JP5100054B2 - Thermally conductive resin composition - Google Patents

Description

  The present invention relates to a heat conductive resin composition, and more specifically, a heat conductive resin composition containing a specific magnesium oxide filler for blending a resin and giving a molded product excellent in moldability, heat conductivity and water resistance. About.

Magnesium oxide is widely used as a heat-resistant material, an abrasive, a filler, and the like because it has properties such as a high melting point, high thermal conductivity, and nontoxicity. In recent years, various treatments have been performed on the surface of magnesium oxide according to the purpose to improve performance.
Patent Document 1 discloses magnesium oxide having an average secondary particle diameter of 20 μm or less, obtained by firing magnesium hydroxide having a specific particle diameter and BET specific surface area under specific conditions.
Patent Document 2 discloses a magnesium oxide powder coated with glass mainly composed of PbO.
Patent Document 3 discloses a thermoplastic resin composition containing polyamide resin, glass fiber, and magnesium oxide having a particle diameter of 100 μm or less and a BET specific surface area of 5 m ² / g or less.
Patent Document 4 discloses a fluid heat conductive silicone rubber composition containing magnesium oxide surface-treated with a coupling agent after dead burning and baking magnesium hydroxide.

Patent Document 5 discloses a resin composition containing coated magnesium oxide having a coating layer containing a double oxide of Si and / or Al and Mg on the surface.
Patent Document 6 discloses a magnesia powder having a purity of 90% by mass or more, a specific surface area of 5 m ² / g or less, and an average particle size of 50 μm or less.
Patent Document 7 discloses magnesium oxide for a friction material having an average particle diameter of 1 to 50 μm and a specific surface area of 0.1 to ⁵ m ² / g.

Japanese Patent Laid-Open No. 6-171928 JP-A-7-188579 JP-A-11-148007 JP-A-11-199776 JP 2004-27177 A JP-A-8-12321 JP 2002-212543 A

  However, it cannot be said that the thermal conductivity of a molded product obtained by molding the resin composition to which such filler is added by extrusion molding, injection molding or the like is sufficient. In addition, there is a problem that water resistance is deteriorated, and there is a problem in that the intended use is limited.

  The objective of this invention is providing the heat conductive resin composition which gives the molded article excellent in moldability, heat conductivity, and water resistance.

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have obtained a molded article excellent in molding processability, thermal conductivity and water resistance by a composition containing a specific magnesium oxide filler for compounding a resin. As a result, the present invention has been completed.

The present invention is shown below.
1. In a thermally conductive resin composition containing a thermoplastic resin and a magnesium oxide filler for resin blending,
The thermoplastic resin is a rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer comprising a diene polymer, Or it consists of a mixture of the rubber-reinforced vinyl resin and a copolymer of vinyl monomers containing an aromatic vinyl compound and a vinyl cyanide compound, and the content of the rubbery polymer is 36 to 60% by mass A rubber-reinforced resin, a polycarbonate resin, a polybutylene terephthalate resin, a polypropylene resin and a polyethylene resin,
The magnesium oxide filler for resin blending has a purity of 95.0% by mass or more, a BET specific surface area of 5.0 m ² / g or less, a volume average particle diameter (Dv) of 0.5 to 60 μm, and a volume average particle diameter. A mixture containing 100 parts by mass of magnesium oxide having a ratio Dv / Dn of (Dv) to the number average particle diameter (Dn) of 10 to 55 and 0.1 to 10 parts by mass of an organosilicon compound is 100 to 800 ° C. It was obtained by heating at a temperature of
Content of the said magnesium oxide filler for resin mixing | blending is 100-500 mass parts with respect to 100 mass parts of said thermoplastic resins, The heat conductive resin composition characterized by the above-mentioned.
2. ^2. The heat conductive resin composition according to 1 above, wherein the magnesium oxide has a BET specific surface area of 0.3 to 1.2 m ² / g.
3. The thermoplastic resin is a rubber reinforced resin, and the rubber reinforced resin is obtained by polymerizing a vinyl monomer containing styrene and acrylonitrile in the presence of a rubbery polymer made of polybutadiene. 1 or above, wherein the rubber or the rubber-reinforced vinyl resin is a mixture of a vinyl monomer containing styrene and acrylonitrile, and the content of the rubbery polymer is 36 to 60% by mass. 2. The heat conductive resin composition according to 2.
4). 4. The thermally conductive resin composition according to any one of 1 to 3, wherein the organosilicon compound is silicone oil.
5. Furthermore, it contains a flame retardant composed of 1,3-phenylenebisdixylenyl phosphate,
The thermoplastic resin is composed of the rubber-reinforced resin, the polycarbonate resin, and the polybutylene terephthalate resin, and these ratios are 35 to 75% by mass when the thermoplastic resin is 100% by mass, respectively. , 12-37 wt% and 1-7 wt%,
Content of the said magnesium oxide filler for resin compounding is 200-400 mass parts with respect to 100 mass parts of said thermoplastic resins,
The heat conductive resin composition according to any one of 1 to 4 above, wherein a content of the flame retardant is 33.3 to 36.4 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
6). The thermal conductive resin composition according to any one of 1 to 5 above, wherein the thermal conductivity is 0.5 W / m · K or more.

According to the heat conductive resin composition of the present invention, a molded product excellent in moldability, heat conductivity and water resistance can be obtained.
Moreover, when this composition contains a flame retardant, V-0 in UL94 specification can be achieved and it is excellent in a flame retardance.

The present invention will be described in detail below.
In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and methacrylic.

The magnesium oxide filler for resin blending (hereinafter also referred to as “magnesium oxide filler (I I )”) contained in the heat conductive resin composition of the present invention has a purity of 95.0% by mass or more and a BET specific surface area of 5 0.0 m ² / g or less, volume average particle diameter (Dv) of 0.5 to 60 μm, and ratio of volume average particle diameter (Dv) to number average particle diameter (Dn) Dv / Dn is 10 to 55 . A magnesium filler (hereinafter also referred to as “magnesium oxide filler (I)”) is surface-treated with an organosilicon compound .

  Magnesium oxide of the magnesium oxide filler (I) is not particularly limited, and lightly burned magnesia obtained by firing carbonate (magnesite), nitrate, hydroxide, etc. at 1,400 ° C. or lower, from the above temperature A hard-fired magnesia (also called “high-temperature fired magnesia clinker”) obtained by sintering at a high temperature (eg, 1,800 ° C. or higher) and natural magnesite or seawater magnesia are melted in an electric arc furnace, Then, electrofused magnesia obtained by crushing is mentioned. These can be used alone or in combination of two or more. In the present invention, electrofused magnesia and hard-fired magnesia are preferred.

  The purity of magnesium oxide is 95.0% by mass or more, preferably 96.0 to 100% by mass, more preferably 98.0 to 100% by mass, still more preferably 98.5 to 100% by mass, particularly preferably. It is 99.0-100 mass%. If the purity is too low, water resistance and thermal conductivity may not be sufficient when a resin molded product is obtained. The purity can be measured according to JIS K6224.

The BET specific surface area of the magnesium oxide filler (I) is 5.0 m ² / g or less, preferably 0.1 to 3.5 m ² / g, more preferably 0.15 to ³ m ² / g, still more preferably. Is 0.2 to ² m ² / g, particularly preferably 0.2 to 0.8 m ² / g. If the BET specific surface area is too high, water resistance may not be sufficient when a resin molded product is obtained. The BET specific surface area can be measured using a commercially available apparatus.

The volume average particle diameter (hereinafter referred to as “Dv”) of the magnesium oxide filler (I) is 0.5 to 60 μm, preferably 2 to 50 μm, more preferably 5 to 35 μm. If this Dv is too large, the desired thermal conductivity may not be obtained in the case of a resin composition, and the appearance and mechanical properties of the resin molded product may be deteriorated. On the other hand, if Dv is too small, water resistance and thermal conductivity may not be sufficient when a resin molded product is obtained.
Moreover, ratio Dv / Dn of said Dv and a number average particle diameter (henceforth "Dn") is 10-55, Preferably it is 12-50, More preferably, it is 15-40. If this ratio is too large, the water resistance may be insufficient when a resin molded product is obtained. On the other hand, if it is too small, the desired thermal conductivity may not be obtained.
The above Dv and Dn can be measured by a laser diffraction scattering method, a dynamic light scattering method, or the like.

  The magnesium oxide filler (I) may be a combination of two or more magnesium oxide fillers in an arbitrary ratio as long as each of the above physical properties falls within the above ranges.

On the other hand, the magnesium oxide filler (II) is produced by heating a mixture containing 100 parts by mass of the magnesium oxide filler (I) and 0.1 to 10 parts by mass of the organosilicon compound at a temperature of 100 to 800 ° C. der made Te Ru.

  Examples of the organosilicon compound include silicone oil, silane coupling agent, alkoxysilane compound, silylating agent and the like. Of these, silicone oil and silane coupling agents are preferred, and silicone oil is particularly preferred.

As the silicone oil, any of unmodified silicone oil and modified silicone oil may be used, or a combination thereof may be used. Non-modified silicone oils include dimethyl silicone oil whose polysiloxane side chains and terminals are all methyl groups, methyl phenyl silicone oil whose polysiloxane side chains are partially phenyl groups, and part of polysiloxane side chains. Methyl hydrogen silicone oil in which is a hydrogen atom. The modified silicone oil includes alkoxy modification, amino modification, carboxyl modification, epoxy modification, silazane modification, phenol modification, carbinol modification, methacryl modification, mercapto modification, polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester. Modification, fluorine modification, hydrophilic special modification and the like can be mentioned, but the presence or absence of reactivity is not particularly limited.
Of these, alkoxy-modified silicone oil and methyl hydrogen silicone oil are preferable, and alkoxy-modified silicone oil is particularly preferable.
The said silicone oil can be used individually by 1 type or in combination of 2 or more types.

  The kinematic viscosity (25 ° C.) of the silicone oil is preferably 0.5 to 10,000 cSt, more preferably 1 to 5,000 cSt, and still more preferably 1.5 to 3,000 cSt. If the viscosity is too high, the water resistance may not be improved. On the other hand, if the viscosity is too low, it may be difficult to prepare the mixture before the heating step, and the water resistance may not be improved. The viscosity of the silicone oil can be measured by the Ostwald method or the like at 25 ° C.

As silane coupling agents, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldichlorosilane, 3-chloropropylmethyldiethoxy Silane, 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl triethoxysilane, and the like.
The said silane coupling agent can be used individually by 1 type or in combination of 2 or more types.

Examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, and methyltriethoxysilane.
The said alkoxysilane compound can be used individually by 1 type or in combination of 2 or more types.

Examples of the silylating agent include trimethylchlorosilane and hexamethyldisilazane.
The said silylating agent can be used individually by 1 type or in combination of 2 or more types.
Moreover, said silicone oil, a silane coupling agent, an alkoxysilane compound, a silylating agent, etc. may each be used independently and may be used in combination.

  The amount of the organosilicon compound used is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the magnesium oxide filler (I). is there. If the amount of the organosilicon compound used is too small, the water resistance improvement effect by the modified magnesium oxide filler (II) may not be sufficient. On the other hand, if the amount is too large, the thermal conductivity may not be improved.

  A method for preparing the mixture containing the magnesium oxide filler (I) and the organosilicon compound is not particularly limited, and a known charging method, stirring method, and the like can be applied in a known container. By stirring, the entire surface of the magnesium oxide filler (I) is coated with the organosilicon compound.

The mixture is heated using an industrial furnace such as an electric furnace or a gas furnace at a temperature in the range of 100 to 800 ° C, preferably 200 to 600 ° C, more preferably 250 to 400 ° C. The heating time in that case is 10 minutes-5 hours normally, Preferably it is 30 minutes-4 hours, More preferably, it is 30 minutes-3 hours.
In both cases where the heating temperature is too low and the heating time is too short, the effect of improving water resistance by the modified magnesium oxide filler (II) tends to be insufficient. On the other hand, when the temperature is too high and when the heating time is too long, the water resistance tends to decrease.
In particular, when silicone oil is used as the organosilicon compound, the adhesiveness between the silicone oil and the magnesium oxide filler and the hydrophobicity that develops with the temperature and time conditions at which the silicone oil is completely decomposed tend to decrease.

Magnesium oxide filler (II) may be obtained by the above heating step, and may further include phosphate ester, higher fatty acid and its metal salt, higher fatty acid ester, higher fatty acid amide, higher alcohol, hydrogenated oil, etc. What was processed with the surface treating agent may be used.
By using these surface treatment agents, the water resistance may be further improved, and the dispersibility in the thermoplastic resin may be further improved.

  Phosphoric esters include phosphate esters of mono and di-saturated alcohols such as mono-stearyl acid phosphate, di-stearyl acid phosphate, mono-lauryl acid phosphate, di-lauryl acid phosphate, mono-myristyl Acid Phosphate, Di-Myristyl Acid Phosphate, Mono-Palmityl Acid Phosphate, Di-Palmityl Acid Phosphate, Mono-Arakil Acid Phosphate, Di-Arakil Acid Phosphate, Mono-Beher Acid Phosphate Di-beher acid phosphate, mono-lignoseryl acid phosphate, di-lignoseryl acid phosphate, and the like. These can be used alone or in combination of two or more.

As the higher fatty acid, those having 12 or more carbon atoms are preferable, and examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, and caprylic acid. These can be used alone or in combination of two or more.
Examples of the higher fatty acid metal salts include Na salts, K salts, Al salts, Mg salts, Ca salts, Zn salts, Ba salts and the like of the above higher fatty acids. These can be used alone or in combination of two or more.

  Examples of higher fatty acid esters include alkyl esters of the above higher fatty acids such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate. , Isopropyl myristate, isopropyl palmitate, octyl palmitate, coconut fatty acid octyl ester, octyl stearate, special beef tallow fatty acid octyl ester, lauryl laurate, stearyl long stearate, long chain fatty acid higher alcohol ester, behenyl behenate, Monoesters such as cetyl myristate; neopentyl polyol long chain fatty acid ester, neopentyl polyol long chain fatty acid ester partially esterified product, neopentyl polyol fatty acid ester Neopentyl polyol medium chain fatty acid esters, neopentyl polyol C9 chain fatty acid esters, dipentaerythritol long chain fatty acid esters, such as heat-resistant special higher fatty acid esters such as complex medium chain fatty acid ester. These can be used alone or in combination of two or more.

  Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, palmitic acid amide, linoleic acid amide, lauric acid amide, caprylic acid amide, and behenic acid amide. These can be used alone or in combination of two or more.

As the higher alcohol, those having 8 or more carbon atoms are preferable, and examples thereof include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and the like. These can be used alone or in combination of two or more.
Examples of the hardened oil include beef fat hardened oil and castor hardened oil. These can be used alone or in combination of two or more.

  Although the usage-amount of a surface treating agent is not specifically limited, Preferably it is 0.05-5 mass parts with respect to 100 mass parts of magnesium oxide filler (II), More preferably, it is 0.1-4 mass parts, More preferably 0.2 to 3 parts by mass.

  In the treatment method using the surface treatment agent, a desired amount of the surface treatment agent is added to the magnesium oxide filler (II) and heated to a temperature equal to or higher than the melting temperature, for example, 50 to 150 ° C, more preferably 80 to 130 ° C. While stirring and mixing. The heating time is 5 minutes to 3 hours, preferably 10 minutes to 1 hour.

  The magnesium oxide filler (II) for blending a resin may be a combination of two or more magnesium oxide fillers in an arbitrary ratio.

  The magnesium oxide filler (II) for blending a resin can have a water absorption of 1% by mass or less, preferably 0.5% by mass or less after standing for 8 days in an atmosphere of a temperature of 60 ° C. and a relative humidity of 90%. It can be.

The thermally conductive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes a thermoplastic resin (hereinafter also referred to as “component [A]”) and the magnesium oxide filler for resin blending. (II) (hereinafter also referred to as “component [M]”). As this component [M], the magnesium oxide filler (II) may be used alone or in combination.
Content of component [M] in the composition of this invention is 100-500 mass parts with respect to 100 mass parts of component [A]. If the content of the component [M] is too small, the thermal conductivity is not sufficient. On the other hand, if the content is too large, the moldability and the appearance and impact resistance of the molded product may be deteriorated.

Component [A] is a rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer composed of a diene polymer. Or it consists of a mixture of the rubber-reinforced vinyl resin and a copolymer of vinyl monomers containing an aromatic vinyl compound and a vinyl cyanide compound, and the content of the rubbery polymer is 36 to 60% by mass It is at least one selected from a certain rubber-reinforced resin, polycarbonate resin, polybutylene terephthalate resin, polypropylene resin and polyethylene resin .

The rubber-reinforced resin is a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer composed of a diene polymer (hereinafter referred to as “rubbery polymer (a)”). Rubber reinforced vinyl resin (hereinafter referred to as “rubber reinforced vinyl resin (A1)”) obtained by polymerizing the body (hereinafter referred to as “vinyl monomer (b)”), or the rubber reinforced resin. A mixture of a vinyl resin (A1) and a copolymer of a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound (hereinafter referred to as “copolymer (A2)”). .

The rubbery polymer (a) is a diene polymer, and may be a homopolymer or a copolymer. These may be used alone or in combination. Further, the rubbery polymer (a) may be a non-crosslinked polymer or a crosslinked polymer.

Diene polymers include homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymers such as styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers; hydrides of the above (co) polymers, and the like.
Each of the above copolymers may be a block copolymer or a random copolymer.

  The size and shape of the rubber polymer (a) are not particularly limited, but are preferably particulate, and the weight average particle diameter is preferably 50 to 3,000 nm, more preferably 100 to The thickness is 2,000 nm, particularly preferably 120 to 800 nm. When the weight average particle diameter is less than 50 nm, the impact resistance of the composition of the present invention and a molded article containing the composition tends to be inferior, and when it exceeds 3,000 nm, the surface appearance of the molded article tends to be inferior. The weight average particle diameter can be measured by a laser diffraction scattering method, a dynamic light scattering method, or the like.

  The rubbery polymer (a) may be, for example, JP-B-4-79366, JP-A-59-93701, JP-A-56-56 as long as the weight average particle diameter is within the above range. What was enlarged by well-known methods, such as the method described in 167704 gazette etc., can also be used.

Examples of the method for producing the rubber polymer (a) include emulsion polymerization and solution polymerization. Of these, emulsion polymerization is preferred because it is easy to adjust the average particle size. In this case, the average particle size can be adjusted by selecting the production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Another method for adjusting the average particle size (particle size distribution) may be a method of blending two or more rubbery polymers (a) having different particle sizes. The rubbery polymer (a) obtained by producing by emulsion polymerization is suitable for producing the rubber-reinforced vinyl resin (A1) by emulsion polymerization.
When the rubbery polymer (a) is produced by solution polymerization or the like, it can be made into a polymer having a predetermined average particle diameter by a method such as re-emulsification. A dispersion of the rubbery polymer (a) obtained by re-emulsification is also suitable for producing the rubber-reinforced vinyl resin (A1) by emulsion polymerization.

  The rubbery polymer (a) contained in the rubber-reinforced resin, the rubbery polymer (a) contained in the component [A], and the rubbery polymer (a) contained in the composition of the present invention ) Is the same as the above weight average particle size, and by being in the above range, a molded product having excellent impact resistance and molded appearance can be obtained. The number average particle diameter can be determined from an electron micrograph.

The vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1) is an aromatic vinyl compound (hereinafter also referred to as “aromatic vinyl compound (b1)”) and a vinyl cyanide compound. And a compound copolymerizable with the aromatic vinyl compound such as a (meth) acrylic acid ester compound, a maleimide compound, and an acid anhydride, either individually or in combination of two or more. Can be used.
As the vinyl monomer (b), a monomer in which at least one aromatic vinyl compound is combined with at least one vinyl cyanide compound can be used.

  The aromatic vinyl compound (b1) is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of the (meth) acrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, acrylic Examples include ethyl acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and the like. These can be used alone or in combination of two or more.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used.
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.

  In addition to the above compounds, vinyl compounds 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 can be used as necessary. For example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxystyrene, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-diethyl-p-aminomethylstyrene Glycidyl methacrylate, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, 3,4-oxycyclohexyl acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, methacrylic acid, acrylic acid And vinyl oxazoline. These can be used alone or in combination of two or more.

The vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1) is preferably used in the following combinations. By using a vinyl cyanide compound, the physical property balance of chemical resistance and discoloration resistance is improved.
(1) An aromatic vinyl compound and a vinyl cyanide compound.
(2) Aromatic vinyl compounds, vinyl cyanide compounds and other compounds.

When the vinyl monomer (b) is an aromatic vinyl compound (b1) and a vinyl cyanide compound (hereinafter also referred to as “vinyl monomer (b2)”), the aromatic vinyl compound The polymerization ratio (b1) / (b2) between (b1) and the vinyl monomer (b2) is preferably (2-95) mass% / (98- 5)% by mass, more preferably (10 to 90)% by mass / (90 to 10)% by mass. If the amount of the aromatic vinyl compound (b1) used is too small, the moldability tends to be inferior. If it is too large, the chemical resistance, heat resistance, etc. of the composition of the present invention and the molded product containing the composition are not sufficient. There is a case.

  The rubber-reinforced vinyl resin (A1) is obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a). The rubber-reinforced vinyl resin (A1) may be one or more of rubber-reinforced vinyl resins (ii) obtained using the monomer (1) as the vinyl monomer (b). Further, it may be one or more rubber-reinforced vinyl resins (iii) obtained by using the monomer (2) as the vinyl monomer (b). Furthermore, these may be combined appropriately.

As described above, when a rubber reinforced resin is used as the component [A], the rubber reinforced resin may be only the rubber reinforced vinyl resin (A1), or the rubber reinforced vinyl resin (A1). And a copolymer (A2) obtained by polymerization of a vinyl monomer may be used. The vinyl monomer includes aromatic vinyl compounds and vinyl cyanide compounds. Therefore, the copolymer (A2) is a polymer obtained by polymerizing components having exactly the same composition as the vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1). Alternatively, it may be a polymer obtained by polymerizing the same type of monomer with different compositions, or may be a polymer obtained by polymerizing different types of monomers with different compositions. May be. Two or more of these polymers may be contained.

Examples of the copolymer (A2) include the following ( 5 ) to ( 6 ). In addition, the compound used for formation of the said rubber reinforced vinyl-type resin (A1) can be applied to each monomer, and a preferable compound is also the same.
(5) One or more types of copolymers obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.
( 6 ) One or more kinds of copolymers obtained by polymerizing aromatic vinyl compounds, vinyl cyanide compounds and other compounds.
These can be used alone or in combination of two or more.

  Accordingly, specific examples of the copolymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / styrene / N-phenyl. A maleimide copolymer etc. are mentioned.

Next, a method for producing the rubber-reinforced vinyl resin (A1) and the copolymer (A2) will be described.
The rubber-reinforced vinyl resin (A1) is manufactured by preferably subjecting the vinyl monomer (b) to emulsion polymerization, solution polymerization, and bulk polymerization in the presence of the rubbery polymer (a). Can do.
In the production of the rubber-reinforced vinyl resin (A1), the rubber polymer (a) and the vinyl monomer (b) are present in the reaction system in the presence of the total amount of the rubber polymer (a). In addition, the vinyl-based monomer (b) may be added all at once, or divided or continuously. Moreover, the method which combined these may be used. Furthermore, you may superpose | polymerize by adding the whole quantity or one part of rubber-like polymer (a) in the middle of superposition | polymerization.
When producing 100 parts by mass of the rubber-reinforced vinyl resin (A1), the amount of the rubbery polymer (a) used is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 15 to 60 parts by mass.
Moreover, about each usage-amount of rubber-like polymer (a) and a vinyl-type monomer (b), the usage-amount of a vinyl-type monomer (b) with respect to 100 mass parts of rubber-like polymers (a), Usually, 25 to 1,900 parts by mass, more preferably 60 to 560 parts by mass.

When the rubber-reinforced vinyl 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.
As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Furthermore, the polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b) whole quantity, Preferably it is 0.2-0.7 mass%.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, terpinolene, α -A dimer of methylstyrene or the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b).

  As an emulsifier used in the case of emulsion polymerization, sulfate ester of higher alcohol, alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, aliphatic sulfonate such as sodium lauryl sulfate, higher aliphatic carboxylate, phosphoric acid Anionic surfactants such as nonionic surfactants such as alkyl ester type and alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b) whole quantity.

The latex obtained by emulsion polymerization is usually purified by coagulation with a coagulant to make the polymer component into powder, and then washing and drying. Examples of the coagulant include 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.
In addition, in the case of using a plurality of rubber-reinforced vinyl resins (A1) in combination, they may be mixed after isolation, but as another method, they are mixed after producing a latex containing each resin, Thereafter, the rubber-reinforced vinyl-based resin (A1) can be obtained by solidifying or the like.

  A known method can be applied to the method for producing the rubber-reinforced vinyl resin (A1) by solution polymerization and bulk polymerization. When the rubber-reinforced vinyl resin (A1) is produced by solution polymerization and bulk polymerization, the rubbery polymer (a) obtained by any method may be used. That is, latex (including rubber polymer (a) particles) obtained by emulsion polymerization may be used as it is, or rubber polymer (a) obtained by removing the medium may be used. Further, the rubbery polymer (a) obtained by solution polymerization may be used as it is, or a re-emulsified liquid thereof may be used.

The graft ratio of the rubber-reinforced vinyl resin (A1) is preferably 10 to 200% by mass, more preferably 15 to 150% by mass, and particularly preferably 20 to 100% by mass. When the graft ratio of the rubber-reinforced vinyl resin (A1) is less than 10% by mass, the surface appearance and impact resistance of the composition of the present invention and a molded article containing the composition may be lowered. On the other hand, if it exceeds 200%, the moldability is inferior.
Here, the graft ratio is x grams of the rubber component in 1 gram of the rubber-reinforced vinyl resin (A1), and y is insoluble when 1 gram of the rubber-reinforced vinyl resin (A1) is dissolved in acetone. It is a value obtained by the following formula when it is expressed in grams.
Graft ratio (mass%) = {(y−x) / x} × 100

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the soluble component of acetone of the rubber-reinforced vinyl resin (A1) is preferably 0.1 to 1.0 dl / g, more preferably 0. .2 to 0.9 dl / g, particularly preferably 0.3 to 0.7 dl / g. By setting it as this range, it is excellent in molding processability, and the impact resistance of the composition of this invention and a molded article containing it is also excellent.
The graft ratio and intrinsic viscosity [η] are the types and amounts of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, etc., when the rubber-reinforced vinyl resin (A1) is produced. It can be easily controlled by changing the polymerization temperature or the like.

  The copolymer (A2) is obtained by using, for example, a polymerization initiator applied to the production of the rubber-reinforced vinyl resin (A1), monomer components, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization. It can manufacture by superposing | polymerizing etc. by thermal polymerization which does not use a polymerization initiator. These polymerization methods may be combined.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the copolymer (A2) is preferably 0.1 to 1.0 dl / g, more preferably 0.15 to 0.7 dl / g. . When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. The intrinsic viscosity [η] of the copolymer (A2) can be controlled by adjusting the production conditions as in the case of the rubber-reinforced vinyl resin (A1).

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the rubber-reinforced resin with acetone is preferably 0.1 to 0.8 dl / g, more preferably 0.15 to 0.7 dl / g. g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

Here, when the rubber-reinforced resin is a rubber-reinforced vinyl resin (A1), and a copolymer (A2) obtained by polymerization of a rubber-reinforced vinyl resin (A1) and a vinyl monomer. In any case of the mixture consisting of the above, the content of the rubbery polymer (a) in the composition of the present invention is 36 to 60 % by mass. If the content of the rubbery polymer (a) is too small, the impact resistance of the composition of the present invention and a molded product containing the composition tends to be inferior, and if too large, the moldability and the surface appearance of the molded product. , Rigidity, heat resistance and the like tend to be inferior.

The polypropylene resin and the polyethylene resin may be crystalline or 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 resin is preferably 40 ° C. or higher.
The molecular weight of the 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 0.01 to 500 g / 10 min. Preferably it is 0.05-100 g / 10min, and what has the molecular weight corresponded to each value is preferable.

The intrinsic viscosity of the polybutylene terephthalate resin is not particularly limited. However, when a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (mass ratio 6: 4) is used, it is preferably 0. Each range is 5 to 1.5 dl / g, more preferably 0.5 to 1.2 dl / g, and still more preferably 0.6 to 1.0 dl / g.
Further, the melt flow rate measured at a temperature of 250 ° C. and a load of 2.16 kg according to ISO 1133 is preferably 10 to 50 g / 10 min, more preferably 15 to 40 g / 10 min. If the melt flow rate is less than the above range, the mechanical strength may be lowered, and if it exceeds the above range, formability may be insufficient.

  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, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). This polycarbonate resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aromatic polycarbonate include those obtained by melting a transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine and phosgene. What was obtained by the pyridine method using a reaction product etc. can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic dihydroxy 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. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferable.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is preferably 12,000 to 40,000, more preferably 14,000 to 30,000 when converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent. Especially preferably, it is 16,000-26,000. When this viscosity average molecular weight is too high, the fluidity is not sufficient, and the moldability may be lowered. On the other hand, if it is too low, impact resistance, toughness and chemical resistance may not be sufficient.
The polycarbonate resin may be used by mixing two or more polycarbonate resins having different viscosity average molecular weights as long as the overall viscosity average molecular weight falls within the above range.

  The melt flow rate measured at a temperature of 230 ° C. and a load of 1.2 kg according to ISO 1133 is preferably 5 to 50 g / 10 min, more preferably 10 to 40 g / 10 min.

As described above, the polybutylene terephthalate resin and the polycarbonate resin can be used as an alloy in combination with each other or in combination with other resin components.
Therefore, when the component [A] is an alloy of a polybutylene terephthalate resin and a polycarbonate resin, the use ratio thereof is preferably 90 to 99% by mass and 1 to 10% by mass, respectively. Preferably they are 93-99 mass% and 1-7 mass%. However, the total of the polybutylene terephthalate resin and the polycarbonate resin is 100% by mass.

Further, when the component [A] is an alloy of a polybutylene terephthalate resin, a rubber reinforced resin and a polycarbonate resin (ii), the use ratio of these can be selected according to the properties of the molded product.
When it is set as the molded product excellent in heat resistance, the use ratio of each component is preferably 30 to 80% by mass, 10 to 40% by mass, and 1 to 10% by mass, and more preferably 35 to 75% by mass. 12-37% by mass and 1-7% by mass.
Moreover, when it is set as the molded article excellent in impact resistance, the usage rate of each component becomes like this. Preferably they are 10-40 mass%, 30-80 mass%, and 1-10 mass%, respectively, More preferably, 12- They are 37 mass%, 35-75 mass%, and 1-7 mass%.

However, the total of the polybutylene terephthalate resin, the rubber reinforced resin and the polycarbonate resin is 100% by mass. By containing the three components in the above ranges and further using a flame retardant in combination, a molded article having more excellent flame retardancy can be obtained.

  The composition of the present invention may contain an additive depending on the purpose and application. Examples of the additive include a filler, a heat stabilizer, an antioxidant, an ultraviolet ray inhibitor, a flame retardant, an antiaging agent, a plasticizer, an antibacterial agent, and a colorant.

Examples of the filler include heavy calcium carbonate, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyrophyllite clay, silane-treated clay, and synthetic silicic acid. Calcium, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, magnesium hydroxide, kaolin, sericite, talc, fine talc, wollastonite, zeolite, zonotrite, asbestos, PMF (Processed Mineral Fiber), cucumber powder, sepiolite, titanium Potassium acid, elastadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbon balun, barium sulfate, aluminum sulfate, potassium sulfate Siumu, molybdenum disulfide, and the like. These can be used alone or in combination of two or more.
The content in the case of using the filler is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 2 to 20 parts by mass with respect to 100 parts by mass of the component [A]. is there.

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

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
The content in the case of using the antioxidant is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component [A].

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
When using the ultraviolet absorber, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the component [A]. .1 to 5 parts by mass.

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.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toki Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element; polytetrafluoroethylene and the like. These can be used alone or in combination of two or more.

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. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

When the flame retardant is used, the content thereof is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and further preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component [A]. is there.
In addition, when making the composition of this invention contain a flame retardant, it is preferable to use a flame retardant adjuvant. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

Examples of the antiaging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Thiobisphenol compound, hindered phenol compound, phosphite compound, imidazole compound, nickel dithiocarbamate salt compound, phosphate compound and the like. These can be used alone or in combination of two or more.
The content in the case of using the anti-aging agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the component [A]. .1 to 5 parts by mass.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like. These can be used alone or in combination of two or more.
When the plasticizer is used, the content thereof is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component [A]. Part.

Examples of the antibacterial agents include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver-silica gel, glass antibacterial agents, calcium phosphate antibacterial agents, and zirconium phosphate antibacterial agents. Silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc .; formaldehyde releasing agents, halogenated aromatic compounds, road Organic antibacterial agents such as propargyl derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; inorganic and organic Hybrid antibacterial agent; natural anti Agent, and the like. These can be used alone or in combination of two or more.
When the antibacterial agent is used, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.00 with respect to 100 parts by mass of the component [A]. 1 to 5 parts by mass.

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

  The composition of this invention can be manufactured by kneading | mixing a raw material component with an extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, etc. The method of using the raw material components is not particularly limited, and the respective components may be mixed and kneaded in a lump, or may be mixed and mixed in multiple stages.

  The composition of the present invention is excellent in thermal conductivity and water resistance. In particular, in thermal conductivity, the thermal conductivity measured by the method described in the examples below is preferably 0.5 W / m · K or more, more preferably 0.8 to 3 W / m · K, and still more preferably. 1 to 2.5 W / m · K.

  Moreover, when the composition of this invention contains a flame retardant, it is excellent in combustibility and can achieve V-0 or more according to UL94 specification.

The composition of the present invention can be formed into a molded article by a known molding method such as injection molding, extrusion molding (sheet extrusion, profile extrusion), hollow molding, compression molding, vacuum molding, foam molding, blow molding or the like. That is, the molded article of the present invention contains the above heat conductive resin composition.
The molding temperature is usually 220 to 280 ° C., preferably 230 to 260 ° C. in terms of cylinder temperature.

  Examples of the molded article containing the composition of the present invention include a housing, a substrate, a panel, a heat sink, a heat radiating fin, a fan, and packing.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded, and in the following, parts and% are particularly Unless otherwise noted, it is based on mass.

1. Magnesium oxide filler The following magnesium oxide filler was used. The BET specific surface area, Dv, Dv / Dn, and water absorption of each filler were measured by the following methods and are shown in Table 1.
1-1. Electrofused magnesia (M1)
Magnesium oxide (trade name “A-10”) manufactured by Kamishima Chemical Co., Ltd.
1-2. Electrofused magnesia (M2)
Magnesium oxide (trade name “A-25”) manufactured by Kamishima Chemical Co., Ltd.
1-3. Electrofused magnesia (M3)
Magnesium oxide (trade name “A-45”) manufactured by Kamishima Chemical Co., Ltd.
1-4. Electrofused magnesia (M4)
Magnesium oxide (trade name “A-45 200 mesh on”) manufactured by Kamishima Chemical Co., Ltd.
1-5. Electrofused magnesia (M5)
Magnesium oxide (trade name “A-45 325-200”) manufactured by Kamishima Chemical Co., Ltd.
1-6. Electrofused magnesia (M6)
Magnesium oxide (trade name “A-45 325th”) manufactured by Kamishima Chemical Co., Ltd.
1-7. Electrofused magnesia (M7)
Magnesium oxide (trade name “A-45 500th”) manufactured by Kamishima Chemical Co., Ltd.
1-8. Lightly burned magnesia (M8)
Magnesium oxide (trade name “Starmag P”) manufactured by Kamishima Chemical Co., Ltd.
1-9. Electrofused magnesia (M9)
The above M1 and M2 are mixed at a mass ratio of 8: 2.
1-10. Electrofused magnesia (M10)
The above M1 and M2 are mixed at a mass ratio of 1: 1.
1-11. Electrofused magnesia (M11)
The above M1 and M3 are mixed at a mass ratio of 2: 1.
1-12. Hard-fired magnesia (M12)
Magnesium oxide (trade name “SL”) manufactured by Kamishima Chemical Co., Ltd.

(1) BET specific surface area A betasorb automatic surface area meter (model name “4200”) manufactured by Nikkiso Co., Ltd. was used.
(2) Dv and Dv / Dn
About 0.2 g of a measurement sample is collected, dispersed in 50 ml of ethanol, dispersed for 3 minutes using an ultrasonic dispersion apparatus (model name “US-330T”) manufactured by Nippon Seiki Seisakusho, and then manufactured by Nikkiso Co., Ltd. Dv and Dn were measured by a track particle size distribution meter (model name “model HRA”).
(3) Water absorption rate About 3 g of the measurement sample was collected in a weighing bottle and precisely weighed, and left in an atmosphere of a temperature of 60 ° C. and a relative humidity of 90% without a lid. After 8 days, the weighing bottle was taken out, covered, and the mass after 3 hours at 23 ° C. was measured.

2. Magnesium oxide filler treated with an organosilicon compound Using the above magnesium oxide fillers M1 to M11 and the following organosilicon compounds S1 to S4, the following silicon compound treated magnesium oxide filler was obtained. The resulting silicon compound-treated magnesium oxide filler was measured for water absorption and shown in Table 2. The water absorption was measured in the same manner as for the untreated magnesium oxide filler.

2-1. Silicone oil (S1)
An alkoxy-modified silicone oil (trade name “AFP-1”) manufactured by Shin-Etsu Chemical Co., Ltd. was used. The kinematic viscosity at 25 ° C. is 5 cSt.
2-2. Silicone oil (S2)
Methyl hydrogen silicone oil (trade name “KF-99”) manufactured by Shin-Etsu Chemical Co., Ltd. was used. The kinematic viscosity at 25 ° C. is 20 cSt.
2-3. Silicone oil (S3)
Methyl phenyl silicone oil (trade name “KF-54”) manufactured by Shin-Etsu Chemical Co., Ltd. was used. The kinematic viscosity at 25 ° C. is 400 cSt.
2-4. Silane coupling agent (S4)
This is vinyltriethoxysilane (trade name “KBE-1003”) manufactured by Shin-Etsu Chemical Co., Ltd.

Preparation Example 1
100 parts of the magnesium oxide filler M1 was placed in a Henschel mixer and stirred while gradually adding 1 part of the organosilicon compound S1. After addition of the entire amount, the mixture was further mixed for 15 minutes, then transferred to a stainless steel tray, and heated in an air atmosphere at a temperature of 300 ° C. for 1 hour using a blow dryer to obtain a silicon compound-treated magnesium oxide filler M1-1.

Preparation Examples 2 to 4 and Comparative Preparation Example 1
Except having changed the usage-amount of organosilicon compound S1 into the quantity shown in Table 2, it carried out similarly to the preparation example 1, and obtained silicon compound process magnesium oxide filler M1-2-5.

Preparation Example 5
After 100 parts of magnesium oxide filler M1 and 2 parts of organosilicon compound S1 were treated in the same manner as in Preparation Example 1, 2 parts of phosphate ester (trade name “ADK STAB BAP-7”) was used as surface treating agent H1. , Manufactured by Asahi Denka Kogyo Co., Ltd.) while gradually adding. After addition of the entire amount, the mixture was further mixed for 15 minutes, transferred to a stainless steel tray, and heated in an air atmosphere at a temperature of 120 ° C. for 30 minutes using a blow dryer to obtain a silicon compound-treated magnesium oxide filler M1-6.

Preparation Examples 6-10
Except having changed the heating temperature and heating time into the conditions shown in Table 2, it carried out similarly to the preparation example 2, and obtained the silicon compound process magnesium oxide filler M1-7-11.

Preparation Examples 11-13
Silicon compound-treated magnesium oxide fillers M12 to M14 were obtained in the same manner as in Preparation Example 2, except that the organic silicon compound S2, S3, or S4 was used in place of the organic silicon compound S1.

Preparation Examples 14-21 and Comparative Preparation Examples 2-4
Silicon compound-treated magnesium oxide fillers M2-1 to M12-1 were obtained in the same manner as in Preparation Example 2, except that magnesium oxide fillers M2 to 11 were used instead of the magnesium oxide filler M1.

3. Production and Evaluation of Thermally Conductive Resin Composition Using the above magnesium oxide filler or silicon compound-treated magnesium oxide filler and the following thermoplastic resin and auxiliary agent, a thermally conductive resin composition was produced and evaluated. .

3-1. Thermoplastic resin (1) Rubber reinforced vinyl resin (R1)
Styrene and acrylonitrile are emulsion-polymerized in the presence of a latex containing polybutadiene rubber particles having a weight average particle size of 300 nm and toluene-insoluble content of 80% by mass, to give 60% polybutadiene rubber, 28.5% styrene unit amount and 11% acrylonitrile unit amount. A 5% rubber-reinforced vinyl resin was obtained.
The graft ratio of this resin R1 is 34%, and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component is 0.27 dl / g.
(2) Rubber reinforced vinyl resin (R2)
Styrene and acrylonitrile are emulsion-polymerized in the presence of a latex containing polybutadiene rubber particles having a weight average particle size of 280 nm and toluene insoluble content of 80% by mass, resulting in 41.5% polybutadiene rubber, 43.5% styrene unit amount and acrylonitrile unit amount. A 15% rubber-reinforced vinyl resin was obtained.
The graft ratio of the resin R2 is 55%, and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component is 0.45 dl / g.
(3) Acrylonitrile styrene resin (R3)
A copolymer having a styrene unit amount of 70.5% and an acrylonitrile unit amount of 29.5% was used. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is 0.70 dl / g.

(4) Polycarbonate resin (R4)
A polycarbonate resin (trade name “NOVAREX 7022PJ”) manufactured by Mitsubishi Engineering Plastics was used. Using methylene chloride as a solvent, the viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 20 ° C. is 18,000.
(5) Polybutylene terephthalate resin (R5)
Polybutylene terephthalate resin (trade name “Novaduran 5007”) manufactured by Mitsubishi Engineering Plastics was used. Using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (mass ratio 6: 4) as a solvent, the intrinsic viscosity measured at 25 ° C. is 0.71 dl / g.
(6) Polypropylene resin (R6)
A polypropylene resin (trade name “Novatec PP FY6C”) manufactured by Nippon Polypro Co., Ltd. was used. The MFR according to JIS K7210 is 2.5 g / 10 minutes.
(7) Polyethylene resin (R7)
A polyethylene resin (trade name “Novatech LL UJ960”) manufactured by Nippon Polyethylene Co., Ltd. was used. The MFR according to JIS K6922-2 is 5 g / 10 min.

3-2. Auxiliary agent (1) Lubricant (D1)
Ethylene bis stearic acid amide (trade name “Kao wax EG-P”) manufactured by Kao Corporation was used.
(2) Flame retardant (D2)
1,3-phenylenebisdixylenyl phosphate (trade name “aromatic condensed phosphate PX-200”) manufactured by Daihachi Chemical Co., Ltd. was used.
(3) Antioxidant (D3)
Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name “Irganox 1010”) manufactured by Ciba Specialty Chemicals was used.
(4) Antioxidant (D4)
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name “ADK STAB PEP-36”) manufactured by Asahi Denka Kogyo Co., Ltd. was used.

3-3. Evaluation Item (1) Molding Processability Using an injection molding machine manufactured by Toshiba (model name “EC-60”), a cylinder set temperature of 230 ° C., an injection pressure of 100%, an injection speed of 60 mm / sec, and a mold temperature of 50 ° C. Spiral flow test pieces having a thickness of 2 mm, a width of 10 mm, and an interval of 10 mm were obtained. The length of the obtained test piece was used and evaluated according to the following criteria.
○: L / T value is 10 or more ×; L / T value is less than 10.
(2) Thermal conductivity The thermal conductivity at 25 ° C. was measured using a laser flash method thermal constant measuring device (model name “TR-7000R”) manufactured by ULVAC-RIKO. The test piece is a disc having an inner diameter of 10 mm and a thickness of 1.5 mm.
(3) Water Absorption Rate A plate-shaped test piece having a length of 80 mm, a width of 40 mm, and a thickness of 3 mm was obtained using a Japanese steel injection molding machine (model name “J100E”) at a cylinder set temperature of 240 ° C. The obtained test piece was allowed to stand for 28 days in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90%, then the surface adhering water was wiped off, and the weight after being left in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 3 hours It was measured.
(4) Flammability Using a test piece having a length of 127 mm, a width of 13 mm, and a thickness of 2 mm, a vertical combustion test was conducted according to the UL94 standard.

Experimental example 1
After mixing 100 parts of magnesium oxide filler M1, 60 parts of rubber reinforced vinyl resin R1, 40 parts of acrylonitrile / styrene resin R3 and 1.8 parts of auxiliary agent D1 with a mixer for 5 minutes, plastic Using an extruder (trade name “PLABOR PT40S230-1”) manufactured by Engineering Laboratory Co., Ltd., melt-kneading extrusion was performed at a cylinder setting temperature of 245 ° C. and a screw rotation speed of 140 rpm, to obtain pellets (thermally conductive resin composition).

  Then, the obtained pellet was fully dried, the test piece according to the said evaluation item was produced, and evaluation was performed. The results are shown in Table 3.

Experimental Examples 2-44
With the formulations shown in Tables 3 to 6, using each material, in the same manner as in Experimental Example 1, pellets were manufactured, and predetermined test pieces were prepared and evaluated. The results are shown in Tables 3 to 6.

As apparent from Tables 3 to 6, Experimental Example 31 was an example in which the content of the magnesium oxide filler was as small as 5 parts, and was inferior in thermal conductivity. In addition, Experimental Example 36 is an example in which the content of the magnesium oxide filler is as large as 1,200 parts, and the molding processability was inferior.
Experimental Examples 5, 8, 9, 12, and 21 were examples using magnesium oxide fillers outside the scope of the present invention, and were inferior in thermal conductivity.

  Since the heat conductive resin composition of the present invention is excellent in molding processability, the shape and size are highly selective. Moreover, even if it does not contain a component having a high thermal conductivity such as a metal or an alloy, it can be formed into a molded product having excellent thermal conductivity, and is excellent in electrical insulation. Therefore, it can be used as a housing, a substrate, a panel, a heat sink, a heat radiation fin, a fan, a packing, and the like. These members are suitable for electronic components such as circuit boards, chips, thermal heads, motors, etc .; electrical devices such as televisions, radios, cameras, video cameras, audios, videos, lighting fixtures, etc. It is suitable for a housing, a heat sink and a fan for releasing the heat of the outside, an audio back panel, a liquid crystal plate fixing member of a liquid crystal television, and the like.

Claims (6)

In a thermally conductive resin composition containing a thermoplastic resin and a magnesium oxide filler for resin blending,
The thermoplastic resin is a rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer comprising a diene polymer, Or it consists of a mixture of the rubber-reinforced vinyl resin and a copolymer of vinyl monomers containing an aromatic vinyl compound and a vinyl cyanide compound, and the content of the rubbery polymer is 36 to 60% by mass A rubber-reinforced resin, a polycarbonate resin, a polybutylene terephthalate resin, a polypropylene resin and a polyethylene resin,
The magnesium oxide filler for resin blending has a purity of 95.0% by mass or more, a BET specific surface area of 5.0 m ² / g or less, a volume average particle diameter (Dv) of 0.5 to 60 μm, and a volume average particle diameter. A mixture containing 100 parts by mass of magnesium oxide having a ratio Dv / Dn of (Dv) to the number average particle diameter (Dn) of 10 to 55 and 0.1 to 10 parts by mass of an organosilicon compound is 100 to 800 ° C. It was obtained by heating at a temperature of
Content of the said magnesium oxide filler for resin mixing | blending is 100-500 mass parts with respect to 100 mass parts of said thermoplastic resins, The heat conductive resin composition characterized by the above-mentioned. The thermally conductive resin composition according to claim 1, wherein the magnesium oxide has a BET specific surface area of 0.3 to 1.2 m ² / g.   The thermoplastic resin is a rubber reinforced resin, and the rubber reinforced resin is obtained by polymerizing a vinyl monomer containing styrene and acrylonitrile in the presence of a rubbery polymer made of polybutadiene. 2. A resin or a mixture of a rubber-reinforced vinyl resin and a copolymer of vinyl monomers containing styrene and acrylonitrile, and the content of the rubbery polymer is 36 to 60% by mass. Or the heat conductive resin composition of 2. The thermally conductive resin composition according to any one of claims 1 to 3, wherein the organosilicon compound is silicone oil. Furthermore, it contains a flame retardant composed of 1,3-phenylenebisdixylenyl phosphate,
The thermoplastic resin is composed of the rubber-reinforced resin, the polycarbonate resin, and the polybutylene terephthalate resin, and these ratios are 35 to 75% by mass when the thermoplastic resin is 100% by mass, respectively. , 12-37 wt% and 1-7 wt%,
Content of the said magnesium oxide filler for resin compounding is 200-400 mass parts with respect to 100 mass parts of said thermoplastic resins,
The heat conductive resin composition according to any one of claims 1 to 4, wherein a content of the flame retardant is 33.3 to 36.4 parts by mass with respect to 100 parts by mass of the thermoplastic resin.   The thermal conductivity resin composition according to any one of claims 1 to 5, wherein the thermal conductivity is 0.5 W / m · K or more.