JP6431680B2 - Polyolefin resin composition - Google Patents

Description

  The present invention relates to a polyolefin resin composition. More specifically, the present invention relates to a polyolefin resin composition excellent in moldability and a molded body using the same, which can obtain a lightweight resin molded product while having flame retardancy and heat dissipation (high thermal conductivity).

In recent years, with the increase in functionality of electric and electronic devices such as mobile phones, personal computers, and televisions, the amount of heat generated from displays has increased, and heat dissipation technology has become a major issue. Moreover, in electrical and electronic equipment, it is necessary to convert metal parts into resins in order to reduce costs and weight. However, when using resin, the provision of flame retardancy and heat dissipation (high thermal conductivity) becomes a problem.
As a resin component used for electrical and electronic equipment, for example, in Patent Document 1, a thermoplastic resin composition containing an aromatic polyester resin and a conductive filler in a base material layer made of an aromatic polyester resin is used. A conductive plastic sheet is disclosed which is formed by laminating conductive layers to be used and used for packaging ICs and electronic device parts using ICs. In Patent Document 2, a thermoplastic resin composition comprising polyamide, polyphenylene ether and an impact modifier, and low temperature impact and fluidity are improved by adding polyphenylene ether to melted polyamide and melt kneading. Is disclosed.
In any of the above-mentioned patent documents, a technique for imparting flame retardancy and heat dissipation properties to an engineering plastic such as an aromatic polyester resin, polyamide, and polyphenylene ether has been proposed.

JP 2003-251778 A JP 2004-143242 A

  However, from the viewpoint of moldability, the above-described resin composition using engineering plastics requires high-temperature kneading and high-temperature molding, requires special equipment, can be injection-molded but is difficult to extrude. There was a problem that handling was difficult, and the specific gravity was large and it was difficult to reduce the weight.

  Then, this invention makes it a subject to provide the resin composition and molded object which were light in specific gravity compared with the case where an engineering plastic was used, and were excellent in the moldability, provided with a flame retardance and heat dissipation.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a polyolefin resin composition containing a heat conductive filler and a flame retardant in a specific amount with respect to a polyolefin resin.
That is, the present invention relates to the following polyolefin resin composition.

1. 100 parts by weight of the polyolefin resin to 160 parts by mass of 30 to the thermally conductive filler, 33 to 80 parts by weight of Ha androgenic flame retardant, and the flame retardant aid include from 0.05 to 24.15 parts by weight,
The heat conductive filler is a scaly graphite particle having a weight average particle diameter (D50) of 40 to 150 μm ,
The halogen flame retardant is tetrabromobisphenol A and derivatives thereof, tetrabromobisphenol S and derivatives thereof, ethylenebis (pentabromodiphenyl) and derivatives thereof, tris (bromoneopentyl) phosphate and derivatives thereof, ethylenebistetrabromophthalimide and its derivatives, and Ri der one or more selected tris (2,3-dibromopropyl) isocyanurate and derivatives thereof from,
A polyolefin resin composition, wherein the flame retardant aid is at least one selected from antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide,
The polyolefin resin composition whose thermal conductivity of the test piece for heat dissipation evaluation obtained with the injection molding machine of this resin composition is 1-8 W / m * K in the evaluation by the method based on ASTM E1461 .
2. 2. The polyolefin resin composition according to 1, wherein the polyolefin resin is a resin containing one or more selected from a polypropylene resin and a polyethylene resin.
3 . A molded article obtained by injection molding the polyolefin resin composition described in 1 or 2 above.
4 . 3. An extruded product obtained by extruding the polyolefin resin composition described in 1 or 2 above.
5 . 5. A molded product obtained by processing or molding the extruded product according to 4 .
6 . A pellet obtained from the polyolefin resin composition according to 1 or 2 above.

  According to the present invention, by adding a specific flame retardant and a heat conductive filler to a polyolefin-based resin, which is a general-purpose plastic, with a case where engineering plastic is used while having flame retardancy and heat dissipation (high heat conductivity) In comparison, it is possible to provide a resin composition and a molded body that are lightweight and excellent in moldability.

[Polyolefin resin]
As the polyolefin resin, for example, a polypropylene resin, a polyethylene resin, a polybutene resin, a polypentene resin, or the like can be used. Among these, from the viewpoint of moldability, low specific gravity, and chemical resistance, the polyolefin resin is preferably a resin containing one or more selected from polypropylene resins and polyethylene resins.
When this polyolefin resin contains two or more kinds of polyolefin resins, the mixing method is not particularly limited. For example, mixing involving copolymerization or mixing by melt kneading may be used.

As a polypropylene resin, it can be comprised by 1 type, or 2 or more types chosen from the homopolymer of propylene, the copolymer which has a propylene as a main component, etc.
Although there is no restriction | limiting in particular as a homopolymer of propylene, From the viewpoint of making it lightweight and excellent in a moldability, the propylene single weight whose melt mass flow rate in 230 degreeC and load 2.16kg is 0.1-200 g / 10min. From the viewpoint of the rigidity and impact resistance of the resin composition, it is more preferable that the melt mass flow rate at 230 ° C. and a load of 2.16 kg is 0.2 to 60 g / 10 min.

The copolymer having propylene as a main component is not particularly limited, and is, for example, a random copolymer of one or more α-olefins other than propylene and propylene, and other than propylene and propylene. Examples thereof include block copolymers with one or more α-olefins. Among copolymers mainly composed of propylene, a propylene copolymer having a melt mass flow rate of 0.1 to 200 g / 10 min at 230 ° C. and a load of 2.16 kg from the viewpoint of light weight and excellent moldability. Further, from the viewpoint of the rigidity and impact resistance of the resin composition, the melt mass flow rate at 230 ° C. and a load of 2.16 kg is more preferably 0.2 to 60 g / 10 min.
Examples of α-olefins other than propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.

As a polyethylene-type resin, it can be comprised by 1 type, or 2 or more types chosen from the homopolymer of ethylene, the copolymer which has ethylene as a main component, etc.
Examples of the homopolymer of ethylene include low-density polyethylene, linear low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. From the viewpoint of light weight and excellent moldability, the density is 0.910. An ethylene homopolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at ˜0.965 g / cm ³ , 190 ° C. and a load of 2.16 kg is preferred. If the melt mass flow rate at 190 ° C. and a load of 2.16 kg is within the above range, there is no risk of problems in the fluidity of the resin composition and the surface appearance of the molded article, and it is 0.01 to 60 g / 10 min. Is more preferable.

Examples of the copolymer containing ethylene as a main component include, for example, a random copolymer of one or more α-olefins other than ethylene and ethylene, and one or more of other than ethylene and ethylene. And a block copolymer with an α-olefin. Among copolymers containing ethylene as a main component, an ethylene copolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at 190 ° C. and a load of 2.16 kg from the viewpoint of light weight and excellent moldability. Is preferred. Moreover, if the melt mass flow rate at 190 ° C. and a load of 2.16 kg is within the above range, there is no risk of problems in the fluidity of the resin composition and the surface appearance of the molded body, and 0.01 to 60 g / 10 min. More preferably.
Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.

  In addition to the above-mentioned polyolefin resin, vinyl resin, diene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), and thermoplastic elastomer may be added. You may use it in combination of 2 or more types.

Examples of the vinyl resin include ethylene-vinyl acetate copolymer, (meth) acrylic resin [(meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. (Co) polymers of one or more monomers selected from 2-ethylhexyl and the like] and styrene resins [polystyrene, AS resin, ABS resin, styrene-butadiene resin, styrene-maleic anhydride resin, styrene -Acrylic ester resin, HIPS and the like]. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the diene rubber include butadiene rubber, butyl rubber, chloroprene rubber, isoprene rubber, nitrile rubber [acrylonitrile-butadiene copolymer and the like] and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the thermoplastic elastomer include styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), and styrene. -Isoprene-styrene block copolymer (SIS), styrene-isoprene rubber (SIR), styrene-ethylene-propylene-styrene block copolymer (SEPS), polystyrene-poly (ethylene / butylene) block copolymer, polystyrene- Examples thereof include poly (ethylene / propylene) block copolymers, styrene-ethylene-butylene-ethylene block copolymers, and derivatives obtained by hydrogenating these. These may be used individually by 1 type and may be used in combination of 2 or more type.

[Thermal conductive filler]
It does not specifically limit as a heat conductive filler, The filler which consists of various materials which show heat conductivity can be used. Among these, from the viewpoint of heat dissipation, it is preferable to use one or more selected from carbon black, graphite particles, carbon fiber, metal powder, metal oxide, and metal fiber, with low specific gravity and low Mohs hardness. From the viewpoint of preventing deterioration due to wear on the molding machine, it is more preferable to use graphite particles.
A heat conductive filler may be used individually by 1 type, and may be used in combination of 2 or more type. When mixing and using 2 or more types of combinations, it is not particularly limited, but a combination of graphite particles and carbon fibers can be used.

  Examples of the graphite particles include spherical graphite, scaly graphite, and earthy graphite. Among them, scaly graphite is preferable from the viewpoint of easy overlapping of the particles and easy development of heat dissipation. The graphite particles have a weight average particle diameter (D50) of 10 to 200 μm from the viewpoint of the appearance of the molded body, and in particular, the weight average particle diameter (D50) of 40 to 150 μm from the viewpoint of moldability. Is more preferable.

  The said weight average particle diameter (D50) can be measured by classifying with a JIS sieve, for example, measuring the weight of each particle size component with an electronic balance, and obtaining a weight distribution curve.

(Content ratio)
In the polyolefin resin composition of the present invention, the content ratio of the heat conductive filler is 30 to 200 parts by mass, preferably 50 to 180 parts by mass, and more preferably 80 to 160 parts by mass with respect to 100 parts by mass of the polyolefin resin. Part by mass. If the content ratio of the heat conductive filler is less than 30 parts by mass, the desired thermal conductivity cannot be obtained, and if it exceeds 200 parts by mass, the polyolefin resin composition cannot be obtained.

[Flame retardants]
The flame retardant is not particularly limited, and known ones can be used. From the viewpoint of achieving both weight reduction and flame retardancy, it is possible to use a halogen-based flame retardant and a non-halogen flame retardant excluding a hydroxide compound. preferable. A flame retardant may be used individually by 1 type and may be used in combination of 2 or more type.

Although it does not specifically limit as a halogen-type flame retardant, For example, tetrabromobisphenol A (TBA), ethylenebis (pentabromodiphenyl), ethylenebistetrabromophthalimide, dibromomethyl-dibromoscrohexane, tetrabromocyclooctane, hexabromo Cyclododecane, decabromodiphenyl oxide, tetradecabromodiphenoxybenzene, halogenated polycarbonate and (co) polymer of halogenated polycarbonate, oligomers thereof (TBA carbonate oligomer), decabromodiphenyl ether, TBA epoxy oligomer, halogenated polyolefin, Halogen-containing acrylic resin [halogenated polybenzyl (meth) acrylate resin such as poly (pentabromobenzyl (meth) acrylate) Brominated polybenzyl (meth) acrylates such as relate), homo- or copolymers of halogenated benzyl (meth) acrylates such as poly (pentachlorobenzyl (meth) acrylate), halogen-containing styrenic resins [eg halogenated] Polystyrene (halides obtained by halogenating styrene resins such as brominated polystyrene and chlorinated polystyrene, homo- or copolymers of halogenated styrene monomers), halogen-containing polycarbonate resins (eg, brominated) Polycarbonate, halogenated polycarbonate such as chlorinated polycarbonate], halogen-containing epoxy compounds [for example, bromine-containing epoxy resins (brominated epoxy resins, etc.), halogen-containing epoxy resins such as chlorinated epoxy resins [halogenated epoxy resins, etc.]; bromine Contains fu Halogen-containing phenoxy resins (halogenated phenoxy resins, etc.) such as nonoxy resins [brominated phenoxy resins, etc.], halogen-containing phosphate esters [for example, tris (bromoethyl) phosphate, tris (mono or dibromopropyl) phosphate, tris ( Mono- or dibromobutyl) phosphate, tris (mono to tribromoneopentyl) phosphate, bis (tribromoneopentyl) phenyl phosphate, bromine-containing phosphate esters such as tris (bromophenyl) phosphate, etc.], halogen-containing triazine compounds [for example Bromine-containing triazine compounds such as tris (tribromophenoxy) triazine], halogen-containing isocyanuric acid compounds [for example, tris (2,3-dibromopropyl) isocyanurate, tris (2,3,4) -Bromo-containing isocyanuric acid compounds such as tribromobutyl) isocyanurate and tris (pentabromobenzyl) isocyanurate], halogenated polyaryl ether compounds [for example, bis (octa to decabromodiphenyl ether, octa to decachlorodiphenyl ether, etc. Halogenated aryl) ether (eg, bis (halogenated phenyl) ether); halogen-containing polyphenylene oxide resin such as brominated polyphenylene ether], halogenated aromatic imide compound [eg, bromine such as ethylenebisbrominated phthalimide aromatic imide compound (e.g., bisimide compounds), etc.], halogenated bis-aryl compound [e.g., bis (halogenated C _6-10 aryl) such as brominated diphenyl; brominated bis diphenylmethane Halogenated C _6-10 aryl) C _1-4 alkane; brominated halogenated bisphenol such as bisphenol A or brominated polyester polymerized ethylene oxide adducts of derivatives thereof (halogenated bisphenols) and the like], halogen Kaabura Cyclic hydrocarbons [bridged saturated or unsaturated halogenated alicyclic hydrocarbons, such as halogenated polycycloalkadienes such as dodecachloropentacyclooctadeca-7,15-diene, etc.] and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the halogen-based flame retardants, tetrabromobisphenol A and its derivatives, tetrabromobisphenol S and its derivatives, ethylene bis (pentabromodiphenyl) and its derivatives, tris (bromoneopentyl) phosphate and its derivatives, ethylene bistetra Bromophthalimide and derivatives thereof, tris (2,3-dibromopropyl) isocyanurate and derivatives thereof are preferable, and ethylenebis (pentabromodiphenyl) is more preferable.

Non-halogen flame retardants are not particularly limited, but include, for example, phosphate compounds (for example, ammonium polyphosphate salt, melamine polyphosphate salt, piperazine polyphosphate salt, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate salt). Melamine polyphosphate, melamine orthophosphate, calcium phosphate, and magnesium phosphate, etc.) and their derivatives or mixtures thereof, melamine derivatives (eg, melamine, melamine cyanurate compound, melamine sulfate, melamine borate, etc.), red Phosphorus [including various types of surface-treated red phosphorus by organic compounds, inorganic compounds, etc.], silicone compounds [silicone oil, silicone rubber, silicone resin, etc.], and alkoxyimino group hindered amine compounds [imino group of piperidine ring > N—H) as long as it is a NOR-type hindered amine compound in which H is substituted with an alkoxyl group (—OR) and derivatives thereof, for example, N, N ′, N ′ ″-tris {2,4 -Bis [(1-hydrocarboxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine , N, N ′, N ″ -tris {2,4-bis [(1-hydrocarboxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazine-6 -Yl} -3,3'-ethylenediiminodipropylamine and its crosslinked derivatives, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1- Octyloxy , 2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, and bis (1-cyclohexyloxy-) 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate and the like] and derivatives thereof It is done. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among the non-halogen flame retardants, phosphate compounds and derivatives thereof or mixtures thereof, melamine sulfate, red phosphorus, alkoxyimino group hindered amine compounds and derivatives thereof are preferable, and phosphate compounds and derivatives thereof are more preferable.

  The halogen-based flame retardant and the non-halogen-based flame retardant may be used alone or in combination. When used by mixing, it is not particularly limited, but includes a combination of ethylenebispentabromodiphenyl and a phosphate compound.

(Content ratio)
In the polyolefin resin composition of the present invention, the content ratio of the flame retardant is 1 to 80 parts by mass, preferably 5 to 75 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin. Part. When the content ratio of the flame retardant is less than 1 part by mass, flame retardancy cannot be exhibited. Moreover, when it exceeds 80 mass parts, heat dissipation will fall remarkably.

[Flame retardant aid]
The resin composition of the present invention may further contain a flame retardant aid as necessary.
Examples of flame retardant aids include antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, silicon dioxide hydrotalcite, magnesium bicarbonate, zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, zirconium oxide , Vanadium oxide, molybdenum oxide and surface-treated products thereof, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol, tris (2-hydroxyethyl) isocyanurate, and polytetrafluoroethylene. These may be used individually by 1 type and may be used in combination of 2 or more type. Of these, antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide are preferable.

  When using a halogen-based flame retardant, the flame retardant aid is particularly preferably, for example, antimony trioxide, and when using a non-halogen flame retardant, for example, polytetrafluoroethylene is particularly preferable. .

(Content ratio)
In the polyolefin resin composition of the present invention, the content ratio of the flame retardant aid is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass with respect to 100 parts by mass of the polyolefin resin. is there. If the said content rate of a flame retardant is 0.01 mass part or more, a flame retardance can be improved further. Moreover, if it is 20 mass parts or less, there is no possibility that the specific gravity of a polyolefin resin composition may become high.

[Additive component]
The polyolefin resin composition of the present invention may further contain various additives as necessary. Examples of the additives include ultraviolet absorbers, light stabilizers, antioxidants, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial / antifungal agents, and pigments. The content of the additive is not particularly limited as long as the properties of the resin composition are not impaired.

The ultraviolet absorber is a component that absorbs ultraviolet rays that promote deterioration of the resin component, and is not particularly limited, and examples thereof include benzophenone compounds, triazole compounds, and benzoate compounds.
Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone) and the like 2 -Hydroxybenzophenones; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazo- 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazol, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazol 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6- 2- (2′-hydroxyphenyl) benzotriazoles such as benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol Monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; Ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-me Cyanoacrylates such as xylphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, 2- (2-hydroxy -4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-ditert-butylphenyl) And triaryltriazines such as -s-triazine. These may be used individually by 1 type and may be used in combination of 2 or more type.

The light stabilizer is a component that takes in radicals that promote deterioration of the resin component, and is not particularly limited, and examples thereof include an NH type hindered amine compound and an N-methyl type hindered amine compound.
Specifically, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl -4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bi (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4- Piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8, 12-tetrakis [ , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl)] Amino) -s-triazin-6-yl] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) ) Amino) -s-triazin-6-yl] hinder doors such as aminoundecane And the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
In addition, although an ultraviolet absorber and a light stabilizer may each be used independently and may be mixed and used, it is preferable to mix and use from a viewpoint that deterioration of a resin component can be prevented more.

Although it does not specifically limit as antioxidant, A phenolic antioxidant, phosphorus antioxidant, thioether type antioxidant, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
Specific examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl). -4-hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m -Cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6- Tributyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) ) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert Tributyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [ 3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] Terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane , Triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl. Phenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4 -Ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) penta Erythritol diphosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; pentaerythritol tetra (β-alkylmercaptopropionic acid) Examples include esters, etc. These may be used alone or in combination of two or more.

The lubricant is not particularly limited, and examples thereof include fatty acid amide lubricants, fatty acid ester lubricants, fatty acid lubricants, and fatty acid metal salt lubricants. These may be used individually by 1 type and may be used in combination of 2 or more type.
Specific examples of the aliphatic amide lubricant include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, and ethylene bis lauryl. Examples include acid amides. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the aliphatic ester lubricant include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, myristic Isopropyl acid, isopropyl palmitate, octyl palmitate, octyl palm fatty acid octyl stearate, beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, linear C28-30 Unbranched saturated monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerin ester, montanic acid and butylene glycol ester, montanic acid and trimethylol eta Ester, montanic acid and trimethylolpropane ester, montanic acid and pentaerythritol ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, polyoxy Examples include ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the fatty acid lubricants, specific examples of saturated fatty acids include lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) ), Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid (Hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid, etc. are mentioned, and lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid are particularly mentioned.

Among the fatty acid lubricants, unsaturated fatty acids include myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid), ricinoleic acid (Octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid (9,11, 13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid) and the like.
One of these fatty acid-based lubricants may be used alone, or two or more thereof may be used in combination.
Examples of the fatty acid metal salt lubricant include lithium salt, calcium salt, magnesium salt and aluminum salt of the fatty acid of the fatty acid lubricant. These may be used individually by 1 type and may be used in combination of 2 or more type.

The crystal nucleating agent is not particularly limited, and examples thereof include sorbitols, phosphorus nucleating agents, rosins, and petroleum resins.
Specifically, sorbitols such as alkyl-substituted benzylidene sorbitol (1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3-o- Methylbenzylidene 2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethylbenzylidene) Sorbitol, etc.), phosphorus nucleating agents (bis (4-t-butylphenyl) sodium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, organic phosphate Composite products, etc.), sodium benzoate, aluminum pt-butylbenzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin Leh, talc, rosin, petroleum resins, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The softening agent is not particularly limited, and examples thereof include liquid paraffin, mineral oil softener (process oil), and non-aromatic rubber mineral oil softener (process oil). These may be used individually by 1 type and may be used in combination of 2 or more type.

The antistatic agent is not particularly limited, and examples thereof include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, and fatty acid partial esters such as glycerin fatty acid monoesters.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate , (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate Alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, monoglyceride stearate , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. These may be used individually by 1 type and may be used in combination of 2 or more type.

Although it does not specifically limit as a metal deactivator, A hydrazine type metal deactivator, a nitrogen compound type metal deactivator, a phosphite ester type metal deactivator, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of hydrazine-based metal deactivators include N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, Examples include decanedicarboxylic acid disalicyloylbidrazide, oxalic acid bisbenzylidenehydrazide, and the like.
Nitrogen-based metal deactivators include N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide metal deactivator, melamine and the like.
Phosphite-based metal deactivators include tris [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5-t-butyl) phenyl-5-methyl] phosphite, etc. Is mentioned.
These metal deactivators may be used individually by 1 type, and may be used in combination of 2 or more type.

The antibacterial / antifungal agent is not particularly limited, and examples thereof include an organic compound antibacterial / antifungal agent, a natural organic antibacterial / antifungal agent, and an inorganic antibacterial / antifungal agent. These may be used individually by 1 type and may be used in combination of 2 or more type.
Organic compound antibacterial / antifungal agents include thiabendazole, 2-n-octyl-4-isothiazolin-3-one, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, N- (fluorocyclomethylthio)- Phthalimide, bis (1-hydroxy-2 (1H) pyridinethionate-O, S) zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 10,10′-oxybisphenoxyarsine Etc.
Examples of natural organic antibacterial and antifungal agents include allyl isothiocyanate.
Inorganic antibacterial / antifungal agents include silver-supported silica gel, silver-supported zeolite, silver ions-supported hydroxyapatite, silver ions-supported water glass, silver ions-supported zirconium phosphate, and silver ions. Examples include supported ammonium polyphosphate, zeolite supporting silver and copper ions, and zeolite supporting zinc.
One of these antibacterial / antifungal agents may be used alone, or two or more thereof may be used in combination.

Although it does not specifically limit as a pigment, An inorganic pigment, an organic pigment, etc. are mentioned.
Inorganic pigments include titanium oxide, bengara, alumina white, yellow iron oxide, cadmium red, vermilion, yellow lead, molybdate orange, gypsum, barium sulfate, calcium carbonate, lead white, ultramarine, manganese violet, cobalt violet, emerald green. , Bitumen, carbon black, aluminum powder, zinc powder and the like.
Examples of organic pigments include azo pigments, acidic dye lakes, basic dye lakes, and condensed polycyclic pigments.
These pigments may be used alone or in combination of two or more.

[Kneading / Molding]
Although the polyolefin resin composition of this invention is not specifically limited, For example, each raw material can be melt-kneaded and can be prepared as a pellet with a pelletizer. The compounding and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., Henschel mixer (trade name), Banbury mixer, single screw extruder, twin screw extruder, It can be performed by a method using a multi-screw extruder, a kneader or the like.
What is necessary is just to select the heating temperature in the case of kneading | mixing suitably in the range of 200-280 degreeC normally.

  The polyolefin resin composition of the present invention is the above-described melt-kneading molding machine, or an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding, using the obtained pellet-shaped resin composition as a raw material. Various molded bodies can be produced by the method, the vacuum molding method, the foam molding method, and the like. In particular, by the melt-kneading method, a molding raw material that is a pellet-shaped polyolefin resin composition is manufactured, and then this pellet is used for manufacturing an injection-molded body by injection molding and extrusion-molded body by extrusion molding. Can be used. Moreover, after forming into an extrusion molded body such as an extruded sheet by extrusion molding, a molded body may be formed by processing or molding such as thermoforming.

[Physical properties of resin composition]
(Heat dissipation)
The resin composition of the present invention is excellent in heat dissipation, and the heat dissipation can be evaluated by thermal conductivity. From the viewpoint of heat dissipation, it is preferably 1 to 8 W / m · K, More preferably, it is 7 W / m · K. Specifically, the thermal conductivity is measured by the method described in Examples.
(specific gravity)
The resin composition of the present invention has a low specific gravity and is preferably 1.00 to 1.80 g / cm ³ , more preferably 1.10 to 1.60 g / cm ³ from the viewpoint of weight reduction. . The specific gravity is specifically measured by the method described in the examples.

[Molded body]
The molded body of the present invention is formed by molding a polyolefin resin composition obtained by blending a flame retardant and a heat conductive filler in a specific range with the above-described polyolefin resin, and has flame retardancy and heat dissipation (high heat). Compared with the case of using a resin composition containing an engineering plastic, a lightweight molded body can be easily obtained.
Specifically, when the polyolefin resin composition of the present invention is used, compared with the case of using a resin composition containing an engineering plastic, it does not require special equipment and can be used for general injection molding and extrusion molding. Can be molded. Therefore, the molded product of the present invention has a heat dissipation property (high thermal conductivity) and flame retardancy of electrical and electronic parts such as lighting fixtures, copying machines, fax machines, televisions, radios, personal computers, printers, telephones, information terminals, etc. Can be suitably used as a molded product that requires the above.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The performance test of the resin composition obtained in each example was performed as follows.
[performance test]
(1) Specific gravity It measured by the method based on specific gravity ASTM D792 using the test piece (size: 127mmx12.7mm, thickness: 1.6mm) produced by the below-mentioned method.
(2) Flame retardancy Using a test piece (size: 127 mm × 12.7 mm, thickness: 1.6 mm) produced by the method described later, the flame retardancy was evaluated by a method based on the UL94 vertical combustion test. In addition, what was outside the standard of UL94 is shown as “Not V”. The obtained results are shown in Table 1.
(3) Heat dissipation (thermal conductivity)
Using a test piece (size: size: 100 mm × 100 mm, thickness: 3.0 mm) prepared by the method described later, the thermal conductivity was evaluated by a method based on ASTM E1461. The obtained results are shown in Table 1.
(4) Formability Formability was evaluated by injection moldability, extrusion molding, and thermoformability. The obtained results are shown in Table 1.
・ Injection moldability Pellets produced by the method described below are produced by a molding machine having a cylinder temperature of 210 ° C., a mold temperature of 50 ° C., an injection pressure of 80 MPa, and a spiral shaped product having a wall thickness of 2 mm and a width of 10 mm. The flow length (spiral flow) was measured.
・ Extrudability and thermoformability (shapeability)
By using the pellets produced by the method described later, the melt tension was measured to evaluate the formability as an index of extrudability and thermoformability.

Moreover, each component used in each example is as follows.
(resin)
Resin A: Polypropylene resin [manufactured by Nippon Polypro Co., Ltd., trade name: Newcon NBC03HR, propylene ethylene block polymer, density: 0.91 g / cm ³ , 230 ° C., melt mass flow rate at a load of 2.16 kg: 30 g / 10 minutes]
Resin B: Polypropylene resin [manufactured by Prime Polymer Co., Ltd., trade name: E-185G, propylene ethylene block copolymer, density: 0.3 g / cm ³ , 230 ° C., melt mass flow rate at a load of 2.16 kg: 0 .5g / 10min]
Resin C: Polyethylene resin [manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LJ902, homopolymer, density: 0.915 g / cm ³ , 190 ° C., melt mass flow rate at a load of 2.16 kg: 45 g / 10 min]
Resin D: Polyethylene resin [manufactured by Nippon Polyethylene Corporation, trade name: Novatec HE30, homopolymer, density: 0.915 g / cm ³ , 190 ° C., melt mass flow rate at a load of 2.16 kg: 0.5 g / 10 Min)
Resin E: Polyphenylene sulfide resin [manufactured by DIC Corporation, trade name: MB65290G]
(Filler)
Heat conductive filler; graphite particles [Ito Graphite Industry Co., Ltd., scaly graphite, trade name: Z-100, weight average particle diameter (D50): 60 μm]
・ Non-thermal conductive filler: Calcium carbonate [Calfine Co., Ltd., trade name: KS1300]
(Flame retardants)
Halogen flame retardant A; ethylene bis (pentabromophenyl) [manufactured by Albemarle, trade name: SAYTEX 8010]
Halogen-based flame retardant B; 2,2′-bis [4- (2,3- (dibromopropyloxy) -3,5-dibromophenyl] [Propane Daiichi Kogyo Seiyaku Co., Ltd., trade name: Piroguard SR720]
Non-halogen flame retardant A; Phosphate [manufactured by ADEKA Corporation, trade name: ADK STAB FP2100J]
Non-halogen flame retardant B: Magnesium hydroxide [Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5A]
(Flame retardant aid)
・ Flame retardant aid A; antimony trioxide (made by tin mine, antimony industry limited liability company, trade name: TWINKLING STAR)
・ Flame retardant aid B: Polytetrafluoroethylene [Mitsubishi Rayon Co., Ltd., trade name: Metabrene A3800]

[Examples 1 to 5 , Reference Examples 1 to 3 and Comparative Examples 1 to 7]
Each component is blended in the blending amounts shown in Table 1, and melt-kneaded at a screw diameter of 45 mm and a cylinder temperature of 220 to 250 ° C. using a twin-screw extruder (Ikegai Co., Ltd., model name: PCM45) and discharged from a die. The resulting strand was cooled with a cooling bath and cut with a pelletizer to prepare a pelletized polyolefin resin composition (pellet). Only Comparative Example 2 was melt-kneaded at a cylinder temperature of 350 ° C.
Next, using the obtained pellets, a test piece for evaluating specific gravity and flame retardancy (size: 127 mm × 12) in an injection molding machine under molding conditions of a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C. And a test piece (size: 100 mm × 100 mm, thickness: 3.0 mm) for heat dissipation evaluation were prepared, and the above-described performance test was performed. The results are shown in Table 1. In Comparative Example 2, the cylinder temperature was 300 ° C. and the mold temperature was 150 ° C.

  It can be seen from all the examples in Table 1 that the polyolefin resin composition of the present invention is excellent in moldability and can provide a lightweight molded body having flame retardancy and heat dissipation. On the other hand, in the case where the content of the heat conductive filler or the flame retardant is outside the range specified from Comparative Examples 1, 4, and 6, or in the case where the non-heat conductive filler is included from Comparative Example 5, It can be seen that the moldability cannot be improved. Moreover, it turns out that specific gravity becomes large and cannot be reduced in the comparative example 2 which used polyphenylene sulfite resin instead of polyolefin resin. In Comparative Examples 3 and 7, where the flame retardant content was too high, kneading was impossible and a resin composition could not be obtained.

  The polyolefin resin composition of the present invention is a resin composition that is lightweight and excellent in moldability as compared to the case of using engineering plastics while having flame retardancy and heat dissipation (high thermal conductivity). Can be used for resin parts that require heat dissipation (high thermal conductivity) and flame resistance such as electrical and electronic parts such as lighting equipment, copiers, fax machines, televisions, radios, personal computers, printers, telephones, and information terminals. It is.

Claims (6)

100 parts by weight of the polyolefin resin to 160 parts by mass of 30 to the thermally conductive filler, 33 to 80 parts by weight of Ha androgenic flame retardant, and the flame retardant aid include from 0.05 to 24.15 parts by weight,
The heat conductive filler is a scaly graphite particle having a weight average particle diameter (D50) of 40 to 150 μm ,
The halogen flame retardant is tetrabromobisphenol A and derivatives thereof, tetrabromobisphenol S and derivatives thereof, ethylenebis (pentabromodiphenyl) and derivatives thereof, tris (bromoneopentyl) phosphate and derivatives thereof, ethylenebistetrabromophthalimide and its derivatives, and Ri der one or more selected tris (2,3-dibromopropyl) isocyanurate and derivatives thereof from,
A polyolefin resin composition, wherein the flame retardant aid is at least one selected from antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide,
The polyolefin resin composition whose thermal conductivity of the test piece for heat dissipation evaluation obtained with the injection molding machine of this resin composition is 1-8 W / m * K in the evaluation by the method based on ASTM E1461 .   The polyolefin resin composition according to claim 1, wherein the polyolefin resin is a resin containing one or more selected from a polypropylene resin and a polyethylene resin. The molded object obtained by injection-molding the polyolefin resin composition of Claim 1 or 2 . An extruded product obtained by extruding the polyolefin resin composition according to claim 1 or 2 . A molded body obtained by processing or molding the extruded molded body according to claim 4 . The pellet obtained from the polyolefin resin composition of Claim 1 or 2 .