present invention, preferably, as the first mixing step (II), the entire amount of the component [B] is used, and the usage ratios of the polycarbonate resin and the component [B] are respectively determined. 50 to 95% by mass and 50 to 5% by mass (however, the total of these is 100% by mass), and as the second mixing step (II), the first mixing step (II) This is a method of melt-kneading the obtained kneaded product and the rubber-reinforced resin.

To illustrate this method more specifically, in the first mixing step (I), the total amount of the component [B] is used, and the polycarbonate resin is 50 to 95% by mass (preferably 60 to 95% by mass, more preferably 65 to 90% by mass) and the above component [B] 5 to 50% by mass (preferably 5 to 40% by mass, more preferably 10 to 35% by mass) (however, the total of these is 100% by mass). After melt-kneading into a kneaded product (II) such as pellets and masterbatch, in the second mixing step (II), 100 parts by mass of the kneaded product (II) and the rubber-reinforced resin 0.; 950 mass Part (preferably 0.;! To 4,000 parts by mass, more preferably 0.;! To 3,000 parts by mass). In the first mixing step (II), if the content of the component [B] is less than 5% by mass, the heat dissipation resin composition [S1] may not have sufficient thermal conductivity and electromagnetic shielding properties. is there. On the other hand, when the content exceeds 50% by mass, it may be difficult to produce the kneaded product (II). Further, in the second mixing step (II), a composition in which the content of the component [B] is 1 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polycarbonate resin and the rubber reinforced resin; Thus, the amount of the rubber-reinforced resin used is selected. However, if the amount of the rubber-reinforced resin used is too small relative to 100 parts by mass of the kneaded product (II), the moldability and impact resistance are sufficient. It may not be. On the other hand, if the amount used is too large, the heat conductivity and electromagnetic wave shielding properties of the heat-dissipating resin composition [S1] may not be sufficiently obtained.

[0110] The heat-dissipating resin composition [S] of the present invention can be made to contain additives depending on the purpose and application. Examples of the additive include a filler, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an antiaging agent, a plasticizer, a lubricant, an antibacterial agent, and a coloring agent.

[0111] Fillers include heavy calcium carbonate, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, sintered clay, neurophyllite clay, silane treatment Clay, Synthetic calcium silicate, Synthetic magnesium catenate, Synthetic quinolate, Magnesium carbonate, Magnesium hydroxide, Ferrine, Sericite, Talc, Fine talc, Wollastonite, Zeolite, Zonolite, Asbestos, PMF (Processed Mineral Fiber), pepper, sepiolite, potassium titanate, elestadite, gypsum fiber, glass balun, silica balun, hydrite talcite, flyer schbaln, carbon balun, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide Or the like. These can be used alone or in combination of two or more.

The content of the filler is usually 1 to 30 parts by mass, preferably 2 to 25 parts by mass, more preferably 2 to 20 parts by mass when the component [A] is 100 parts by mass.

[0112] Examples of the heat stabilizer include phosphites, hindered phenols, and thioethers. These can be used alone or in combination of two or more. The content of the heat stabilizer is usually 0.01 to 5 parts by mass when the component [A] is 100 parts by mass.

[0113] Examples of the antioxidant include phosphites, hindered amines, hydroquinones, hindered phenols, sulfur-containing compounds and the like. These can be used alone or in combination of two or more.

The content of the antioxidant is usually from 0.0;! To 5 parts by mass, preferably from 0.05 to 3 parts by mass, more preferably from 0.00 when the component [A] is 100 parts by mass. ! ~ 2 parts by mass.

[0114] Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic ester, and metal complex salts. These can be used singly or in combination of two or more. The content of the ultraviolet absorber is usually 0.0;! To 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0, when the component [A] is 100 parts by mass. ; ~~ 5 parts by mass.

[0115] Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.

[0116] Examples of the organic flame retardant include brominated epoxy resin, brominated alkyltriazine compound, brominated bisphenol epoxy resin, brominated bisphenol phenol resin, brominated bisphenol polycarbonate resin, Halogenated flame retardants such as brominated polystyrene resin, brominated crosslinked polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenol ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, Triethyl phosphate, Tripropinorephosphate, Tributinorephosphate, Tripentinorephosphate, Trihexinorephosphate, Tricyclohexinorephosphate, Tripheninophosphate, Tricredinole phosphate Phosphate esters such as fete, trixyleninophosphate, credinoresinenophosphate, dicresinorefeninophosphate, dimethylenoretinophosphate, methinoresive chinorephosphate, ethenoresipropyl phosphate, hydroxyphenyl diphenyl phosphate And compounds obtained by modifying these with various substituents, various condensed phosphoric ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing a phosphorus element and a nitrogen element; polytetrafluoroethylene, and the like. These can be used alone or in combination of two or more. Can be used together.

[0117] Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based, molybdenum-based, zinc stannate, guanidine salt, silicone-based, and phosphazene-based compounds. It is done. These can be used alone or in combination of two or more.

[0118] Examples of the reactive flame retardant include tetrabromobisphenol A, dibromophenol daricidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol , Poly (pentabromobenzyl polytalylate), chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dib-mouthed mocresyl glycidyl ether, and the like. These can be used alone or in combination of two or more.

Yes

[0119] The content of the flame retardant is usually 1 to 30 parts by mass, preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass when the component [A] is 100 parts by mass. is there.

[0120] When the heat-radiating resin composition of the present invention contains a flame retardant, it is preferable to use a flame retardant aid. These flame retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide. And ammonium polyphosphate, tin oxide, iron oxide and the like. These can be used alone or in combination of two or more. Silicone oil can be added to improve flame retardancy.

[0121] Anti-aging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Examples thereof include compounds, thiobisphenol compounds, hindered phenol compounds, phosphorous acid ester compounds, imidazole compounds, dithiouric acid nickel salt compounds, and phosphoric acid compounds. These can be used alone or in combination of two or more. The content of the anti-aging agent is usually 0.0;! To 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0. ! ~ 5 parts by mass.

[0122] Examples of the plasticizer include dimethyl phthalate, jetyl phthalate, dibutyl phthalate, disobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di (2-ethynolehexyl) phthalate, diisooctyl phthalate, Phthanolates such as diisodecyl phthalate; dimethyl adipate, diisobutyl adipate, di (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di (2-ethylhexyl) azelate, diisooctyl Fatty acid esters such as azelate, diisobutinorebagate, dibutinorebaevagate, di (2-ethinorehexinole) sebagate, dioctylsebagate; trimellitic acid isodecyl ester, trimelli Trimellitic acid esters such as octyl octyl ester, trimellitic acid n octyl ester, and isononyl ester of trimellitic acid; G (2-ethylhexyl) fumarate, jetylene glycol monooleate, glyceryl monoricinoleate, Examples include trilaurinole phosphate, tristearyl phosphate, tri (2-ethylhexyl) phosphate, epoxidized soybean oil, and polyester ester. These can be used alone or in combination of two or more.

The content of the plasticizer is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 1 to 10 parts by mass when the component [A] is 100 parts by mass. is there.

[0123] Examples of the lubricant include fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid. Polydaricol ester

, Aliphatic alcohol, polyhydric alcohol, polydaricol, polyglycerol, metal sarcophagus, silicone, modified silicone, and the like. These can be used alone or in combination of two or more.

The content of the lubricant is usually 0.;! To 5 parts by mass when the component [A] is 100 parts by mass.

[0124] Examples of antibacterial agents include zeolite zeolites such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver silica gel, glass antibacterial agents, and calcium phosphate. Inorganic antibacterial agents such as antibacterial agents, zirconium phosphate antibacterial agents, silicate antibacterial agents such as silver magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc. Release agent, halogenated aromatic compound, rhodopropargyl derivative, isocyanato compound, isothiazolinone derivative, torino, romethylthio compound, quaternary ammonium salt, biguanide compound, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, Organic antibacterial agents such as carboxylic acids and organometallic compounds; inorganic / organic hybrid antibacterial agents; natural antibacterial agents and the like. These can be used alone or in combination of two or more.

The content of the antibacterial agent is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0. 5 parts by mass.

[0125] Examples of the colorant include organic dyes, inorganic pigments, and organic pigments. These can be used alone or in combination of two or more.

[0126] The heat conductivity of the heat-dissipating resin composition [S] of the present invention is superior to that of the component [A] alone, and is preferably lower than the lower limit of the thermal conductivity obtained by the method shown in the following examples. Is lW / (m'K), more preferably 2.5 W / (mK), and even more preferably 3W / (mK). A preferable upper limit is 100 W / (m′K), and more preferably 50 W / (m′K). If this thermal conductivity is too small, sufficient heat dissipation cannot be obtained. For example, the movement speed of heat generated from the heat source may be slow, and cooling in the vicinity of the heat source may be difficult to proceed.

[0127] The Charpy impact strength of the heat-dissipating resin composition [S] of the present invention is preferably 3.5 kj / m ² or more, more preferably 5 kj / m ² or more, and further preferably 6 kj / m ² or more. . If this Charpy impact strength is too small, the impact resistance will be insufficient, and there are cases where the development to applications requiring impact strength is restricted.

[0128] The melt mass flow rate of the heat-dissipating resin composition [S] of the present invention is preferably 4 g / 10 min or more, more preferably 5 g / 10 min or more, and further preferably 6 g / 10 min or more. If the menoret mass flow rate is too small, the moldability will not be sufficient if the fluidity is insufficient, and the degree of freedom in the shape of the product used may be limited.

[0129] Furthermore, the heat-dissipating resin composition [S] of the present invention has excellent electromagnetic shielding properties, and the electromagnetic shielding properties at 100 MHz are preferably 25 dB or more, more preferably 30 dB or more. (30 to 60 dB, particularly preferably (30 to 55 dB).

[0130] In the heat-dissipating resin composition [S] of the present invention, the thermal conductivity is 3 W / (m ′ K) or more, the Charpy impact strength is 5 kj / m ² or more, and the melt mass flow rate is 5 g / By providing the performance of 10 minutes or more, it is possible to obtain a molded product that exhibits a high balance of heat dissipation, molding processability and impact resistance. As an example of the composition of the composition that gives such a molded article, it contains the above-mentioned component [A] containing a rubber-reinforced resin and a polycarbonate resin, and the above-mentioned component [B], and the rubber-reinforced resin and the polycarbonate resin. The content is preferably 25 to 75% by mass and 75 to 25% by mass, particularly preferably 35 to 75% by mass and 65 to 25% by mass, respectively (however, the total of these is 100% by mass). It is an aspect.

[0131] Next, the component [C] contained in the heat-dissipating resin composition [T] of the present invention is not particularly limited with respect to the type, shape, size (aspect ratio, weight average particle diameter, etc.), and the like. . The type may be either a graphite or / 3—graphite. These may be combined. Furthermore, either natural graphite or artificial graphite may be used. These may be combined.

The natural graphite is not particularly limited as long as no band is observed at the wavelength per lseocnT ¹ by laser Raman measurement, and examples thereof include flaky graphite, massive graphite, and soil graphite.

Furthermore, the shape of the component [c] is controlled by the force s such as powder, granule, plate, scale, strip, column, cone, needle or the like.

In addition, with respect to the size of the component [C], the aspect ratio is preferably 1 to 20, and the weight average particle size is preferably;! To 200 m.

[0132] Preferred examples of the component [C] are as follows.

[1] Graphite particles having an aspect ratio of 10 to 20, a weight average particle diameter of 10 to 200 111, and a fixed carbon content of 98% by mass or more (hereinafter referred to as “graphite particles (Cl)”. That said.)

[2] Graphite particles having an aspect ratio of 3 or less, a weight average particle diameter of 1 to 70, and a fixed carbon content of 98% by mass or more (hereinafter referred to as “graphite particles (C2)”). .

[0133] In the graphite particles (C 1) and (C2), since the physical properties are in the above ranges, the heat release and thermal conductivity are further improved. In particular, when a molded product is used, The difference in thermal conductivity is small in the flow direction and the perpendicular direction.

The aspect ratio can be calculated by measuring each length in the vertical and horizontal directions using an electron microscope or the like. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like. The “weight average particle diameter” according to the present invention means the particle diameter (D) obtained by measuring the particle size distribution when the cumulative weight is 50%. The amount of fixed carbon is JIS M85.

50

It can be measured according to 11.

The above graphite particles (C1) and (C2) can be used in combination.

[0134] The aspect ratio of the graphite particles (C1) is 10 to 20, preferably 12 to 18;

Weight average particle diameter (10 to 200 to 111, preferably 15 to 80 to m. The amount of fixed carbon is 98% by mass or more, preferably 98.5% by mass or more. More preferably, it is 99 mass% or more.

[0135] Further, for the graphite particles (C1), the ratio D / Ό of the particle diameters D and D when the cumulative weights obtained by measuring the particle size distribution are 20% and 80%, respectively, is Like

20 80 80 20 or 2 to 12, more preferably 2.5 to 10. Graphite with ratio D / reducing force less than ¾

80 20

If particles are used, it may be difficult to produce the heat-dissipating resin composition [τ], and the thermal conductivity may be insufficient. On the other hand, if the ratio D / repulsive force S 12 is exceeded, impact resistance and surface appearance

80 20

May not be enough.

[0136] The shape of the graphite particles (C1) is preferably flake graphite.

The graphite particles (C1) can be used singly or in combination of two or more.

[0137] The aspect ratio of the graphite particles (C2) is 3 or less, preferably 1 to 3.

The weight average particle diameter is 10 to 70 111, preferably 15 to 60 111. The amount of fixed carbon is 98% by mass or more, preferably 98.5% by mass or more, and more preferably 99% by mass or more.

For the above graphite particles (C2), the ratio D / Ό of the particle diameters D and D when the cumulative weights obtained by measuring the particle size distribution are 20% and 80%, respectively, is Especially limited

20 80 80 20

Not.

As the shape of the graphite particles (C2), spherical graphite is preferred! /. The graphite particles (C2) can be used singly or in combination of two or more.

[0138] In the heat-dissipating resin composition [T] of the present invention, the content of the component [C] is preferably 10 to 300 parts by mass when the component [A] is 100 parts by mass, More preferably 10 to 150 parts by mass, still more preferably 10 to 100 parts by mass, particularly preferably 10 to 50 parts by mass. If the content of the component [C] is too small, the thermal conductivity and electromagnetic wave shielding properties may not be sufficient. On the other hand, if the amount of the component [C] is too large, productivity, molding processability and surface appearance of the molded product may be deteriorated.

[0139] The case where the component [C] is the graphite particles (C1) and the case of the graphite particles (C2) will be described. When the graphite particles (C1) are used as the component [C], a heat-dissipating resin composition having better thermal conductivity than the graphite particles (C2) can be obtained. On the other hand, when the graphite particles (C2) are used as the component [C], a heat-dissipating resin composition superior in molding processability and impact resistance compared to the graphite particles (C1) can be obtained. Therefore, when the component [C] contains both of the above graphite particles (C1) and (C2), all of heat release, molding processability, impact resistance, thermal conductivity and electromagnetic wave shielding properties are highly developed. A heat-dissipating heat-dissipating resin composition can be obtained. The preferred content of graphite particles (C1) and (C2) is:! ~ 99 mass% and 99 ~;! Mass%, respectively, when the total is 100 mass%. Preferably they are 5-95 mass% and 95-5 mass%, More preferably, they are 10-90 mass% and 90-; 10 mass%.

[0140] The heat-dissipating resin composition [T] of the present invention containing the above graphite particles (C1) and (C2) as the component [C], and the component [C] contained in the molded product thereof are known. The aspect ratio and the average particle diameter (specifically, the number average particle diameter) can be determined by observing the test piece prepared by this method with an electron microscope or the like. The above aspect ratio and average particle diameter are usually the same as the aspect ratio and weight average particle diameter of the component [C] before blending, respectively.

[0141] In the heat-dissipating resin composition [T] of the present invention, the content ratios of the component [B] and the component [C] are as follows when the total of these contents is 100% by mass: 20 to 95% by weight and preferably 80 to 5% by weight, more preferably 40 to 90% by weight and 60 to 10% by weight. % By weight, particularly preferably 50 to 90% by weight and 50 to 10% by weight. If the content ratio of the above components [B] and [C] is in the above range, the heat dissipation is excellent, the balance between molding processability and impact resistance is excellent, and furthermore, the thermal conductivity and electromagnetic wave shielding properties are also achieved. Excellent.

[0142] Preferred compositions for the heat-dissipating resin composition [T] of the present invention are exemplified below.

[i] A yarn and composition in which component [A] is a rubber-reinforced resin and component [C] is graphite particles (C1) and / or (C2).

[ii] A composition wherein component [A] is a polycarbonate resin and component [C] is graphite particles (C1) and / or (C2).

[iii] Component [A] is a rubber-reinforced resin and a polycarbonate resin (preferred content ratio;;! to 80 mass% and 99 to 20 mass%), and component [C] is graphite particles (C1) and / or (C2 ) Is a thread and a composition.

[0143] The heat-dissipating resin composition [T] of the present invention is also a filler, heat stabilizer, antioxidant, ultraviolet absorber, flame retardant, anti-aging agent, plasticizer, lubricant, antibacterial agent, colorant, etc. It is possible to make it contain the additive. The content of each additive relative to the component [A] can be the same as that of the heat-dissipating resin composition [S].

[0144] The heat conductivity of the heat-dissipating resin composition [T] of the present invention is superior to that of the above-mentioned component [A] alone. The preferred lower limit of the thermal conductivity obtained by the method shown in the following Examples Is 1.5 W / (mK), more preferably 2.5 W / (mK), still more preferably 3 W / (mK), and particularly preferably 3.5 W / (m'K). A preferable upper limit is 100 W / (m′K), and more preferably 50 W / (m * K). If this thermal conductivity is too small, sufficient heat dissipation cannot be obtained. For example, the movement speed of the heat generated by the heat source may be slow, and cooling near the heat source may not proceed easily.

[0145] The Charpy impact strength of the heat-dissipating resin composition [T] of the present invention is the type of the component [A], the type and content of the component [B], and the type of the component [C]. And the force depending on the content thereof is preferably 1. Okj / m ² or more, more preferably 3. Okj / m ² or more, further preferably 3.5 kj / m ² or more, and particularly preferably 5 kj / m ² or more. If the Charpy impact strength is too small, the impact resistance will be insufficient, and there are cases where the development to applications requiring impact strength is restricted. The Charpy impact strength is, for example, the preferred embodiment [i] In [iii], it is possible to obtain power S.

[0146] Melt mass flow rate of heat-dissipating resin composition [T] of the present invention (in accordance with IS01133, temperature

240 ° C and load 196N) depends on the type of component [A], the type and content of component [B], and the type and content of component [C]. 3 g / l 0 min or more, more preferably 4 g / 10 min or more, still more preferably 5 g / 10 min or more. If the melt mass flow rate is too small, moldability that is not sufficient for fluidity is deteriorated, and the degree of freedom of product shape to be used may be limited. The melt mass flow rate can be obtained, for example, in the preferred embodiments [i] to [iii].

[0147] Further, the heat-dissipating resin composition [T] of the present invention is also excellent in electromagnetic shielding properties, and the electromagnetic shielding properties at 100 MHz are preferably 15 dB or more, more preferably 20 dB or more, and further preferably 25 dB or more. More preferably, it is 30 dB or more. The upper limit is usually 60 dB.

[0148] The heat-dissipating resin composition [T] of the present invention is a raw material component such as components [A], [B] and [C] in various extruders, Banbury mixers, kneaders, rolls, feeder rulers, etc. And can be produced by kneading under heating. Further, this composition [T] is a method of kneading the heat-dissipating resin composition [S] of the present invention (including the heat-dissipating resin composition [S1]), the component [C], etc. It can also be produced by a method of kneading the composition [S], components [A] and [C], a modified method of the heat-dissipating resin composition [S], and the like. The method of using the raw material components is not particularly limited, and each component may be mixed and kneaded in multiple steps, or may be mixed and mixed.

[0149] The molded article of the present invention comprises the above heat-dissipating resin composition [S] or [T] of the present invention, or a component thereof, an injection molding apparatus, a sheet extrusion molding apparatus, a profile extrusion molding apparatus, a hollow Manufacturing force by processing with known molding equipment such as molding equipment, compression molding equipment, vacuum molding equipment, foam molding equipment, blow molding equipment, injection compression molding equipment, gas assist molding equipment, water assist molding equipment S it can. That is, the molded product of the present invention contains the heat-dissipating resin composition [S] or [Τ] of the present invention. Then, as described above, the molded product containing the components [Α], [Β] and [C], that is, containing the heat-dissipating resin composition [T] is observed with an electron microscope or the like, and the component [ C) aspect ratio and average particle diameter Particle diameter) can be obtained. The obtained aspect ratio and average particle diameter are usually the same as the aspect ratio and weight average particle diameter of the component [c] before blending, respectively.

[0150] When the heat-dissipating resin composition [S] is processed using the molding apparatus, the molding temperature and the mold temperature include the type of the component [A], the content of the components [A] and [B]. It is selected according to the ratio. Further, when processing the heat-dissipating resin composition [T], the molding temperature and the mold temperature depend on the type of the component [A], the content ratio of the components [A], [B] and [C], etc. Selected.

For example, when the component [A] contains a rubber reinforced resin, the cylinder temperature during molding is usually 220 to 300 ° C, preferably 230 to 280 ° C. The mold temperature is usually 50-80. C.

When the component [A] contains a polycarbonate resin, the cylinder temperature at the time of molding is usually 240 to 320 ° C, preferably 260 to 300 ° C. The mold temperature is usually 50-80. C.

Further, when the component [A] contains a rubber-reinforced resin and a polycarbonate resin, the cylinder temperature at the time of molding is usually 230 to 280 ° C, preferably 240 to 260 ° C. The mold temperature is usually 50 to 80 ° C.

In any of the above cases, when the molded product is large, the cylinder temperature is generally set higher than the above temperature.

[0151] The molded product of the present invention is the above heat-dissipating resin composition [S] or [T] of the present invention, or other thermoplastic resin composition (ABS resin, olefin resin, polycarbonate resin, polyamide resin). It is possible to force the member made of a composition comprising a polyester resin or the like to be disposed on the surface or the like. Such an article can be manufactured using a multicolor molding apparatus including two-color molding. It can also be an article integrated with a metal member such as aluminum or copper.

[0152] The molded product of the present invention may be provided with a through hole, a groove, a concave portion, and the like at an arbitrary place in accordance with the purpose and application. When the thin portion is provided, the thickness is preferably 1 mm or more, more preferably 2 mm or more.

[0153] The heat-dissipating resin composition comprises molding processability, impact strength, thermal conductivity, and electromagnetic wave sealing. Personal computer with built-in electronic components that generate heat and electromagnetic waves, housings for mobile phones, substrates for mounting electronic components, panels that require heat dissipation and electromagnetic shielding, and CPU It is suitable as a material for heat sinks, radiating fins, fans, packings, etc.

Example

[0154] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist of the present invention. Unless otherwise specified, parts and percentages are on a mass basis.

[0155] 1. Raw material components

The raw material components used in the production of the heat radiating resin composition are shown below.

[0156] 1-1 component (A)

(1) Gen-based rubber reinforced Bull resin (A— 1)

The content of polybutadiene rubber obtained by emulsion polymerization of styrene and acrylonitrile in the presence of latex containing polybutadiene rubber particles having a weight average molecular weight of 280 nm and toluene-insoluble content of 80% as a gen-based rubbery polymer is 41. A gen-based rubber reinforced bull resin with 5% styrene unit strength of 3.5% and acrylonitrile unit content of 15% was used. The graft rate of this gen-based rubber-reinforced bulle resin is 55%, and the intrinsic viscosity [7]] (measured in methyl ethyl ketone at 30 ° C) of acetone-soluble component is 0 · 45 dl / g.

[0157] (2) Acrylonitrile 'styrene resin (A-2)

A copolymer having a styrene unit amount of 74.5% and an acrylonitrile unit amount of 25.5% was used. Intrinsic viscosity [7]] (measured in methyl ethyl ketone at 30 ° C) is 0 · 60dl / g

[0158] (3) Polycarbonate resin (A— 3)

“NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The viscosity average molecular weight by GPC is 22,000.

[0159] (4) ABS resin (A— 4)

“Techno ABS 330” (trade name) manufactured by Techno Polymer Co., Ltd. was used.

[0160] 1 2 · Component [B] A carbon fiber structure “MWNT (Malti Wall Carbon)” (trade name) manufactured by Nano Carbon Technologies was used. The outer diameter of the carbon fiber part is 20 to 60 nm, and the average equivalent circle diameter (area standard) is several to several tens of meters.

[0161] 1 3. Ingredient [C]

(1) flaky graphite (C 1)

“HF-150A” (trade name) manufactured by Chuetsu Graphite Industries Co., Ltd. was used. The aspect ratio is 16, the weight average particle size is 161 m, and the fixed carbon content is 99.8%. And D / Ό is 2.7

80 20

(2) Spheroidal graphite (C 2)

“WF-015” (trade name) manufactured by Chuetsu Graphite Industries Co., Ltd. was used. The aspect ratio is 1, the weight average particle size is 16.8μΐ ^ the fixed carbon content is 99.7%. And D / Ό is 1.7

80 20

Yes

[0162] 1-4. Linear carbon fiber (Ε— 1)

As a comparative example, a vapor grown carbon fiber “VGCF” (trade name) manufactured by Showa Denko KK was used. The average fiber diameter is 150 nm and the average fiber length is 10 μm.

[0163] 1-5. Masterbatch

(l) MB-l

A master batch obtained by melting and kneading 80% of the polycarbonate resin (A-3) and 20% of the component [B] at 280 ° C. was used.

[0164] (2) MB— 2

A master batch obtained by melt-kneading 85% of the above 883 resin (8-4) and 15% of the above component [B] at 260 ° C. was used.

[0165] (3) MB— 3

A master batch obtained by melting and kneading 90% of the ABS resin (A-4) and 10% of the component [B] at 260 ° C. was used.

[0166] 1— 6. Additive

(1) Flame retardant (FR)

Using aromatic condensed phosphate ester flame retardant “PX-200” (trade name) manufactured by Daihachi Chemical Co., Ltd. It was.

(2) Antioxidant (AO— 1)

The phosphite antioxidant “ADK STAB PEP-36” (trade name) manufactured by Ade Riki Co., Ltd. was used.

(3) Antioxidant (AO-2)

The hindered phenolic antioxidant “Adekastab AO-60” (trade name) manufactured by Ade Riki Co., Ltd. was used.

[0167] 2. Evaluation items of heat-dissipating resin composition

(1) Thermal conductivity

Using pellets made of a heat-dissipating resin composition, the melt is located at the center of the bottom surface of a mold (mold temperature: 50 to 80 ° C) with a cylindrical cavity space with a diameter of 10 mm and a length of 50 mm. A cylinder with a diameter of 10 mm and a length of 50 mm was produced by injection molding from the gate. After that, it was cut out in a substantially central part in the length direction so as to be a disc having a thickness of 1.5 mm, and this was used as a test piece (diameter 10 mm and thickness 1.5 mm). In order to measure the thermal conductivity in the flow direction of the heat-dissipating resin composition, a probe is applied to each of the upper and lower surfaces of this test piece, and the laser flash method thermal constant measuring device “TR-7000R” manufactured by ULVAC-RIKO. The thermal conductivity at room temperature (25 ° C.) was measured using a mold, and the unit of the measured value was W / (mK).

[0168] (2) Charpy impact strength

A test piece was produced using an injection molding machine “J-100E type” manufactured by JSW, and Charpy impact strength (Edgewise Impact, with notch) was measured according to IS0179 under the following conditions. The unit of measurement value is kj / m ² .

Specimen type; Type 1

Notch type; Type A

Load ； 2J

Temperature; room temperature

[0169] (3) Surface resistivity

The test piece (diameter lOOmmX thickness 2mm disc) is manufactured by Toshiba Machine Co., Ltd. EP type "was prepared and measured according to JIS K6911-1995. The resistance value was measured by using each measuring instrument shown in Table 1 according to the value. The unit of resistance is Ω

[table 1]

[0171] (4) Tensile elongation

A test piece was prepared using an injection molding machine “J-100E type” manufactured by JSW, and measured using a precision universal testing machine “Autograph AG5000E type” manufactured by Shimadzu Corporation according to IS0527. The unit of measurement is% (distortion).

[0172] (5) Melt mass flow rate

According to ISO 1133, measurement was performed under the conditions of a measurement temperature of 240 ° C and a load of 98N and 196N. The unit of measurement is g / 10 minutes.

[0173] (6) Thermal deformation temperature

A test piece was prepared using an injection molding machine “J-100E type” manufactured by JSW, and measured under a load of 1.80 MPa in accordance with IS075. The unit of measurement is ° C.

[0174] (7) Electromagnetic shielding

Using the spectrum analyzer “R3361A type” and “TR1730A type” manufactured by Advantest Corporation, the electromagnetic wave reflectivity at a frequency of 100 MHz was measured, and the electromagnetic wave shielding property was evaluated. The unit of measurement is dB. The test piece was prepared by injection molding using a mold having a flat plate type cavity of 150 mm length × 150 mm width × 3 mm thickness.

In general, the electromagnetic shielding effect is an index of how much incident electromagnetic wave energy can be attenuated, and the standard is as follows.

0 ~;! OdB; almost no electromagnetic shielding effect! /. 10 to 30 dB; minimum level of electromagnetic shielding effect.

30-60dB; electromagnetic wave shielding effect is an average level.

60-90dB; There is a considerable electromagnetic shielding effect.

90dB or more: Highest grade of electromagnetic shielding effect.

[0175] (8) Thermal fogging test

To prevent the influence of convection in a room at a temperature of 25 ° C, an acrylic resin cover with a height of lm and a width of lm is installed, and a polycarbonate (PC) frame as shown in Fig. 1 is installed at the center. Insert the flat plate (symbol 2) (150mm x 150mm x 3mm) to be used for evaluation into the four sides (bottom, top, and both sides) of the frame composed of the material (symbol 1). Formed. The front and rear surfaces of this box are made of PC walls. Then, install a silicone rubber heater (reference 3) (lOOmmXlOOmm X l.7mm) in the center of the bottom of the box, energize the silicon rubber heater 1 (reference 3) at a voltage of 40V (32W), and after 60 minutes, Temperature at each measurement point in T1 (T1; silicon rubber heater surface, T2; back side of bottom surface, 10 mm away from side surface, T3: 75.Omm below top surface, 10 mm away from side surface) Was measured.

In this thermal cloud test, the heat dissipation is better as T2 is higher and T1 and T3 are lower. If the thermal conductivity of the resin is high, the heat generated from the heater is easy to conduct, so the T2 temperature tends to rise. In addition, the better the heat dissipation to the outside, the more heat is trapped in the box, and the T3 temperature becomes lower. Furthermore, the higher the heat conductivity of the resin and the better the heat dissipation, the more easily the heat generated from the heater is taken away, so the temperature of T1 tends to decrease.

[0176] 3. Production and Evaluation of Heat Dissipating Resin Composition (I)

Example 1 1 9 and Comparative Example 1 1 3

The raw material components in Table 2 and Table 3 were mixed using a Henschel mixer and then melt-kneaded (cylinder temperature 240 280 ° C) using a twin screw extruder. Subsequently, it pelletized and the heat-radiating resin composition was obtained. Various evaluations were performed on the obtained resin compositions, and the results are shown in Tables 2 and 3.

[0177] [Table 2] []

Table 2

* 1 The total amount of A—1, A_2 and A—4. * 2 Percentage for 100 parts of component [A].

Table 3

The total amount of A-1, A-2 and A-4.

Ingredient [A] is a ratio with respect to 100 parts.

[0179] From Table 3, Comparative Example 11 was an example containing no component [B], and the heat conductivity was low and the heat dissipation test result was insufficient, and the heat dissipation was inferior. Comparative Example 12 is an example where the content of component [B] is as small as 0.5 parts per 100 parts of 1S component [A], and the heat dissipation test results with a low thermal conductivity and sufficient heat dissipation It was inferior to. Comparative Example 13 is an example in which linear carbon fiber (E-1) was used in place of component [B], and the heat dissipation test result with low thermal conductivity was insufficient and the heat dissipation was inferior. . Moreover, it was also inferior in fluidity.

[0180] On the other hand, from Table 2, Examples 1 1 ;! to 1 3, 1 5 and 17 to;! 1 9 are excellent in heat conductivity and also have good heat dissipation test results. It was excellent. Furthermore, it was excellent in the balance of molding processability and impact resistance and electromagnetic shielding properties. In particular, Examples 11 and 12 exhibited a high balance of heat dissipation, molding processability and impact resistance.

Further, in both Example 12 and Example 15, the content of the component [B] is 13.6%. As an example, Example 1 2 using a masterbatch containing polycarbonate resin (PC) has better thermal conductivity than Example 15 using a masterbatch containing ABS resin. The This is presumed to be due to the higher compatibility of component [B] in the strength of S and the strength of the polycarbonate resin than in the ABS resin.

Examples 1-7 containing a flame retardant achieved flame retardancy V-0.

[0181] 4. Production and evaluation of heat-dissipating resin composition (II)

Example 2 — ;! ~ 2-8 and Comparative Example 2 — ;! ~ 2-3

The raw material components shown in Table 4 to Table 6 were mixed by a Henschel mixer and then melt-kneaded (cylinder temperature 240 to 280 ° C) using a twin screw extruder. Subsequently, it pelletized and the heat-radiating resin composition was obtained. Various evaluation was performed about the obtained resin composition, and the result was written together in Table 4-Table 6. FIG.

[0182] [Table 4]

Table 4

Ingredient [A] is a ratio with respect to 100 parts.

The sum of component [B] and component [C] was 100%.

Five] Table 5

* 1 Percentage of 100 parts of component [A].

* 2 The total of component [B] and component [G] was 100%.

6] Table 6

* 1 component !: A] The ratio to 100 parts.

* 2 The total of component [B] and component [C] was 100%.

[0185] From Table 6, Comparative Examples 2-1 and 2-2 are examples containing no component [C], and the heat conductivity was low and the electromagnetic wave shielding effect was poor. Comparative Examples 2-3 are also examples not containing the component [C], but the thermal conductivity was low and the fluidity was not sufficient.

[0186] On the other hand, from Table 4 and Table 5, Examples 2— ;! to 2-8 were excellent in heat dissipation due to their excellent thermal conductivity and good results of the hot flash test. Furthermore, it has excellent moldability and impact resistance balance, thermal conductivity and electromagnetic shielding properties. [0187] In addition, as a heat-dissipating resin composition having excellent heat dissipation, a good balance between molding processability and impact resistance, and also excellent in thermal conductivity and electromagnetic wave shielding properties, [A] thermoplastic resin , [B ′] carbon fiber structure, and [C] graphite particles, the content of the carbon fiber structure [Β ′] and the graphite particles [C] is the thermoplastic resin [A] When 100 parts by mass is used, compositions of !! to 80 parts by mass and 10 to 300 parts by mass, respectively, can be used.

Examples of the carbon fiber structure [B ′] include a carbon fiber portion whose outer diameter is not limited (for example, a carbon fiber portion having an outer diameter larger than 10 Onm; an outer diameter of 15 to; carbon fiber in the range of OOnm. And a structure having a bonding portion for bonding a large number of carbon fiber portions can be used.

The types and content ratios of the preferred! / ヽ thermoplastic resin [A] and the graphite particles [C] are the same as those of the heat dissipating resin composition of the present invention. Further, the preferable content ratio of the carbon fiber structure [B ′] can be the same as that of the carbon fiber structure [B] contained in the heat-dissipating resin composition of the present invention.

Industrial applicability

[0188] Since the heat-dissipating resin composition of the present invention is excellent in the balance between moldability and impact resistance, the degree of freedom of the shape of the product to be applied is high. In addition, it is possible to obtain a molded product that is more excellent in heat dissipation than a metal material and excellent in electromagnetic wave shielding properties. Therefore, it can be used as a housing, a substrate, a panel, a heat sink, a heating fin, a fan, a packing, and the like. These members are suitable for electronic components such as circuit boards, chips, thermal heads, motors, etc .; electronic devices such as televisions, radios, cameras, video cameras, audios, videos, lighting fixtures, etc. Suitable for housing, heat sink and fan for escape to outside; audio back panel; display plate fixing member such as liquid crystal and plasma television.

Claims

The scope of the claims

[1] [A] a thermoplastic resin, and [B] an outer diameter of 15 to; a carbon fiber part of OOnm and a joint part for joining a large number of carbon fiber parts, and having a three-dimensional network structure A carbon fiber structure having,

The heat-dissipating resin composition is characterized in that the content of the carbon fiber structure [B] is from! To 80 parts by mass when the thermoplastic resin [A] is 100 parts by mass.

[2] The thermoplastic resin [A] is a rubber-reinforced bull resin obtained by polymerizing a bull monomer (bl) containing an aromatic bull compound in the presence of a rubber polymer, or A rubber-reinforced resin that is a mixture of the rubber-reinforced bulle resin and a (co) polymer of the bulur monomer (b2), and a polycarbonate resin, and the rubber-reinforced resin And the content ratio of the polycarbonate resin is, respectively, !!-80 mass% and 99-20 mass% when the total of these contents is 100 mass%, respectively. Resin composition.

[3] A mixture or kneaded material comprising 50 to 95% by mass of the polycarbonate resin and 50 to 5% by mass of the carbon fiber structure [B] (however, the total of these is 100% by mass) and the rubber When the total of the polycarbonate resin and the rubber reinforced resin is 100 parts by mass, the content of the carbon fiber structure [B] is from! To 80 parts by mass. The heat-radiating resin composition according to claim 2.

[4] The composition according to any one of claims 1 to 3, further comprising a flame retardant, wherein the content of the flame retardant is from! To 30 parts by mass when the thermoplastic resin [A] is 100 parts by mass. A heat-dissipating resin composition according to claim 1.

[5] The heat-dissipating resin composition according to any one of claims 1 to 4, wherein the heat conductivity is 3 W / (m′K) or more.

6. The heat-dissipating resin composition according to any one of claims 1 to 5, wherein the Charpy impact strength is 5 kj / m ² or more and the melt mass flow rate is 5 g / 10 minutes or more.

7. The heat-dissipating resin composition according to any one of claims 1 to 6, wherein the electromagnetic wave shielding property at a frequency of 100 MHz is 30 dB or more.

[8] A method for producing the heat-dissipating resin composition according to claim 1, A first mixing step of melt-kneading a part of the thermoplastic resin [A] and at least a part of the carbon fiber structure [B];

A second mixing step in which the kneaded product obtained in the first mixing step, the remainder of the thermoplastic resin [A], and the remainder of the carbon fiber structure [B] are melt-kneaded;

A process for producing a heat-dissipating resin composition, comprising:

In the first mixing step, the total amount of the carbon fiber structure [B] is used, and the usage ratio of the thermoplastic resin [A] and the carbon fiber structure [B] is 50 to 95% by mass and 50 to 5% by mass (however, the total of these is 100% by mass), and in the second mixing step, the kneaded product obtained in the first mixing step and the thermoplastic resin [ The method for producing a heat-dissipating resin composition according to claim 8, wherein the remainder of A] is melt-kneaded.

A method for producing a heat-dissipating resin composition according to claim 2,

A first mixing step of melt-kneading the polycarbonate resin and at least a part of the carbon fiber structure [B];

A second mixing step of melt-kneading the kneaded product obtained in the first mixing step, the rubber-reinforced resin, and the remainder of the carbon fiber structure [B],

A process for producing a heat-dissipating resin composition, comprising:

In the first mixing step, the total amount of the carbon fiber structure [B] is used, and the usage ratios of the polycarbonate resin and the carbon fiber structure [B] are 50 to 95% by mass and 50 to 50%, respectively. In the second mixing step, the kneaded product obtained in the first mixing step and the rubber-reinforced resin are melted. The method for producing a heat-dissipating resin composition according to claim 10, wherein the heat-dissipating resin composition is kneaded. Furthermore, it contains [C] graphite particles, and the content of the graphite particles [C] is 10 to 300 parts by mass when the thermoplastic resin [A] is 100 parts by mass. The heat-radiating resin composition according to any one of the above.

13. The graphite particles [C] are graphite particles (C1) having an aspect ratio of 10 to 20, a weight average particle diameter of 10 to 200, and a fixed carbon content of 98% by mass or more. The heat-dissipating resin composition described in 1. 14. The heat dissipating resin composition according to claim 13, wherein the graphite particles (C1) have a scaly shape.

Yes

[15] Ratio of particle diameters D and D when cumulative weights obtained by measuring the particle size distribution of the graphite particles (C1) are 20% and 80%, respectively. Claim 1

20 80 80 20

The heat dissipating resin composition according to 3 or 14.

[16] The graphite particles [C] are graphite particles (C2) having an aspect ratio of 3 or less, a weight average particle diameter of !! to 70 111, and a fixed carbon content of 98% by mass or more. The heat-radiating resin composition according to claim 12.

[17] The graphite particle [C] includes the graphite particle (C1) and the graphite particle (C2).

The heat dissipating resin composition according to any one of 13 to 16.

[18] The content ratio of the carbon fiber structure [B] and the graphite particles [C] is 20 to 95% by mass and 80 to 5% by mass, respectively, when the total of these contents is 100% by mass. The heat-dissipating resin composition according to any one of claims 12 to 17, which is%.

[19] A molded article comprising the heat-dissipating resin composition according to any one of claims 1 to 7 and claims 12 to 18.